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Chemotaxonomy of Flowering Plants: Four Volumes
 9780773592889

Table of contents :
Cover
June, 1974 Notes, Queries And Errata
VOLUME I
Copyright
Contents
Preface
Acknowledgments
Abbreviations
History of chemotaxonomy
Criteria used in taxonomy, and some related topics
Chaos in taxonomy
Restriction of distribution of constituents to various categories of plants
Restriction of distribution of constituents within the individual plant
Excretion by plants
Odoriferous constituents of plants
Chemical evolution in plants
Tests used by the author
Conclusion
Plant constituents. Introduction
Acetylenic compounds
Alcohols
Aldehydes
Alkaloids
Amides
Amines and some betaines
Amino-acids, peptides, and proteins (including enzymes)
Amino-sugars
Betalains (betacyanins and betaxanthins)
Carbohydrates
Carboxylic acids
Coumarins
Cyclitols
Depsides and depsidones
α,ω-Diphenyl-alkanes
Elements
Fats and fatty-acids
Flavonoids
Furan derivatives
Glycosides
Gums, mucilages and resins
Hydrocarbons
Ketones
Lactones
Lignans
Lignins
VOLUME II
Melanins
Naphthalene and some of its derivatives
Pyrones
Quinones
Steroids
Sulfur compounds
Tannins
Terpenoids
Waxes
Families and orders of flowering plants. Introduction
Families of flowering plants. Introduction
Families of dicotyledons
Families of monocotyledons
Orders of flowering plants. Introduction
Orders of dicotyledons (to Dumosae)
VOLUME III
Orders of dicotyledons (Ebenales to Volvales)
Orders of monocotyledons
VOLUME IV
Bibliography
Index
Addendum

Citation preview

JUNE, 1974 NOTES, QUERIES AND ERRATA Professor G. Ourisson has very kindly pointed out two errors in the figure included in the promotional leaflet for this book. I am very grateful to him since his action has prompted me to recheck virtually all the formulae in the 189 figures of the text. This hasty check has revealed what is to me a shocking number of errors (mostly of a minor nature), as well as many cases in which I am unsure of the formulae. I have therefore prepared the following list, which I hope is substantially complete. It is but a slight consolation to report the detection of several errors in the reference books available to me, and to note that chemists (I am a botanist) seem as liable to get plant names wrong as I am to err in my formulae. p. 137 Meloscine —H on N; double bond at right of ring at top right? Fig. 12 (p. 141) Acronycine —OCH3 at top right as in evoxanthine Fig. 14 (p. 345) Mescaline —NH,, not —NH3 Fig. 18 (p. 167) Lycoctonine , —C2H5, not —CH2 . CH2OH on N p. 173 Dendrobine —CH3 missing (I have it correctly in fig. 42 on p. 229) Fig.

20

(p. 177) Bufotenine —H on N

Fig. 27 (p. 193) Cylindrocarpine —OCH3 as in aspidospermine? Meloscine double bond on right of ring at top right? Fig. 28 (p. 196) Pyrifoline —COOCH3 in position of —OH of kopsine? Fig. 29 (p. 198) Obscurinervine Add 2 —OCH3 groups to left-hand ring; double bond at right of ring at top right; =0 next to —Din ring at lower right? Aspidoalbine 2 —OCH3 groups (as in obscurinervine)? Fig. 31 (p. 203) Akuammicine —COOCH3i not COOH3. Compactinervine and lochneridine should have each a 2,16 double bond? Geissospermine lacks =CH .CH3 at lower left?

Toxiferine-i

I am unsure of this formula

2 CHEMOTAXONOMY OF FLOWERING PLANTS

Fig. 33 (p. 209) Ajmaline Move top —OH one place to left? Fig. 35 (p. 215) Alstonine Is my formula correct? I have another Fig. 49 (p. 238) Nor-laudanosine Should this have 4 x —OCH3 rather than 4 x —OH? Fig. 51 (p. 244) Crotonosine —OH, not —0, at top left Fig. 56 (p. 263) Reticuline The lower —OCH3 group on the top ring should be —OH? Metaphanine Add —CH3 to N Fig. 7o (p. 294) 8-Phenyl-lobilol —CH3i not —H on N Fig. 77 (p. 315) Supinidine Should have double bond on right of right-hand ring? Thelepogine One source has 3 x —CH3 extra to my formula! Fig. 82 (p. 336) Nupharamine —CH3 at top of ring (as in nupharidine) Fig. 83 (p. 35o) Holarrhimine Move —CH2OH one place to right? Fig. 84 (p. 354) (—)-Cocaine Chain should be —CO .00H3 Fig. 86 (p. 359) Allantoin Add —H to N Fig. 96 (p. 449) 3,4-Furocoumarin Transpose 3 and 4 in diagram Fig. 97 (p. 451) Imperatorin Chain should be —0 . CH2. CH=C(CH3)2 Fig. 98 (p. 453) Archangelin, columbianadin Fig. 99 (p. 455) Allo-xanthoxyletin Top ring should be

Fig. IoI (p. 458) Ellagic acid =0, not =OH, at lower right. Add -3,3',4-trimethyl ether to Flavellagic acid. Fig. Jos (p. 474) Chalcone Add =0 to CH2 Fig. 112 (p. 543) Petunidin —OCH3i not OCH, at top. Rosinidin —OCH3 at position 7 Fig. 114 (p. 548) Hinokiflavone Should the link be to position 6? Fig. 115 (p. 555) Olivin Are there two substances of this name? I find a formula quite different from mine Fig. 118 (p. 558) Guibourtacacidin Add —OH at 4' Fig. 122 (p. 58o) Cycloartocarpin Add —OH at top right (as in dinatin)

NOTES, QUERIES AND ERRATA

3

Fig. 124 (p. 606) Karanjin Left-hand ring should be

Fig. 127 (p. 611) Homopterocarpin Add —OCH3 at 4' Fig. 128 (p. 616) Irisolone Delete —OCH3? Maxima-substance-A Chain at top left should be —OCH2. CH=C(CH3)2. Osajin Add =0 (as in other formulae) Fig. 130 (p. 622) Euparin Add =0 at 6 Fig. 139 (p. 668) Flavesone I find formulae differing from mine Fig. 14o (p. 67o) Calythrone Add =0 at 3? Fig. 142 (p. 677) Arctigenin —OH, not —OCH3 at lower left. Lyoniaxyloside Add —OCH3 next to —OH at left Fig. 146 (p. 686) Opuntiol —CH2OH, not —OH2OH Fig. 149 (p. 694) Jacareubin Should have —OH at 1. Maclura-xanthone should have —OH at I. Have I the correct chain at top? Mangiferin =0 missing Fig. 15o (p. 698) Embelin Add —OH at 5. Plastoquinone, not plastaquinone Fig. 154 (p. 711) Cryptotanshinone Should have 2 —CH3 groups at top of left-hand ring? Fig. 159 (p. 723) Cycloartenol Should have z —CH3 groups (not I) at bottom left (as in butyrospermol)? Elemolic acid —COOH, not —CH3, at a Fig. 161 (p. 745) Oleandrigenin, not Oldeandrigenin. Periplogenin —CH3 omitted (compare other genins) Fig. 162 (p. 747) Digacetigenin I find a formula somewhat different from mine Fig. 166 (p. 766) Sinalbin Is the non-sinapine part of my formula correct? Fig. 169 (p. 790) i,8-Cineole —0— should link to 8 position (not 4) Fig. 173 (p. 797) Mansonone-A Should there be a second double bond (common to the rings)? Fig. 174 (p. 798) Drimenol —CH3 missing (compare with other formulae). Cinnamodial Is an —OH group omitted from top of righthand ring? Farnesiferol-C —CH3 is missing from top right of lefthand ring?

4

CHEMOTAXONOMY OF FLOWERING PLANTS

Fig. 175 (p. 8o1) Petasin Double bond in ring at left? Fig. 177 (p. 8o6) Mexicanin-C Should have =CH2, not —CH3i in ring at right? Fig. 18o (p. 81 z) a-Santonin Is a double bond missing from ring at right? Artemisin Is an —OH missing? Fig. 182 (p. 819) Dodonaea-diterpene Should this be?

HOHLC CH,OH

a-Camphorene Lower end should be —CH=C(CH3)2 (as top end) Fig. 183 (p. 843) Bacogenin-A A formula proposed in 1973 transposes the —CH3 and —CH(OH groups (middle level of my fig.) and has a terminal 5-membered heterocyclic ring Panaxatriol The two —CH3 groups at right should be on the C below (next to the 0) Fig. 184 (p. 856) Samaderine-B Should be?

Swietenine Should the chain at left be —CH2 .CO.00H3 or —CH(OH). CO.00H3? Fig. 185 (p. 857) Arnidiol =CH2, not =0, at top? Limonin Should double bond in ring at left be deleted? Entandrophragmin I am unsure of this formula. Quassin Is my formula correct?

CHEMOTAXONOMY OF FLOWERING PLANTS VOLUME I

/n\

CHEMOTAXONOMY OF

FLOWERING PLANTS R. DARNLEY GIBBS Emeritus Professor of Botany, McGill University, Montreal, Canada

VOLUME I CONSTITUENTS

McGILL-QUEEN'S UNIVERSITY PRESS MONTREAL AND LONDON 1974

© McGill-Queen's University Press 1974

ISBN o 7735 0098 7 Library of Congress Catalog Card No. 73-79096 Legal Deposit 2nd Quarter 1974 Printed in Great Britain at the University Printing House, Cambridge, England (Brooke Crutchley, University Printer)

To the memory of the late Dr E. W. R. (Ned) Steacie, friend and sometime colleague, who, as President of the National Research Council of Canada, did so much for personal research in the universities of his country.

CONTENTS VOLUME I Preface Acknowledgments Abbreviations History of chemotaxonomy Criteria used in taxonomy, and some related topics Chaos in taxonomy Restriction of distribution of constituents to various categories of plants Restriction of distribution of constituents within the individual plant Excretion by plants Odoriferous constituents of plants Chemical evolution in plants Tests used by the author Conclusion Plant constituents. Introduction Acetylenic compounds Alcohols Aldehydes Alkaloids Amides Amines and some betaines Amino-acids, peptides, and proteins (including enzymes) Amino-sugars Betalains (betacyanins and betaxanthins) Carbohydrates Carboxylic acids Coumarins Cyclitols Depsides and depsidones

1 4 7 9 19 30 37 43 45 49 51 54 80 83 85 106 128 134 357 360 367 389 390 394 421 440 460 469

Viii CHEMOTAXONOMY OF FLOWERING PLANTS

a,w-Diphenyl-alkanes

471

Elements

476

Fats and fatty-acids

493

Flavonoids

523

Furan derivatives

619

Glycosides

621

Gums, mucilages and resins

643

Hydrocarbons

647

Ketones

660

Lactones

670

Lignans

673

Lignins

678 VOLUME II

Melanins

681

Naphthalene and some of its derivatives

683

Pyrones

684

Quinones

695

Steroids

715

Sulfur compounds

756

Tannins

767

Terpenoids

770

Waxes

872

Families and orders of flowering plants. Introduction

877

Families of flowering plants. Introduction

880

Families of dicotyledons

882

Families of monocotyledons

1104

Orders of flowering plants. Introduction

1165

Orders of dicotyledons (to Dumosae)

1166

VOLUME III Orders of dicotyledons (Ebenales to Volvales)

1275

Orders of monocotyledons

1854

CONTENTS ix

VOLUME IV Bibliography

1983

Index

2027

Addendum

2303

FIGURES VOLUME I 1. The biogenesis of natural acetylenes

87

2. Some acetylenic derivatives of thiophene

99

3. Some acetylenic compounds with phenyl groups

102

4. Some acetylenes with furyl groups

104

5. Acetylenes with pyran rings 6. Uncommon acetylenes

105

7. Aliphatic alcohols

116

8. Some aromatic alcohols

118

9. Some phenols

123

106

1o. Some phenolic ethers

128

11. Some aromatic aldehydes

134

12. Acridine, acridone, and some acridine alkaloids

141

13. Origin of fl-phenyl-ethylamines and simple isoquinolines

145

14. Some alkaloidal amines

145

15. Alkaloidal peptides 16. Alkaloids of the Amaryllidaceae, etc. 17. Daphniphylline

147

18. Diterpenoid alkaloids

158 160 167

19. Histidine, histamine, and some imidazole alkaloids

169

20. Indole and some derivatives

177

21. Tryptophan, carboline, and some carboline alkaloids

179

22. Some quinazolinocarboline alkaloids

180

23. Hexahydro-pyrrolo[2,3b]indole and some of its alkaloids

182

X CHEMOTAXONOMY OF FLOWERING PLANTS

24. Canthin-6-ones 25. Some eburnamine-vincamine alkaloids and related substances 26. Some oxindole alkaloids 27. Some aspidospermine alkaloids and meloscine z8. Some alkaloids of the aspido-fractinine group 29. Some alkaloids of the aspidoalbine group 3o. Alkaloids of the condylocarpine group 31. Akuammicine and some related alkaloids 32. Some alkaloids of the uleine group 33. Ajmaline-sarpagine alkaloids 34. Yohimbane and some related alkaloids 35. Heteroyohimbane and some heteroyohimbane (ajmalicine) alkaloids 36. Some corynane alkaloids 37. Some z,z'-indolyl-quinuclidine alkaloids 38. Ergoline and some ergoline alkaloids 39. Some iboga and voacanga alkaloids 40. An aspidosperma-iboga dimer 41. Erythrinane and some related alkaloids 42. Some indole and near-indole alkaloids of the Orchidaceae Mesembrane and mesembrine alkaloids 43. 44. Alkaloids of Stemona 45. An indole alkaloid of group XXII 46. Carbazole and carbazole alkaloids 47. Biogenesis of phenanthro-indolizidine alkaloids? 48. Indolizidine and some indolizidine alkaloids 49. Biosynthesis of isoquinolines 5o. Some simple isoquinoline alkaloids 51. 1,I'-Benzylisoquinoline, some related compounds, and some benzylisoquinoline alkaloids 52. Some unusual benzylisoquinolone alkaloids 53. Some bisbenzylisoquinoline alkaloids 54. Some aporphine and near-aporphine alkaloids

183 186 189 193 196 198 200 203 206 209 213 215 218 219 220 223 225 228 229 230 232 232 233 236 236 238 239 244 245 251 259

CONTENTS Xi

55. Cularine alkaloids and a possible parent 56. Some steps in the biosynthesis of morphine (above, after Kirby, 1967) and some morphine alkaloids 57. Theoretical relationships of the protoberberines (see the quotation from Manske and Ashford, above) 58. Some protoberberines 59. Alkaloids of the protopine group 6o. Some phthalide-isoquinoline and related alkaloids 61. Alkaloids of the emetine group 62. Some a-naphthaphenanthridine alkaloids 63. An alkaloid of the Lunaria group 64. Some monoterpenoid alkaloids and related substances 65. Oxazole and oxazole alkaloids 66. Some papaverrubines 67. Purine and some purine bases 68. Pyrazole and some derivatives 69. Pyridine, piperidine, and some pyridine alkaloids of groups I a, I b, and I c 7o. Pyridine alkaloids of group I d 71. Some pyridine alkaloids of groups I e and If 72. Pyridine alkaloids of groups II a and II c 73. Some pyridine alkaloids of group III 74. Some group IV compounds 75. Alkaloids of the Lolium group 76. Pyrrole, pyrroline, pyrrolidine, and derived alkaloids 77. Some necines and pyrrolizidines 78. Biosynthesis of quinazolines 79. Quinazoline and some quinazoline alkaloids 80. Quinoline and some quinoline alkaloids 81. Some quinolizidine alkaloids 8z. Some quinolizidine alkaloids 83. Some steroid alkaloids 84. Tropane and some tropane alkaloids 85. Colchicine and some related alkaloids

261 263 269 269 271 273 275 278 279 281 282 283 286 286 288 294 295 297 299 301 302 304 315 318 318 327 335 336 350 354 357

Xii CHEMOTAXONOMY OF FLOWERING PLANTS

Uric acid and some amides Some amino-acids Amino-sugars Betalains. Possible biogenesis of betanidin and indicaxanthin go. Some monosaccharides gr. Some monosaccharides g2. Some disaccharides 93. Some aromatic carboxylic acids 94. Synthesis of umbelliferone in Hydrangea (after Brown, Towers and Chen) 95. Some `simple' coumarins 96. 3,4-Furocoumarins 97. Some 6,7-furocoumarins 98. Some 7,8-furocoumarins 99. Some chromano-coumarins 100. Coumarono-coumarins and related substances Ioi. 3,4-Benzocoumarins and related substances ioz. Isocoumarins 103. Cyclitols 104. A depside 105. Diphenyl, diphenyl-methane, and some related diphenyls 106. Stilbene and some related substances 107. Some epoxy- and cyclopropenyl- fatty-acids 108. Fatty-acids of the chaulmoogric series 109. Flavonoids (our numbering in brackets) iio. Flavonoids (our numbering in brackets) iii. Some anthocyanidins 112. Some anthocyanidins 113. Aurones 114. Apigenin and biflavonyls 115. Some chalcones, etc. 116. Chalcones and related compounds 117. Flavonoids of Pterocarpus angolensis Ii8. Some flavan-3,4-diols, etc. 86. 87. 88. 89.

359 379 390 394 401 402 406 439 442 448 449 451 453 455 456 458 459 468 471 474 475 517 522 524 525 542 543 546 548 555 556 556 558

CONTENTS xiii

119. Flavan-3-ols 12o. Some flavanones (dihydro-flavones) 121. Some flavanonols (dihydro-flavonols) 122. Some flavones 123. Some flavones 124. Some flavonols 125. Some flavonols 126. 'Homo-isoflavone' and some related flavonoids 127. Some isoflavanones 128. Some isoflavones 129. 2-, 3-, and 4-aryl-chromans and some neoflavanoids 13o. Furan and furan derivatives 131. Aucubin and some related compounds 132. Cyanogenic substances 133. Some phenolic glycosides 134. Frequency of occurrence of n- and branched alkanes 135. n-Alkanes of the leaf-waxes of the Scrophulariaceae (Eglinton et al. for Hebe) 136. n-Alkanes of some plants 137. Some acetophenones 138. Some benzophenones 139. Some aromatic ketones 140. Some cyclic ketones 141. Some lactones 142. Some lignans 143. Substances believed to be involved in lignin(s)

561 565 567 580 581 606 607 609 611 616 618 622 629 634 641 649 650 651 664 665 668 670 672 677 680

VOLUME II 144. Possible melanin units 145. Naphthalene and some derivatives 146. Some a-pyrones 147. Simple y-pyrones 148. Some benzo-y-pyrones (chromones) 149. Some xanthones

682 684 686 687 689 694

XIV

CHEMOTAXONOMY OF FLOWERING PLANTS

150. Some benzoquinones 151. Some naphthaquinones 152. Some anthraquinones 153. Dianthraquinones 154. Phenanthrene, phenanthraquinone, and some related substances 155. Some anthrones 156. Dianthrone and some derivatives 157. Anthranols 158. Structures found in steroids 159. Some sterols and related compounds 16o. Sex hormones which are said to occur in plants 161. Some cardenolide genins 16z. Diginane and some digitenolide genins 163. Some scilladienolide genins 164. Spirostan and some steroidal sapogenins 165. Alliin and allicin 166. Mustard oil glucosides 167. Some thiophene derivatives 168. Biosynthesis of terpenoids 169. Some monoterpenoid substances 170. Some monoterpenoid substances 171. Possible origins of some sesquiterpenoids 172. Some sesquiterpenes of the bisabolene group 173. Some sesquiterpenes of the cadinene group 174. Sesquiterpenoids of the drimenol group 175. Some sesquiterpenes of the eremophilone group 176. Two germacranolides 177. Guaianolides and pseudoguaianolides 178. Guaiane, guaiol, and guaianolides 179. Some pseudoguaianolides 180. Some selinene (eudesmol) sesquiterpenes 181. Some sesquiterpene dilactones 182. Some diterpenoids

698 703 708 710 711 712 713 714 716 723 724 745 747 750 756 760 766 767 771 790 791 793 795 797 798 801 802 806 806 809 812 814 819

CONTENTS XV

183. Some triterpenoid sapogenins 184. Some triterpenoids and derivatives 185. Some triterpenoids and derivatives 186. Carotenoids of chloroplasts 187. Some carotenoids 188. Isoprene and some polymers

843 856 857 866 866 871

VOLUME III 189. Some constituents of the Piperaceae

1536

TABLES VOLUME I 1. HCN in dicotyledons 2. HCN in monocotyledons 3. HCN in angiosperms 4. Aliphatic alcohols of waxes of a few plants (various authors) 5. Manganese in angiosperms

60 67 68 113 486

VOLUME II 6. Phenolic acids of Aristolochiaceae (2-way chromatography by Mrs P. Bahr, 1963) 7. Chemistry of the Campanulales 8. Cigarette and hot-water tests on members of the Campanulales (Cucurbitaceae added for comparison) 9. Sesquiterpene lactones of the Compositae (Data from Herout and Sörm, 1969) 1o. Umbelliferone in Hieracium and Pilosella (after BateSmith et al., 1968) 11. Aurone test A (NH3) as applied to flowers of the Campanulales 12. Chemistry of the Celastrales (fams 1-6) 13. Chemistry of the Celastrales (fams 7-13)

1173 1199 1202 1202 1203 1204 1222 1224

XVi CHEMOTAXONOMY OF FLOWERING PLANTS

14. Fatty-acids of the seed-fats of the Celastrales and Rhamnales (various authors) Chemistry of the Polygonales and Centrospermae 15. (fams 1-6) 16. Chemistry of the Centrospermae (fams 7—I a), Didiereaceae, and Cactales 17. Chemistry of the Dipsacales

1226 1242 1244 1272

VOLUME III 18. Chemistry of the Ebenales 19. Fatty-acids of the seed-fats of the Ebenales (various authors) 2o. Juglone tests on and naphthaquinones, etc. of the Ebenales 21. Chemistry of the Ericales, Diapensiaceae and Cyrillaceae 22. Methyl salicylate and phenolic glycosides of the Ericales, Diapensiaceae and Cyrillaceae (various authors) 23. Chemistry of the Fagales 24. Fatty-acids of the seed-fats of the Fagales (various authors) 25. Chemistry of the Gentianales 26. Alkaloids of the emetine and cinchona groups in the Rubiaceae 27. Chemistry of the Geraniales 28. Fatty-acids of the seed-fats of the Geraniales (various authors) 29. Alkaloids of some species of the genus Croton (Euphorbiaceae) 3o. Chemistry of sub-order i. Dilleniineae of the Guttiferales 31. Chemistry of sub-orders 2. Ochnineae and 4. Ancistrocladineae of the Guttiferales 32. Chemistry of sub-order 3. Theineae of the Guttiferales 33. Xanthones of Kielmeyera 34• Flavonoids of the Eucryphiaceae (Data of Bate-Smith, Davenport and Harborne, 1967). I have added the 5-methoxy-flavonols of the Dilleniaceae

1280 1282 1284 1296 1298 1306 1308 1327 1330 1354 1357 1359 1374 1376 1378 1380

1381

CONTENTS XVii

35. Fatty-acids of the seed-fats of the Guttiferales (various authors)

1382

36. Resins of some Dipterocarpus species (after Bisset et al., 1966) 1383 37. Chemistry of the Juglandales of Melchior (in Syll. 1z, 1964) and of families which others have included in the order

1400

38. Fatty-acids of the seed-fats of the Juglandales. Data from various authors. Those for Pterocarya from Dr Mary Crombie (personal communication)

1402

39. Chemistry of the Magnoliales (group 1 of Buchheim, in Syll. 12, 1964)

1429

40. Chemistry of the Magnoliales (groups z, 4, 5, and 6 of Buchheim, in Syll. 12, 1964) 41. Chemistry of the Magnoliales (group 3 of Buchheim, in Syll. 12, 1964)

1432 1434

42. Fatty-acids of the seed-fats of the Magnoliales (various authors) 1436 43. Chemistry of the Malvales of Schultze-Motel (in Syll. 1z, 1964) 1454 44. Fatty-acids of the seed-fats of the Malvales (various authors) 1456 1484 45. Chemistry of the Myrtales (fams 1-6) 46. Chemistry of the Myrtales (fams 7-12) 1486 47. Chemistry of the Myrtales (fams 13-17) 1488 48. Fatty-acids of the seed-fats of the Myrtales (various authors) 1490 49. 3,4-Benzocoumarins of the Myrtales (various authors) 5o. Chemistry of Haloragidaceae (s.s.), Myriophyllaceae, and Gunneraceae 51. Chemistry of the Oleaceae and `related' families 5z. Chemistry of the Papaverales 53. Fatty-acids of the seed-fats of the Papaverales (various authors) (some unusual acids omitted) 54. The main fatty-acids of the seed-fats of Lesquerella

1491 1491 1504 1520 1522 1524

55• Chemistry of the Piperales and the Lacistemaceae'

1534

56. Chemistry of the Primulales and Plumbaginales 57. The juglone test and plumbagin in the Plumbaginaceae

1560 1562

XViii CHEMOTAXONOMY OF FLOWERING PLANTS

58. Lomatiol in and results of the juglone test on Australian and South American species of Lomatia 59. Chemistry of the Ranunculales 6o. Fatty-acids of the seed-fats of the Ranunculales (various authors) 61. Groups of alkaloids, and phenolic esters and ethers of the Ranunculales and some other groups 62. Chemistry of the Ranunculaceae (s.l.) 63. Nymphaeaceae as treated by Takhtajan (1969), Buchheim (in Syll. 12, 1964), and Airy Shaw (in W. 1966) 64. Chemistry of the Rhamnales 65. Chemistry of the Rosales (fams 1-6) 66. Chemistry of the Rosales (fams 7-13) 67. Chemistry of the Rosales (fams 14-19) 68. Fatty-acids of the seed-fats of the Rosales (various authors) 69. Selenium indicators in Astragalus (data of Rosenfeld and Beath, 1964) 70. The Saxifragaceae of Schulze-Menz (in Syll. 12, 1964) and its treatment by Hutchinson (1969) and Takhtajan (1969) 71. Chemistry of the Rutales. Sub-order Rutineae 72. Chemistry of the Rutales. Sub-orders Malpighiineae and Polygalineae 73. Fatty-acids of the seed-fats of the Rutales (various authors) 74. Chemistry of the Santalales 75. Fatty-acids of the seed-fats of the Santalales (various authors) 76. Chemistry of the Sapindales (sub-orders 1, 2, and 4) 77. Chemistry of the Sapindales (sub-order 3) 78. Fatty-acids of the seed-fats of the Sapindales (various authors) 79. Chemistry of the Sarraceniales 80. Chemistry of the Thymelaeales and Proteales 81. Fatty-acids of the seed-fats of the Thymelaeales and Proteales (various authors)

1569 1585 1588 1589 1590 1591 1598 1651 1654 1656 1660 1663

1664 1683 1686 1688 1698 1700 1714 1716 1718 1725 1738 1740

CONTENTS XiX

82. Chemistry of the Tubiflorae — sub-orders Convolvulineae and Boraginineae 1784 83. Chemistry of the Tubiflorae — sub-orders Verbenineae and Solanineae (part) 1786 84. Chemistry of the Tubiflorae — sub-order Solanineae (part) 1789 85. Chemistry of the Tubiflorae — sub-orders Solanineae (part), Myoporineae and Phrymineae, and of the Plantaginales 1792 86. Fatty-acids of the seed-fats of the Tubiflorae and Plantaginales (various authors) 1794 87. Chemistry of the Umbellales 1808 88. Fatty-acids of the seed-fats of the Umbellales (various authors) 1811 89. Chemistry of the Urticales 1822 go. Fatty-acids of the seed-fats of the Urticales (various authors) 1825 91. Chemistry of the Violales — sub-order Flacourtiineae (fams 1-7) 1846 92. Chemistry of the Violales — sub-orders Flacourtiineae (fams 8 and g) and Cistineae 1848 93. Chemistry of the Violales — sub-orders Tamaricineae, Caricineae, Loasineae, and Begoniineae 1850 94. Fatty-acids of the seed-fats of the Violales (various authors) 1852 1860 95. Chemistry of the Alism(at)ales (sub-orders 1-3) 96. Chemistry of the Alism(at)ales (sub-order 4) 1861 97. Chemistry of the Arales, Pandanales, Cyclanthales, and Arecales 1869 98. Fatty-acids of the seed-fats of the Palmae (various authors) 1875 gg. Chemistry of the Bromeliales (Bromeliaceae only) and Commelinales — sub-order Commelinineae 1885 100. Chemistry of the Commelinales (cont.) — sub-orders Eriocaulineae, Restionineae, and Flagellariineae 1886 tor. Chemistry of the Gramineae; Cyperaceae; and Juncaceae and Thurniaceae 1904 102. Triterpenoids of the Gramineae (after Ohmoto, Ikuse, and Natori, 1970) 1907

XX CHEMOTAXONOMY OF FLOWERING PLANTS

103. Chemistry of the Liliales (sub-order I. Liliineae, fams i-5) 104. Chemistry of the Liliales (sub-order I. Liliineae, fams 6—H) 105. Chemistry of the Liliales (sub-orders z-5) 106. Chief fatty-acids of the seed-fats of the Liliales and Juncaceae (various authors) 107. Chemistry of Hutchinson's Alstroemeriales 108. Chemistry of the Orchidales and Zingiberales

1943 1946 1948 1950 1951 1978

CONSTITUENTS

PREFACE Is it usual for an author to be able to say just when his book was conceived, or what sparked the writing of it ? I have been the part-author of one book, the author of another, and now write the preamble to a third. In each case I can pinpoint the occasion of conception. Ernest J. Holmes and I were dining with our former Professor of Education and Philosophy, the late A. A. Cock. Holmes, then teaching at a secondary school, complained that no suitable textbook of biology was available for the middle school. Cock looked at us over his glasses and said, as nearly as I can remember, `Surely you and Gibbs know enough biology to write one of your own'. We thought we did, and wrote A Modern Biology (1937). About ten years later a cyclotron was built at McGill. Its construction involved the destruction of our greenhouses and effectively ruined a programme of research on which I was engaged. While I was sulking about this an agent of Blakiston's called to discuss books. When I said there was no suitable book for the type of introductory botany course that I gave, he said ` Write one'. At that moment Botany: an evolutionary approach (195o) was conceived. This present book owes its origin to John Hutchinson. I was horrified to note, some time in the 194.os, that in a diagram in his Families of flowering plants (1926) he had what I had been led to believe is a natural order, the Umbelliflorae (or Apiales, or Umbellales), evolving along two lines—his `woody' and `herbaceous' lines. It is true that he put the pieces together again later in the book; but the damage had been done! If these two parts of the old Umbelliflorae had indeed evolved along separate lines, I argued, their chemistry would be different. From that moment I started to collect data on the chemistry of the Umbelliferae, Araliaceae and Cornaceae (s.l.). Quickly the field widened and led, almost 3o years later, to this book. And what is this book ? It is not, and could not be (since it is essentially a one-man book), an exhaustive compilation of all the chemistry of all the species that have been investigated, applied to all the taxonomy of all the plants involved. It is an attempt to gather as much information as possible from the literature, while making as many simple tests as possible on as many flowering plants as possible. The coverage is necessarily patchy. I have not been able to include much from the Russian, or the Chinese, or Japanese. I have not, while writing this book, been able to deal even with the whole of the literature in English. Travel in North America, England, Australia, New Zealand and Jamaica has made possible the study of many plants from those I

GCO

2 CHEMOTAXONOMY OF FLOWERING PLANTS

countries; but the plants of South America, Africa, India and much of Asia have been largely unavailable. It is true that many individuals and institutions have sent me material, often by air, from many parts of the world; and it is true that the botanical gardens to which I have had access have been generous in letting me help myself; but there are many families virtually unrepresented in even the finest gardens. And it is often the taxonomically most interesting plants that are missing! We shall see later how important it may be to test several parts of a plant. Often I have had access only to a fragment of herbarium material —of Malesherbia, for example (though in that case I was looking for HCN, and found it!). Root-material was often not to be had. And this is a good place to mention the vexed question of voucher specimens. I have had great arguments with herbarists about this. Ideally, of course, it would be nice to know that one could check the identity of a plant reported by an investigator to have a particular constituent. But if I had made a voucher specimen for every plant I have tested there would be thousands (I don't exaggerate) of herbarium sheets cluttering herbaria, against the possibility that one or two people might want to check my claims—and I should have had time for many fewer tests. And in all too many cases I have had insufficient plant material to make a voucher specimen. When I, myself, have wanted to check other people's results I have tried to get the species they have claimed to have tested and have made tests for myself. Early in my own work I had to decide whether to make an intensive study of a limited group or an extensive study of as many species as possible. I opted for the latter approach—see the introduction to the section on `tests used by the author'. Had the decision been to study a few plants in depth, then I might have felt differently about voucher specimens. I have, of course, tried to be sure of my material, but that has not always been possible. A few results are queried because of doubt as to identification. Even the best botanical gardens, one finds, have mislabelled plants. In one or two cases the unexpected chemistry of the specimens tested has led me to query the labelling and to find it wrong! And how does one deal with the results of early workers ? Often one finds, in trying to check a name in the great Index Kewensis, that the name used is not recognized, or that it might apply to more than one species as recognized today. And the chemistry may be uncertain, too. Re-examination by modern methods often reveals such inadequacies. Errors crowd in, but only rarely do they mislead us at all seriously. This book is not a textbook of plant biochemistry, but I hope that my lists of constituents may prove useful—they certainly took much of my time! Looking back at it I realize that I often spent far too much

PREFACE

3

time tracking down the chemistry of substances mentioned only by trivial names; just as I wasted time over obscure references to out of the way families. A decision had to be made when writing was started as to the level at which chemotaxonomy was to be discussed. Hegnauer's great work, still incomplete, deals with families in alphabetical order. Could one deal with orders, I wondered, and decided to try. It has become clear that our knowledge of plant chemistry is too limited for this to be generally successful. But I am consoled that Cronquist (1965) finds difficulties even in defining orders: Still another very serious obstacle to the development of a satisfactory general system is that the characters which mark the families and orders are subject to frequent exception. Exceptions to the ordinal characters are indeed so numerous that it is difficult to find criteria sufficiently stable for even the most loose and general characterization of the groups. Some botanists have gone so far as to say that the orders of angiosperms can be defined only by the list of families to be included. This may be an unnecessarily pessimistic position, but it does point up the difficulty. It is, of course, one of the aims of comparative chemistry to try to find chemical characters that are sufficiently stable for the characterization of groups. The reader will learn how few as yet are the chemical characters that are of use at the order level. At higher levels there are virtually none. I soon gave up the attempt to deal with super-orders, sub-classes, and other higher categories.

I-2

ACKNOWLEDGEMENTS The research work included here could not have been done, and this book could not have been written, without the generous help of many associates, friends, correspondents, and institutions. Some helped me but once—with a twig or even a single leaf of some much-desired plant —others have given repeated help over a long period of time. Some now are dead; some who are thanked here will not see this acknowledgement; others helped me so long ago that I have forgotten to add their names— I pray their forgiveness. Please believe, all of you, that I am sincerely grateful. Institutions Arnold Arboretum, Mass., U.S.A. and Dr R. Howard: for specimens. Botanical Garden, Adelaide, Australia: for specimens. Botanical Garden, Brisbane, Australia: for many specimens. Botanic Gardens, Melbourne, Australia: for many specimens. Botanical Garden, Berkeley, Calif., U.S.A.: for specimens. British Museum (Nat. Hist.): for use of the library and much help in locating early source material. Brooklyn Botanical Garden, N.Y., U.S.A.: for many specimens. Cambridge University Botanic Garden, England : for many specimens. Experimental Farm, Ottawa: for specimens. Fairchild Tropical Garden, Florida, U.S.A.: for specimens. Golden Gate Park, San Francisco, Calif., U.S.A.: for specimens. Linnean Society of London, England: for bibliographic help. McGill University, Montreal, Canada (my working home for more than 40 years) and colleagues there: for numberless favours, including (from McGill) grants for equipment. Montreal Botanical Garden and M. Marcel Raymond: for great assistance over many years, including garden and laboratory space, and hundreds of specimens. National Research Council of Canada: for numerous grants in aid of research; for a travel grant which made possible my second round-theworld voyage (during which I made tests on more than 700 species of plants in England, Australia, New Zealand, and Jamaica); and for grants used in the preparation and publication of this book. New York Botanical Garden, N.Y., U.S.A.: for specimens. Nuffield Foundation: for financial assistance in 1960-i. Rancho Santa Ana Botanic Garden and Dr R. F. Thorne: for specimens. [4]

ACKNOWLEDGEMENTS

5

Royal Botanical Garden, Edinburgh, Scotland : for many specimens. Royal Botanic Gardens, Kew, England: for many specimens; for facilities at the Jodrell Laboratory (Dr C. R. Metcalfe—who has helped me in other ways, too); and for use of the library and assistance in tracking down early references. Royal Botanic Gardens, Sydney, Australia: for specimens. Royal Horticultural Society's Gardens, Wisley, England: for specimens. University of Adelaide and Dr H. B. S. Womersley, Miss Constance M. Eardley, and others: for facilities for research, hospitality, etc. University of Auckland, N.Z., and Professor V. J. Chapman and others: for facilities for research, hospitality, etc. University of Canterbury, Christchurch, N.Z., and Professor W. R. Philipson: for assistance. University of Melbourne, Australia, and Professor J. S. Turner and others: for laboratory facilities, hospitality, etc. University of Otago, Dunedin, N.Z., and Professor G. T. S. Baylis: for help and hospitality. University of Queensland, Australia, Professor Herbert and Dr H. T. Clifford and others: for laboratory facilities, hospitality and much assistance. University of Southampton, England, and many friends: for my undergraduate training; for laboratory facilities in many summers; and for much generous help. University of Sydney, Australia and Professor R. L. Crocker, Dr R. C. Carolin and others: for providing laboratory facilities, hospitality and assistance. University of Western Australia, Nedlands and Professor B. J. Grieve and others: for laboratory facilities, hospitality and much assistance. University of the West Indies, Mona, Jamaica and Professor A. D. Skelding, Dr C. D. Adams, Dr P. Hunt, Dr K. L. Stuart and others: for laboratory accommodation, hospitality and assistance. Individuals (a) Student and other laboratory assistants (mostly aided by grants from the National Research Council of Canada) : Andrew Taussig and Arthur Dawson (1952); R. Buckridan (1953); Ruth L. McCulloch (Mrs J. Lowther) (1954); Eva Tobolt (1955); Irene Karpishka (1956); Brian Goodwin (1954); Marion Bourke (1958); Mrs Patsy Bahr (for several years); Dr Deirdre Edward, as an assistant and as a colleague; Elizabeth Shaw (Hamamelidales); Marilyn Galang (Geraniales);

6

CHEMOTAXONOMY OF FLOWERING PLANTS

U. N. Jha (`Amentiferae'); Monica Scott (Mrs E. Peter) (Rhoeadales or Papaverales); Maria Wehrli; G. H. N. Towers, as a student and as a colleague; Sally Liau (Rutales). (b) Others as individuals: Mr P. E. Ballance, for analyses of fats of Pterocarya; Mr E. C. Bate-Smith, for help; Mr A. A. Bullock, for much help with the list of families; the late Prof. H. F. Copeland, for help with names of orders, etc.; Mr E. M. Counsell, for translations from the Latin; Dr W. L. M. Crombie, for analyses of fats of Pterocarya; Dr Otto Degener, for material of Degeneria; Mrs G. du Boulay, for specimens and for help with identifications; Professor J. T. Edward, for generous assistance over many years in matters of chemistry, etc.; Dr Joseph Ewan; Dr Clarrie Frankton, for much assistance and hospitality; Dr D. A. Fraser, for specimens; Dr Robert Goodland, for material of Thurnia, etc.; Dr Marjorie Harbert, for specimens, etc.; the late Dr H. H. Hatt, for help and hospitality ; Dr C. Y. Hopkins, for fat analyses of Floerkea, and other assistance; Mr Trevor Jones; Professor R. Klibansky, for translations from the Latin; Dr Levy, for translations from the Italian; Dr Paul Maycock, for specimens; Dr McKee, for material of Phelline; Dr W. H. Minshall, for help and hospitality; Mr C. E. C. Nicholls, for help and hospitality; Professor J. C. Nicholson, for translations from the Russian; Dr G. T. Prance, for material of several unusual families; Professor Laurie Richardson, for help and hospitality; Dr W. W. Sanford, for data on raphides in orchids; Dr A. J. Sharp, for specimens; Professor W. L. Stern, for material of Columellia, etc.; Professor A. Taurins, for help in matters of chemistry; Dr Len Webb, Bill Jones and others at Brisbane, for generous help, many specimens and (Webb) for permission to use manuscript results; Professor V. C. Wynne-Edwards, for specimens. (c) Those concerned with the preparation of this book: Miss Beverly Johnston and Miss M. E. Simpson of the McGill-Queen's Press, for their patience and understanding in editorial matters; David Wynne, for preparing the figures; Mrs Evelyn Fung-a-ling, Mrs Alice Holmes, Helen Caldwell and Monica Brant, for their skill in typing from a sometimes difficult manuscript; Miss Ruby Mayhew, who has helped me so often and in so many ways; and, lastly, my wife: for making many Cigarette Tests (I am not a smoker!), and some Hot-Water Tests; for helping to prepare the index; and for taking a second place to this book (and with only moderate complaint) during its long gestation!

ABBREVIATIONS Some of the abbreviations used are too obvious to require listing here. Names of orders are often abbreviated by dropping -ales; of families by dropping -aceae; of sub-families by dropping -oideae; e.g. Ros. for Rosales; Ros. for Rosaceae; Ros. for Rosoideae. Family names not ending in -aceae may be variously abbreviated: Comp., Compos. for Compositae; Leg., Legum. for Leguminosae. ab.-gd pts above-ground (or aerial) parts BH, or B. and H. Bentham and Hooker, Gen. pl. bk bark bl. blue bu. bulb C. and E. Chadefaud and Emberger, Traite de bot. Cig. Test Cigarette Test cot. cotyledon cv. cultivar dp deep (of colour) dry wt dry weight D.-S. Dykyj-Sajfertova (Hot-Water Test) EPi, EPz Engler and Prantl, Die natürlichen Pflanzenfam., ist and znd editions f.a. fatty-acid fam., fams family, families fl. flower fluor. fluorescence frt fruit fr. wt fresh weight herb. herbarium htwd heartwood H.-W. Test Hot-Water Test infl. inflorescence ING Index nominum genericorum lf, lys leaf, leaves M. Manske, Alkaloids M. and C. Metcalfe and Chalk, Anat. of dicots M. and H. Manske and Holmes, Alkaloids mag. magenta mat. material n.c. conserved name (after a family name) o.r. Oxalis reaction p. page, pale (of colour) [7]

8

CHEMOTAXONOMY OF FLOWERING PLANTS

pet. petiole plt plant rhiz. rhizome rt root rtbk rootbark rtsk rootstock sap., sapog. saponin, sapogenin sd seed sdlg seedling spwd sapwood st. stem stbk stembark Syll. xi, Syll. xi' editions ii and rz of Engler's Syll. d. Pflanzenfam. tu. tuber v. very v., var. variety v.T. and C. van Tieghem and Constantin, Elem. de bot. W. 1966 Willis, Diet. of flow. pl. and ferns, 7th edition, 1966 (ed. H. K. Airy Shaw) yell. yellow yg young

THE HISTORY OF CHEMOTAXONOMY Some years ago I wrote (in Swain, 1963) a brief history of our subject. Here I shall attempt to give an even briefer history, adding, however, a paragraph or two about omissions from the 1963 paper. Botany arose largely from man's efforts to describe the plants used by him for food and more particularly for medicine. Thus the rootgatherers and the herbalists began to group plants for their `virtues' or medicinal properties. In the seventeenth century this grouping came to assume a modern look. Thus we find Nehemiah Grew (1641-1712) writing in An Idea of a Phytological History Propounded (1673). From hence likewise the Natures of Vegetables may be conjectured. For in looking upon divers Plants, though of different names and kinds; yet if some affinity may be found betwixt them, then the nature of any one of them being well known, we have thence ground of conjecture as to the nature of all the rest. So that as every Plant may have somewhat of nature individual to it self; so as far as it obtaineth any visible communities with other Plants, so far may it partake of common Nature with those also. Thus the Wild and Garden Cucumers have this difference, that the one purgeth strongly, the other not at all; yet in being Diuretick, they both agree. The Natures of Umbelliferous Plants we know are various; yet 'tis most probably that they all agree in this one, scil. in being Carminative ... So Tulips, Lilies, Crocuses, Jacynths, and Onions themselves, with many others in their several degrees, are all allied. If therefore Crocuses, Onions, Lilies agree in one or more faculties, then why may not all the rest ? as in being anodyne .... James Petiver, in a paper dated 10 May 1699, and titled `Some Attempts made to prove that Herbs of the same Make or Class for the generallity, have the like Vertue and Tendency to work the same Effects', starts out: Having by some Persons been asked what Method might be best proposed toward the discovering of the Vertues of Plants, amongst others I thought that this might not prove an altogether unsuccessful conjecture, Viz. That Plants of the same Figure or Likeness, have for the generallity much the same Vertues and Use: Especially if we consider, that the Organs or Structure of ye Plants of the same Family or Class, must have much the same Vessels and Ductus's to consummate that Regular formation, and consequently the Juices Circulated and strained thro' them cannot be very Heterogeneous; and that as for [9]

IO CHEMOTAXONOMY OF FLOWERING PLANTS

the most part, the Scent and Tast have great affinity, so of course their Vertue likewise cannot be very dissonant. He goes on to distinguish, on the grounds of `vertue', what we would call Umbelliferae, Labiatae and Cruciferae, and he writes entertainingly about them. In the same year as Petiver's paper appeared there was printed De Convenientia Plantarum in Fructification et Viribus—a thesis defended by Georg Friedrich Gmelin with Camerarius presiding. Steam (1957), in his introduction to the Ray Society's facsimile edition of Linnaeus' Species Plantarum points out that theses were often primarily or entirely the work of the director, and we find that Camerarius, rather than Gmelin, is sometimes credited with this work. We may place it alongside of Petiver's as a pioneering effort in this field. The next milestone in our history is the Essai sur les proprretes medicales des Plantes, comparees avec leur formes exterieures et leur classification naturelle by A. P. DeCandolle, published in 1804. The author says that Camerarius (above) was the first writer to express clearly the connections between forms and properties of plants. He gives Linnaeus some credit, too. A second edition of the Essai appeared in 1816. DeCandolle notes here that differences in soils do not greatly affect the composition of plants growing in them: C'est un phenomene continuellement present å notre examen, que de voir diverse plantes nees dans un sol parfaitement semblable, produire des matieres tres-differentes, tandis que des vegetaux analogues, nees dans les sols differens, y forment des produits semblables.' Although in 1804 he did not separate the Jasmineae from the Oleineae, in 1816 he does, and notes that insects can detect the differences between the two groups: `les cantharides attaquent d'abord les frenes, puis se jettent sur les lilas et les troenes et jusque sur les oliviers [all Oleineae] ... Elles n'attaquent au contraire les jasmins, qu'on avais mal-å-propos reunis å la familie des Oleinees, et que forment aujourd'hui une famille particuliere [Jasmineae].' He notes, too, that experiments on grafting support the split into two families. Lindley (183o) quotes from him (but translates): However heterogeneous the Olive tribe may appear as at present limited, it is remarkable that the species will all graft upon each other; a fact which demonstrates the analogy of their juices and their fibres. Thus the Lilac will graft upon the Ash, the Chionanthus and the Fontanesia, and I have even succeeded in making the Persian Lilac live ten years on Phyllirea latifolia. The Olive will take upon the Phyllirea, and even on the Ash: but we cannot graft the Jasmine

THE HISTORY OF CHEMOTAXONOMY II

on any plant of the Olive tribe; a circumstance which confirms the propriety of separating these two tribes. Somewhat later we come upon further milestones in the works of Rochleder—overlooked in my earlier essay. In 1847 he published Beiträge zur Phytochemie and in 1854 Phytochemie. I quote briefly from a translation of the latter by a student of mine, Maria Wehrli (the original is in German): `At the present time there are many more gaps in the knowledge of the chemistry of the plant kingdom than wellestablished and well-interpreted facts. Knowing about these deficiencies, we have done already the first step towards the solving of the problem ... My aims in writing this book were to compile the few facts that we know and to reveal the many gaps that exist, and in doing that I hope to stimulate further investigations that [will] lead either to the support or defeat of some of my suppositions.' I can echo Rochleder's aims in this present work! In discussing ash analyses he says that those of members of the Gramineae show much more `silicic acid' than do those of the Leguminosae and Papaveraceae. But he says also that the ashes of two such closely related plants as Calluna vulgaris and Erica carnea differ as much as do those of wheat straw and Aesculus hippocastanum—an argument against facile generalization. Rochleder gives several examples of substances which have odd distributions in plants—caffeine, chrysophanic acid and indigo—which might be used in arguments against correlation of `form' and composition. But he says that all members of the Rubiaceae studied have similar tannins, as do members of the Ericaceae, which also have ericolin; and he gives further examples of correlation in a list of about zoo orders (families) of dicotyledons alone, including almost 6o from which `no results' are available. A few of these latter could be so listed today! He concludes : Only a number of careful and scientifically up to date plant analyses will enable us to reach our goal: to replace all the now existing classification systems by one single natural system. This can be achieved only by considering all factors, morphological and anatomical as well as chemical ones. Whoever studies the plant kingdom has to be familiar with the morphology of plants as well as with the chemical composition and biosynthesis. The botanist cannot work without a knowledge of chemistry, the chemist cannot work without a knowledge of botany, if they are to promote science. We pass on now to the `modern pioneers', as I have called them. Helen C. de S. Abbott must have been a remarkable woman, writing as she did on chemotaxonomy in the 188os. She says: `The vegetable

I2 CHEMOTAXONOMY OF FLOWERING PLANTS

kingdom does not usually claim our attention for its intellectual attainments, although its members would certainly seem to possess greater chemical skill than a higher race of beings exhibit in laboratories.' And, prophetically: There has been comparatively little study of the chemical principles of plants from a purely botanical view. It promises to become a new field of research.' An early centre for research in the tropics was established in the great botanical garden at Buitenzorg (now Bogor) in Java (plant anatomy and physiology, 1884; pharmacology, 1888). From these laboratories came a stream of papers, some of which are of interest here. We find Eykman (1888) discussing alkaloids and their botanical distribution, and Greshoff (1891) writing, among other things, of laurotetanine in the Lauraceae. He had found this alkaloid in several plants of that family and says: Mans les notes jointes å [Hernandia, Illigera, Gyrocarpus, Cassytha—in which he also found alkaloids] l'auteur rappelle les opinions divergentes de la place naturelle de ces quatres genres, qu'on a ranges dans les familles tres differentes. Peut-etre le phytochimiste pourra renseigner le systematicien aussitot que paraitra l'identite ou l'analogie de structure de ces alkaloides avec lauro-tetanine.' A little later van Romburgh published extensively on the distribution of acetone, methyl salicylate and HCN. Treub, in several papers, and de Jong, also investigated plants for HCN—their work in this field being more reliable than that of some later workers in the tropics! Gorter's work on chlorogenic acid (1910) also came from Buitenzorg. Greshoff, whom we mentioned above, also worked at Kew, and published (1909) a summary of tests on many plants for tannins, saponins, HCN and alkaloids. Writing of HCN in Platanus he brings out, in a striking way, the high concentration in the leaves: `Indeed, in the ordinary plane-tree of the London streets (P. acerifolia), there is so much hydrocyanic acid present that the amount from every London plane-leaf would be enough to kill a London sparrow.' He is ambitious for chemotaxonomy, as witness: ` Strictly speaking one might demand that every accurate description of a genus or of a new species should be accompanied by ['should include' would be better] a short "chemical description" of the plant.' If Greshoff was ambitious for his subject, McNair was perhaps overambitious in attempting to apply comparative chemistry generally to taxonomy. Twenty-six of his papers, which appeared from 1916 to 1945, have recently been reprinted (1965). In his first paper he notes that Japan `wax' (a fat) from Asiatic species of Rims is similar to the fruit-coat fats of two N. American species of the genus. He continued to be interested in fats, and in 1929 discussed those of 30o plants (from 83 families), in relation to climate and taxonomy. He concluded

THE HISTORY OF CHEMOTAXONOMY 13

that fats and oils of closely related plants are closely similar, and that in general the plants of the tropics tend to store fats or non-drying oils of higher melting-points than those of plants from temperate regions. In 1935 he is writing of alkaloids. He says that each species of a large genus, such as Aconitum, may have a different member of a group of closely related alkaloids; that any one alkaloid may occur in many members of one family (e.g. protopine in the Papaveraceae); but that few individual alkaloids occur in more than one family. In 1935, too, he has a paper called `Angiosperm phylogeny on a chemical basis'. Here he claims that plants high in the evolutionary scale have constituents with larger molecules and fats with higher iodine numbers than have those lower in the scale. He uses these facts' to argue that trees are more primitive than herbaceous plants. In this paper he contrasts publications by Standley and Rusby. The former had written on Rubiaceae in 1ß31, the latter—who had published on Cinchona in 1887—writes, in 1931–a : ' It is doubtful if any other genus of equal size has received such thorough study, as to gross and microscopical structure, chemistry, reproduction, embryology, horticulture, ecology and geography, as has Cinchona ... [yet] In the most recent publication on the Bolivian cinchonas, Standley's The Rubiaceae of Bolivia, all this information is ignored, with the result of so many errors that I can regard the publication only as a misfortune to Cinchona literature.' Rusby may have been unfair, but he does emphasize the importance to taxonomy of including data from all fields when making taxonomic judgments. In 1945 McNair is concluding on chemical grounds that monocotyledons are more primitive than dicotyledons, and that in the latter group the Sympetalae are the most advanced. He has other papers, too, along similar lines. We must applaud McNair for his courage in using comparative chemistry on such a sweeping scale, but we must question some of his. assumptions and conclude that he was before his time' in many respects. Now that we are well into the twentieth century with our history it is convenient to deal with some individual topics, some of which receive considerable attention elsewhere in this book. (a) Raphides I have myself been particularly interested in raphides and have looked for them in sections of many plants—more especially in the control sections when carrying out the Syringin Test (p. 71). Early workers,

14. CHEMOTAXONOMY OF FLOWERING PLANTS

and some later ones, have included small, unoriented acicular crystals among their raphides'. We define them as slender, needle-shaped crystals of calcium oxalate, arranged parallel to each other in tight bundles and occurring in special raphide-sacs. I don't know who first used this definition, or who first used raphides as a diagnostic character. Gulliver (see below) says that Lindley used them in 1839, but Robert Brown (1773-1858) made use of presence or absence of these crystals as a diagnostic character in a paper prepared in 1831 and published in 1833. He was among many things, an authority on the Orchidaceae and noted the nucleus—he was the first, I think, to use the name—in cells of members of that family. He also saw raphides and wrote: `My concluding observation on Orchideae relates to the very general existence and great abundance, in this family, of Raphides or acicular crystals in almost every part of the cellular tissue.' In a later paper (184.5) he decided that the reticulated sheath through which the flower of Rafesia bursts when emerging from its host plant is part of that host because it has raphides: That the whole of this covering belongs to the stock, is proved by its containing those raphides or acicular crystals which are so abundant in the root of the Vitis or Cissus, and which are altogether wanting in the parasite.' Gulliver (1804-1882), a British anatomist and microscopist, made a careful study of raphides, defining them as I have done. His many papers appeared from 1861 to 1880. He says (1866) that: `Only 3 orders [we should say families] of British Dicotyledons can as yet be characterized as raphis-bearers, and these are—Balsaminaceae, Onagraceae, and Rubiaceae.' He was correct in this. He knew that some non-British members of the Rubiaceae do have raphides. He saw that Trapa (not a native of Britain) lacks raphides, and therefore perhaps does not really belong to the order Onagraceae'. Today we have a family Trapaceae for it. In I 88o (his last paper ?) Gulliver says that he has not seen raphides in the many members of the Saxifragaceae which he has examined, but that they occur in Hydrangea: `Here then is a natural and sharp diagnostic between Saxifrages and Hydrangeas.' We must not pursue this particular point further here, but see my earlier history (pp. 52-4) and our discussion of the Saxifragaceae (p. 1645 of this book). Presence or absence of raphides is a character used more recently by Tomlinson (1962) in discussing the families of the Zingiberales (italics mine): In contrast to the randomness just discussed, three features suggest that the eight families fall into four natural groups. These are the

THE HISTORY OF CHEMOTAXONOMY 15

structure of the guard cells, the presence or absence of raphide sacs, and the structure of the root stele... . The first of the four groups includes Heliconiaceae, Musaceae, and Strelitziaceae, which have raphide sacs, symmetrical guard cells ... and anomalous root structure at least in the last two families. The second includes Costaceae, Marantaceae, and Zingiberaceae, which have asymmetrical guard cells ... and lack raphide sacs and anomalous root structure.. .. The third has Cannaceae without raphide sacs. The fourth group consists of Lowiaceae with its raphide sacs, asymmetrical guard cells, and normal root structure. Note that some have included Heliconiaceae, Musaceae, Strelitziaceae and Lowiaceae, the only families of the eight with raphide sacs, in Musaceae (S.!.). Tomlinson concluded that occurrence of raphides is a primitive feature. It is of interest to note that there is some evidence that raphides are primitive in the dicotyledons, too (see Gibbs, 1954). (b) Cyanogenesis It has Iong been known that many plants, but still a small minority, yield under some conditions appreciable amounts of HCN (prussic acid, hydrocyanic acid). Such plants are said to be cyanogenic. We deal elsewhere in this book with cyanogenic glycosides, but a few notes on the history of their use in chemotaxonomy are in order here. The earliest reference that I have found is in Lindley (183o). He says that Amygdaleae are: `Distinguished from Rosaceae and Pomaceae by their fruit being a drupe, their bark yielding gum, and by the presence of hydrocyanic acid; from Leguminosae by the latter character, and.. from Chrysobalaneae by their hydrocyanic acid...' Lindley also noted that cyanogenic plants may be toxic. Endlicher (1836-4o) also used presence of HCN in Amygdaleae to distinguish that group from the Chrysobalaneae. These pioneers were followed during the next century by a host of others who tested plants for HCN. I have listed many of these, from Jorissen (1884) to Hegnauer and myself in the present. Not all reports are trustworthy—some workers have used faulty methods—but we do have a large body of information (p. 6o). A weakness is the relative scarcity of negative records, some lists reporting only positive results. Another weakness is that few of the records tell us which of the dozen or more cyanogenic substances is/are responsible for cyanogenesis in particular cases. In my own very extensive testing, for example, I have dealt only with presence or absence of cyanogenesis. In the course of my work I have noticed some atypical results (p. 59).

16 CHEMOTAXONOMY OF FLOWERING PLANTS

These suggest that further work is necessary before we can be sure that all `positive' results are indeed due to HCN. We must note also, as so often in this book, that only a minority of the known species of flowering plants have as yet been tested for cyanogenesis. A lot of testing remains to be done before we can say that any given taxon is non-cyanogenic. And this is made the more difficult because some plants are cyanogenic only at times, others only in some organs (p. 43). (c) Amino-acids and proteins Amino-acids, the building-blocks of proteins, are universally present in plants, and may be considered first. More than twenty are in all proteins; others are common constituents of plants; yet others seem to be very restricted in their distribution and these can be important taxonomic markers. Here we are concerned with the historical aspect. The first amino-acid to be isolated was asparagine (Vauquelin and Robiquet, 18o6), and until the work of Ritthausen (1860-72) it was the only amino-acid known to occur in plants. When E. Schulze finished his work (about 1906) fifteen protein amino-acids had been found. Only after the introduction of chromatography (see below) was there a very rapid increase in the number of non-protein amino-acids known. Fowden (1962) has a graph showing this, the numbers being roughly: 2 in 1915, 4 in 193o, 8 in 194o, 13 in 1950, 40 in 1955, 7o in 196o, and perhaps loo in 1965, with no indication of a levelling off. It must be emphasized that much remains to be done, even for the known aminoacids, for we know little as yet about their distribution. Today we have sophisticated methods for the investigation of proteins, and two of these may be referred to briefly here: serology and amino-acid sequence determinations. Serology has now a rather lengthy history. Its use in taxonomy is based on the idea that each kind of living organism has its own characteristic proteins; that the proteins of nearly related organisms are closely similar; that those of organisms more distantly related are less alike; and so on. We have discussed serology elsewhere (Gibbs, 1963) and in this book (p. 384). Its history really began more than 7o years ago. It was considered by some to be the answer to the taxonomists' prayer for a certain means of determining relationships; was bitterly attacked; fell into disrepute; and only with more sophisticated modern techniques has it been restored to respectability. Perhaps it may be replaced as a tool by amino-acid sequence determinations, which we have also discussed elsewhere in this book (p. 383). It does seem, on the face of it, that we are here at last determining the ultimate structures of

THE HISTORY OF CHEMOTAXONOMY 17

the stuffs of life, and justifying the optimism of Boulter, Laycock, Ramshaw, and Thompson (197o), quoted on p. 384. Let us hope that this optimism is not misplaced. In discussing the history of biology with my students I have had again and again to stress the fact that progress in biology has often been hampered by lack of tools. The detailed study of anatomy had to wait in turn for the lens, the compound microscope and the electron microscope. The early student of the biogenesis of complicated substances lamented the absence of a `flag' by which to follow elements during synthesis and/or degradation. He now has the technique of `labelling' which gives him a set of flags. The techniques of chromatography have made possible the rapid detection and estimation of very many substances important to chemotaxonomy. Let us briefly relate its history. Pliny (A.D. 23-79) is said to have used papyrus impregnated with an extract of gall-nuts (tannins) for the detection of ferrous sulphate, essentially our Tannin Test A in reverse! But it was the work of Schönbein (1861), Goppelsroeder (1901) and others on `capillary analysis' which was the real beginning of chromatography. Day (1897, 1903) used `fractional diffusion', and he was followed by Gilpin and others (1908, 1910, 1913). While this was going on Tswett (two papers in 1906) was separating plant pigments by adsorption. We translate: There is a certain adsorption series by which substances can be arranged. On this law rests the following important application. If one filters a petrol—ether solution of chlorophyll through an adsorption column (I used chiefly calcium carbonate, densely packed in narrow glass tubes) the colouring matter is separated into zones from top to bottom, according to the adsorption series...This separation becomes practically complete, if after the passage of the coloured solution into the adsorption column, one then uses a stream of the pure solvent... Such a preparation I call a chromatogram and the corresponding method a chromatographic method. How modern this sounds! But there was a long pause before chromatography `caught on' in a big way. Martin and Synge (1941) and Consden, Gordon and Martin (1944) have been credited by Block, Durrum and Zweig (1958) with the present-day popularity of the subject. They used liquid—liquid counter-current techniques, and oneway and two-way paper chromatography. Only a few years ago the determination of the fatty-acids from a fat was a major operation. Today, using gas-chromatography, one can get quantitative results in a very brief time. This is reflected in the rapidly increasing numbers of analyses available. In Hilditch (1st, 2nd and

I8 CHEMOTAXONOMY OF FLOWERING PLANTS

3rd editions; 1940, 1947 and 1956) we find analytical data on roughly 400, 45o and 60o plant fats. In Hilditch and Williams (1964) we find goo, and in a paper by Wolff (1966) an estimate of moo. We have referred above to the increase in our knowledge of the amino-acids, and we shall note the use of chromatography in the detection of the phenolic constituents of plants. Illustrations could be multiplied, though not all of our increase in knowledge is due to chromatography. It is only a few years ago that the structure of the first aucubin-type glycoside was determined; now, in 1971, a review paper on iridoids and seco-iridoids by Plouvier and Favre-Bonvin refers to 317 papers! We may conclude this brief essay by a reference to a remark by Alston (when, where ?) that it is time for a shift in emphasis in chemotaxonomy from problem-exposing to problem-solving. This book, as we shall see, reveals that there is still a lot of the former, and not as yet a great deal of the latter!

CRITERIA USED IN TAXONOMY, AND SOME RELATED TOPICS INTRODUCTION Robyns, in his presidential address (1964) to the general assembly of the International Association for Plant Taxonomy (I.A.P.T.), said (the italics are mine) : All scientific taxonomists aim indeed at the best biological classification possible, by using information and data from any and all available sources of information, integrating them into a synthesis in order to formulate a complete knowledge of each taxon actually living or extinct, with its relationships, its origin, its variation and its chorology. As our knowledge of plants is always subject to revision in time as new and relevant data arise, the field of taxonomy is revived and increasing so that systematics, instead of being old-fashioned and obsolete, as is sometimes claimed, is still and will always remain very much alive and at the same time greatly progressive, with unlimited possibilities as a most essential basis for all other branches of biological research. There is much that is pertinent to this section in the thoughtful review by Lincoln Constance (1964) entitled Systematic botany, an unending synthesis. I must content myself with a single quotation: Every few years some new approach or technique is proclaimed which this time is going to be successfully exploited to get the stone— that is, taxonomy—over the crest of the ridge dividing intuitive art from exact science. Anatomy, paleobotany, embryology, palynology, cytology, and genetics, to name a few, have all had their try; chemistry and mathematics are chafing eagerly in the wings to have their day upon the stage. One may be reasonably sure that other actors lurk behind these, although their features are not as yet quite discernible. The notes that follow are intended to illustrate the many criteria that have been and are being used by systematists in their search for a truly phylogenetic system of classification. We have arranged them in a more or less historical sequence—for general morphology, for example, obviously preceded numerical taxonomy—but such an apparently simple arrangement presents many difficulties. 1. General morphology The ordinary, easily observable morphological characters of plants have been used from the beginnings of taxonomy, and have undoubted [19]

20 CHEMOTAXONOMY OF FLOWERING PLANTS

worth. Even here, however, we find that simple morphology may be misleading, and controversy still rages. Is the woody character primitive when contrasted with the herbaceous ? Are numerous floral parts more primitive than few ? Sporne (1954) has tried to make a list of supposedly primitive characters (mostly morphological) which will enable him to estimate the degree of advancement of any given family. He concluded that: `...the most reliable indicators of primitiveness are : woody habit, presence of secretory cells, leaves alternate, stipules present, flowers actinomorphic, petals free, stamens pleiomerous, carpels pleiomerous, seeds arillate, two integuments, integumentary vascular bundles, nuclear endosperm, carpels free, axile placentation.' Sporne realized that some characters which: ' are believed to have been present in ancestral dicotyledons and, therefore, are primitive in certain families ...(may) have also appeared secondarily in certain advanced families. These are: unisexual flower, haplochlamydy and small number of seeds.' He calculated, using the selected characters, ' advancement indices' for families of dicotyledons, the families with the lower values being regarded as the more primitive. He came up with the following (I give only some) : Magnoliaceae 14 Bombacaceae and Flacourtiaceae 15 Annonaceae, Leguminosae, Malvaceae and Myristicaceae 18 Rhizophoraceae 21 Guttiferae, Nymphaeaceae and Platanaceae 32 Medusagynaceae, Nepenthaceae, Sonneratiaceae and Ulmaceae 42 Proteaceae 55 Casuarinaceae and Piperaceae 6o Podostemonaceae 7o Brunoniaceae, Campanulaceae, Dysphaniaceae, Gentianaceae, Goodeniaceae and Scrophulariaceae 82 Balanophoraceae and Phrymaceae 92 Hippuridaceae, Hydrostachyaceae, Martyniaceae and Valerianaceae Ioo I have tried to use Sporne's results on the arrangement of orders, and of families in orders and sub-orders, in the nth Syllabus (1936) as compared with the later 12th Syllabus (1964). In some cases, the Centrospermae for example, his figures support the supposedly better system in the latter, in other cases little ' improvement' is evident. An interesting extrapolation would be to assume that ' chemical characters' of families with low advancement indices are ' primitive' and those of families with high indices are ' advanced'. Bate-Smith and Metcalfe (1957) actually tried this out for tannins in dicotyledons. They

CRITERIA USED IN TAXONOMY 2I

found that families with tannins had advancement indices between iq. and 75; those in which few members had them were between 32 and 93 ; while those lacking tannins were between 36 and loo. They concluded that the capacity to synthesize tannins is a primitive character. We could give many examples of the usefulness of even single morphological characters in taxonomy, but one must suffice here. Metcalfe and Clifford (1968) report that Festucoid grasses lack microhairs, while in Panicoid grasses they are almost universal. Anatomy We have seen that general morphology has been used from the beginnings of botany in classifying plants. The use of anatomy, except of the grossest kind, had to wait until microscopes became available, but it seems to have been slow to get under way even with their help. Reynolds Green (19o9) said that Radlkofer was the father of the use of comparative anatomy in taxonomy. He wrote: z.

The founder of the method as one of general application ...was Radlkofer, who gave a new impetus to it in his great monograph of the Sapindaceous genus Serjania, published in 1875 ... If Radlkofer may be regarded as the founder of this movement, the great importance which came to be attached to it towards the end of the century was in large measure due to his pupil Solereder. As recently as 1967 Metcalfe writes: Two of the most important problems in systematic anatomy are these. Firstly to collect comparative histological data on a scale that is large enough to permit them to form an integral part of the descriptive matter on which taxonomy is based. The second, more exciting stage is reached when enough descriptive data have been assembled to enable us to throw further light on the interrelationships and phylogeny of the plants in which they are exemplified. One of the greatest current dangers is that some botanists may find themselves tempted to move on to the second of these z stages before the first has been sufficiently completed.... He applies comparative anatomy to the subject of relationship between the Gramineae and Cyperaceae and concludes that: The histological differences between the Cyperaceae and Gramineae are ...sufficiently great to support the view that, if both families have evolved from a common prototype, it must have been very remote from the present day species of which the 2 families consist.

22 CHEMOTAXONOMY OF FLOWERING PLANTS

Metcalfe warns that parallel development may occur in anatomy, as in other characters, and that this may mislead the unwary. The occurrence of vessels in the Gnetales may be a case in point. It has been argued that their presence indicates relationship with the angiosperms. Some anatomists, however, say that they arise in a manner different from that leading to vessels in the latter and that this is a strong argument against relationship! Metcalfe points out that different anatomical characters may be important in different groups: If we turn to Rhododendron, the trichomes on the leaves are at least as taxonomically interesting as the structure of the wood, whilst in a family such as the Dipterocarpaceae we cannot afford to study the structure of the wood whilst ignoring that of the bark or the fascinatingly complex vascular structure of the petioles. In 1967(8) he writes: It is, however, when we turn to the Monocotyledons that the irrelevance of wood structure is most apparent, for in these plants there is little if any secondary xylem at all. Nevertheless, recent work at the Jodrell Laboratory has shown that in the taxonomically `difficult' family Restionaceae it is often easier to identify species from characters visible in transverse sections of the stem than it is from the exomorphic characters that are normally employed for this purpose! 3. Pollen morphology and anatomy Use of pollen characters in taxonomy is using micro-morphological and anatomical characters and is therefore comparatively modern. Nevertheless, it is said, in the Hist. bot. en France (I.B.C., Paris, 1954) to have been used almost 15o years ago: `En 1825, A. Guillemin fit une etude approfondie d'un grand nombre de grains de pollen et, dans un essai de classification, souligna l'importance de l'etude des pollens pour deceler les affinites entre les familles.' In recent years whole books have been published on pollen by Erdtman (1952), Wodehouse (1935), etc., with many examples of the usefulness of pollen characters. We shall note only a few examples from recent papers. Thomas (196o) notes that the pollens of the three genera (Cyrilla, Cliftonia and Purdiaea) that he would include in the Cyrillaceae are very similar. He also says: Pollen studies have also added further evidence to [sic] a close relationship between the Cyrillaceae and the Ericales. The only

CRITERIA USED IN TAXONOMY 23

group which has pollen that closely resembles that of the Cyrillaceae is the genus Clethra [Clethraceae, included in Ericales] ... In the Aquifoliaceae and the Celastraceae, on the other hand, the pollen is quite unlike that of the Cyrillaceae as was pointed out by Erdtman (1952). An examination of the pollen of Cyrillopsis has added further evidence for excluding this genus from the Cyrillaceae. The pollen of Cyrillopsis is similar to that found in some members of the Celastraceae, but quite unlike that of the Cyrillaceae. Lewis (1961) merged the genera Oldenlandia L. and Houstonia L. with Hedyotis L. More recently (1965) he studied the pollens of some of these plants and concluded: `The evidence from palynology also supports the treatment of Hedyotis and Houstonia as congeneric.' Finally we may note that Jeffrey in 1962 proposed a new classification of the Cucurbitaceae. In 1964, after examining a set of pollen-slides, he concluded that they supported rather closely his classification, but he made some changes as a result of these studies. 4. Embryology In recent times the subject embryology has come to embrace much more than study of the embryo itself. This is made clear by Maheshwari in his An introduction to the embryology of angiosperms (195o). There he has chapters on the microsporangium, the megasporangium, the female gametophyte, the male gametophyte, fertilization, the embryo (at last!), apomyxis, polyembryony, embryology in relation to taxonomy and experimental embryology. His chapter on embryology in relation to taxonomy gives interesting examples. The little family Empetraceae has baffled the taxonomists. Don (1827) put it in or near to the Euphorbiaceae; Pax (1896) placed it in the Sapindales near Celastraceae and Buxaceae; and several authors believe it to be related to the Ericaceae. Maheshwari writes: `That this last view is the correct one and that the Empetraceae is to be classed under the Ericales have now been definitely established on the basis of the embryological data brought forward by Samuelsson (1913) ... The Empetraceae show a close correspondence in all respects [with the Ericales], while the Sapindales and Celastrales differ in so many ways that there is no doubt as to the correctness of Samuelsson's view.' We shall see that the chemistry of the Empetraceae is also in line with a position in the Ericales. The Cactaceae, on embryological grounds, are said to be nearer to the Portulacaceae than to the Passifloraceae. This, too, is supported by the chemical evidence.

24 CHEMOTAXONOMY OF FLOWERING PLANTS

Trapa was formerly included in the Onagraceae. Its eight-nucleate embryo-sac, and other embryological features, mark it off from the true Onagraceae. It is treated today as a separate family, Trapaceae or Hydrocaryaceae, and the absence of raphides from Trapa is in line with this. Reeder (1962) actually uses the character of the embryo itself in dealing with the grasses. He writes: `Using the embryo type as the principal criterion, one may recognize 6 basic groups of grasses. These are : festucoid, bambusoid (including oryzoid-olyroid), centothecoid, arundinoid-danthonioid, chloridoid-eragrostoid, and panicoid ... The author's previous interpretation of the bamboo embryo as distinct from the oryzoid-olyroid type is shown to be erroneous.' We could multiply these examples, but enough has been said to make it clear that comparative embryology, as might be expected, is a valuable tool in taxonomy. 5. Biosystematics, including cytology and genetics The nature of biosystematics' was discussed at the 9th International Botanical Congress held in Montreal in 1959, and an international committee on biosystematic terminology was set up. Heywood and Löve reported from this in 1961. We quote: biosystematics and its subdivisions, cytotaxonomy and experimental taxonomy s.str., are to be regarded as an approach to taxonomy employing the methods of cytology and genetics to its problems, and not as a replacement of classical taxonomy.' The committee agreed that its activities embrace experimental taxonomy, cytotaxonomy, cytogeography, genecology, biometry, microevolutionary studies and speciation. That nearby subjects are comparative developmental physiology, comparative phytochemistry and comparative embryology. That biosystematics is not necessarily aimed at taxonomy. There are so many examples of the use of cytology and genetics in systematic botany that we shall not bother to cite any. 6. Grafting It has long been known that it is possible in some cases to graft successfully one plant upon another, while in other cases this proves impossible. Some years ago (1954) I wrote: A graft may almost be likened to a parasite. The scion—the `parasite' —grows upon the stock—its `host', and absorbs materials from it. Unless scion and stock are `compatible' union does not occur and

CRITERIA USED IN TAXONOMY 25

the scion dies. In general scions grow only upon stocks of closely related plants and we may suppose that chemical as well as other factors are involved. Interspecific grafts are not uncommon and intergeneric grafts are possible in some cases, as in the Cactaceae. Herrmann (1951) has given some examples of intergeneric grafts-

Picea on Abies and vice versa, Picea on Larix, on Pseudotsuga, and on Pinus. These genera are all within the Pinaceae. From the dicotyledons he gives Fagus and Castanea upon Quercus (all Fagaceae); and Hallmodendron and Caragana (Leguminosae). Melnick, Holm and Struckmeyer (1964) grafted young fertilized ovules (7-20 days from pollination) with some placental tissue (as scion) on to the placentas of growing attached fruits of Capsicum frutescens L. var. California wonder (Solanaceae, as host), and got the following results. Intervarietal: C. frutescens L. var. Wisconsin lakes—seeds germinated and grew into normal plants. Interspecific: C. annuum—ditto. Intergeneric: Lycopersicum esculentum Mill. var.—ditto. Solanum melongena L. var.—the seeds formed were dormant. S. pseudocapsicum L.—ditto. Interfamilial: Fragaria virginiana hort. var. (Rosaceae)—seeds germinated and grew into seedlings. We give these examples to show that a successful graft does not prove close relationship in every case. Nevertheless, success in grafting is usually a proof of near-relationship. We have noted elsewhere in this book the use of this in the Oleaceae. Garrya (in `our' Garryaceae) has been grafted upon Aucuba (Cornaceae), and we shall see that many believe these genera to be related. Didierea has been grafted on members of the Cactaceae, and we shall see that there are other reasons, too, for believing that the Didiereaceae and the Cactaceae are related. 7. Parasites and predators Some parasites are quite specific, each kind using a single host. Others are less so, parasitizing a few host plants. Yet others seem to be catholic in their tastes, growing on many quite unrelated hosts. One may be reasonably sure that these differences are due in large part to the differing requirements, physical and chemical, of the parasites. At the one extreme are root-parasites which grow almost independently,

26 CHEMOTAXONOMY OF FLOWERING PLANTS

but which attach their roots to the roots of any, or almost any, plants they can reach. It is said that in Colorado the Bastard toadflax (Comandra umbellata), a member of the Santalales, occurs upon at least 45 different hosts. The Broomrapes (Orobanche spp.) are complete parasites and some of them are highly specific. We may suppose that Comandra umbellata needs little from its host, but that the highly specific species of Orobanche require many substances that they are unable to make for themselves. We may suppose, too, that in the case of the most specialized parasitism hosts and parasites have evolved together, and this makes possible some very interesting speculation. Can we deduce the relationships within groups of parasites by noting the plants upon which they grow? Or/and can we, by noting their parasites, get clues to the relationships of the host plants ? Savile (1962) studied the rusts of Allium and other plants and concluded: It appears from this evidence that Allium is related to, but more primitive than Scilla and related genera. If the inflorescence characters emphasized by Hutchinson are a reliable indication of relationship to the amaryllids, the most satisfactory disposition of Allieae seems to lie in restoring the group to family rank. Alliaceae may then be regarded as close to the immediate common ancestor of Liliaceae and Amaryllidaceae. Hutchinson's arrangement [of 1934], with Amaryllidaceae derived from Liliaceae and containing Allieae, is unrealistic, both because it denies the proximity of Allium to Liliaceae, and because it suggests that Allieae are more modern than Liliaceae whereas the rust relationships indicate the reverse. In 1968 Savile considered Filipendula from a similar approach. It is a rosaceous genus of about 10 species which, it has been suggested, should be in the Spiraeoideae rather than in the Rosoideae (where it is usually placed). Savile noted that it is attacked by rusts of the genus Triphragmium. Rusts of related genera all attack members of the Rosoideae, and therefore: `It appears, by inference, that Filipendula also belongs to this subfamily.' Turning to predators, we find Kontuniemi (1955) arguing that a sawfly can distinguish between Lysimachia and Naumburgia, which botanists combine. Fryxell and Lukefahr (1967) have used the presence of the bollweevil in Hampea as an argument for placing the genus in a tribe Gossypieae of the Malvaceae, rather than in the Bombacaceae, where it is usually placed. Fryxell would include in Gossypieae: Hampea Schlechtd.: the primary host of the weevil ?

CRITERIA USED IN TAXONOMY 27

Gossypium L.: now the usual host. Thespesia Corr.: some species of which are fed upon by the weevil. Cienfuegosia Cay.: the weevil feeds on C. affinis. 8. Palaeontology In attempting to assemble the phylogeny of a group for which ample fossils are available one turns to them for a trustworthy record of the history of the group. `Primitive' characters are those appearing early: `advanced' ones those appearing late. One can see positive evidence of parallel and convergent evolution, and so on. For some groups of organisms, plant and animal, the story is as easy as this: for the flowering plants with which we are concerned it is very different. Darwin realized this. In a letter to Hooker, written in 1879, he wrote: The rapid development as far as we can judge of all the higher plants within recent geological times is an abominable mystery.' Today, almost a century later, we may say the same. We do not know for certain from what group of plants the flowering plants arose. We cannot say with certainty that monocotyledons arose from dicotyledons: that woody plants are more `primitive' than herbaceous ones. If the angiosperms came from gymnosperms, then we may well conclude that some, at least, of the characters that appeared early in the gymnosperms and are to be found today in the angiosperms are indeed `primitive', but only if they did not arise independently in the two groups. There are so many `ifs' in dealing with angiosperm phylogeny that we are continually guessing. And there are still some botanists who believe the dicotyledons to be polyphyletic, while others argue for a single origin! Because of the many uncertainties there is a grave danger that we may argue in circles. That because we believe the Magnoliaceae, for example, to be primitive, then any character detected in that family is necessarily a primitive one. Only a few fossils of flowering plants are known from the Jurassic. From the Cretaceous we have many, but they include the remains of plants which represent both primitive' and `advanced' familiesMagnoliaceae, Lauraceae, Nymphaeaceae, Salicaceae, Juglandaceae, Betulaceae, Fagaceae, Araliaceae, Cornaceae, etc. This does not mean that taxonomy gets no help from palaeontology. It gets relatively little. 9. Comparative chemistry `The application of comparative plant chemistry to the solution of problems in the taxonomy of flowering plants' was a `sort of' omnibus

28 CHEMOTAXONOMY OF FLOWERING PLANTS

title for this book! We deal elsewhere (p. 9) with the history of our subject, and we deal over and over again in the following pages with problems which may well be solved by comparative plant chemistry. But we must be modest in our claims for chemotaxonomy. In its present state of development it perhaps poses more problems than it solves. One is still faced with matters of judgment, as in traditional taxonomy. How important is the presence or absence of an unusual substance or group of substances ? This will vary from case to case. The presence of caffeine might be relatively unimportant of itself, since it seems to occur more or less sporadically in flowering plants. But given a genus of caffeine-producers in a family not otherwise noted for the substance, the presence or absence of it in a species which might or might not be included in that genus would then loom large. If Picrodendron is close to Juglans, as some have said, then the presence of juglone in it would be of great significance (I did not find it; but have not had sufficient material of the genus as yet). We have several bits of chemical evidence supporting a relationship between the Pittosporaceae and the Araliaceae. Any additional evidence would be really significant. But how much chemical evidence do we need to warrant shifting the Pittosporaceae to an order including the Araliaceae? How much more evidence do we need before we are happy in separating the Papaveraceae from the Capparidaceae, Cruciferae, Resedaceae, etc. ? The reader will find these problems, and more, in the following pages. One more point may be discussed here. A quite eminent plant chemist has said that negative evidence—records of absence of substances—is unimportant. I disagree. It seems to me almost as vital to establish the complete absence of a particular substance from a group, as to establish its constant presence in another group. Let us remember our dichotomous keys, which are based very largely on presence or absence of characters. The Theaceae include in some interpretations plants devoid of raphides, in others three raphide-containing genera—Tetramerista, Pelliceria and Trematanthera—are included. But are all the rest of the family really devoid of raphides ? I would be willing to bet that many members have never been examined for this character, and until all have been studied we cannot with certainty define a family Theaceae as raphideless. The Chrysobalanaceae are said to be non-cyanogenic: but on what evidence ? I can find very little. to. Numerical taxonomy This would better be defined as an approach to taxonomy, for it makes use of criteria of all types—morphological, anatomical, bio-

CRITERIA USED IN TAXONOMY 29

chemical and so on. It sometimes tries to avoid judgments by treating all characters as of equal weight, but judgments creep in. If we use large-leaved' as against `small-leaved' or broad-leaved' as against `narrow-leaved' (which may be good taxonomic characters) we have to judge small as against large, and broad as opposed to narrow. And we use judgment in deciding what characters we are to feed into the computer. I am not arguing against numerical taxonomy here, but against the view that it can eliminate subjective judgments. Perhaps I am in agreement with a review by George Gaylord Simpson (1964) of a book Principles of numerical taxonomy by Sokal and Sneath (1963). Simpson wrote: The present ferment in taxonomy is a healthy sign. Eventually taxonomy will surely profit by the incorporation of a "numerical taxonomy", less rigid and less fanatical. This book by Sokal and Sneath will be a milestone in that desired development, but in the meantime I fear that its biased attitude has done not only some good but also some harm to taxonomy and, indeed, to its own basic thesis.' Kalkman (1966) has an amusing article, resulting from a paper by Sokal and Sneath (1966) and called Keeping up with the Joneses in which he pokes fun at the numerical taxonomists. Much of what he says will be applauded by `traditional' taxonomists. One important point that I have not seen made is suggested to me by the title of Kalkman's paper. Computers are expensive to buy and to operate, and botanists in the under-privileged centres must continue to do taxonomy without their help. We may conclude this little section with a couple of examples, taken more or less at random. Taylor has monographed the genus Lithophragma (Saxifragaceae), using traditional taxonomic methods and has also made a taximetric' study (1966) of it. We quote from his abstract: A taximetric analysis of Lithophragma ...reveals a close similarity to the taxonomy proposed by the author ...using the traditional intuitive approach. The taximetric method is based on a neo-Adansonian approach utilizing the same characters used in the intuitive study, but arbitrarily giving equal weight to all unit-characters... The conclusion is reached that taximetrics may help place plant taxonomy on an objective basis ...Its application, however, must await extensive documentation of plant taxa on a broad basis. Watson, Williams and Lance (1966) used 20 characters for 24 genera of the Epacridaceae and analysed these with a program of similarity' type. They came up with a classification which: seems, judged by external criteria, to represent an improvement on that of Bentham, whose scheme appears in turn to be superior to that of Drude.'

CHAOS IN TAXONOMY I have on many occasions lectured my students on `Chaos in taxonomy', trying to impress on them the many uncertainties which exist and the defeats taxonomists have suffered in their efforts to establish a stable system. Melchior (1959) points out that: ' Seit 1940 sind nicht weniger als 16 naturliche Systeme der Dikotyledonen and Monokotyledonen publiziert worden, von denen keines dem anderen gleicht.' It is good for us to be reminded that our judgments are faulty, that groups that we have thought to be natural ones are often shown to be quite unnatural, that we often accept judgments by others that are based on inadequate information. Again and again in this book I point out how little we know about many of the taxonomically most interesting taxa. Here I select a very few of the problems that are as yet unsolved. (a) Cornaceae In EP1 (1897) Harms recognized a family Cornaceae with 15 genera. It is true that he had no less than 7 sub-families, indicating that he considered it to be a rather heterogeneous assemblage. In the notes that follow I have put together some of the views that have been expressed about the genera included by Harms. Garrya (15-18) is usually made a family—Garryaceae—of its own. Some have made an order Garryales for it. Nyssa (8-1o) has been put in the Santalaceae. It is more often made the type genus of a family Nyssaceae, with Camptotheca (1) and sometimes Davidia (1). The family has been included in the Myrtales. Davidia has also been made a family of its own—Davidiaceae. The next genus in Harms' arrangement is Alangium (17-18) which is often made a family Alangiaceae, and this has been placed in Myrtales and in Santalales. Airy Shaw (in W. 1966) adds a genus Metteniusa (3) to the Alangiaceae. Mastixia (25) is yet another genus which has had a family—Mastixiaceae—of its own. Curtisia (1) has also been made a family, Curtisiaceae. It has been placed, too, in the Aquifoliaceae, and has been included in the Sapindales and Celastrales. We come now to the 8 genera which Harms considered to be sufficiently similar to form a single sub-family, Cornoideae. One might expect a measure of agreement here, but one is disappointed. Helwingia (3-5) is placed by Hutchinson (1959) in the Araliaceae. Others have a family Helwingiaceae for it. This was put by Lindley [ 30]

CHAOS IN TAXONOMY

31

(1853) in his Garryales and, if Lindley was correct, Helwingia `should' have aucubin. Does it ? Corokia (3-6) is of very doubtful position. It has been put in Saxifragaceae and in Escalloniaceae, and thus in the Rosales (see also below). Chemical evidence may favour its retention in the Cornaceae. We come now to Cornus (4-45) itself. Even this genus has been placed elsewhere—in the Hederaceae! And what do we mean by Cornus? Melchior has 45 species; Airy Shaw (in W. 1966) has 4! Hutchinson (1959) has Cornus, Afrocrania, Chamaepericlymenum, Cynoxylon, Dendrobenthamia and Thelycrania to embrace what some call Cornus (s.l.). Who is right? Torricellia (3)—which should be Toricellia ?—has been made a family of its own, Torrkelliaceae or Toricelliaceae. Melanophylla (3) and Kaliphora (1) have not, I think, been pushed around. Aucuba (3-4) has been made the type of a family, Aucubaceae. It has also been placed in Loranthaceae (and Caprifoliaceae ?). It has been cross-grafted with Garrya—and both have aucubin! Griselinia (6) may be related to Melanophylla. Philipson (1967) has suggested that it might be removed from the Cornaceae—but where should it go ? What a lot of problems this small group of plants proposes! We shall see that what we know of the comparative chemistry of the Cornaceae' by no means solves these problems. (b) Saxifragaceae We shall deal further with this family when we meet it in our list of familie sand again when considering the Rosales as an order (pp. 1645 and table 7o). Here we point out only that what Schulze-Menz (in Syll. xII, 1964) treats as a single family of about 8o/two has been split into at least 25 families and distributed among several orders! And the family itself has been variously placed. (c) Musaceae Here, to illustrate diversity of opinion, I list only a small selection of those who have recognized this family. Pulle (1952): 6/15o. Presumably Musa, Strelitzia, Heliconia, Ravenala, Phenakospermum and Orchidantha (Latvia). Potztal (in Syll. xii, 1964): 6/22o. Musa (6o), Ensete (to), Strelitzia (4), Heliconia (ca. 15o), Ravenala (1) and Phenakospermum. Orchidantha is placed in Lowiaceae.

32 CHEMOTAXONOMY OF FLOWERING PLANTS

Winkler (in EP1, 1930):5 genera. Musa (incl. Ensete), Strelitzia, Heliconia, Ravenala (incl. Phenakospermum) and Orchidantha (Lowia). Benson (1957): 5 genera, only 3 named. Dumortier (1829): 4 genera. Musa, Strelitzia, Heliconia and Ravenala. A. L. de Jussieu (1789), whose name is conserved: 3 genera. Musa,

Heliconia, Ravenala. Airy Shaw (in W. 1966): 2/42. Musa (35), Ensete (7). He has Strelitziaceae with Strelitzia, Ravenala and Phenakospermum; Heliconiaceae with Heliconia; and Lowiaceae with Orchidantha. Good (1956): 1 genus. Musa (ca. 8o). Hutchinson (1959): 1 genus. Musa (incl. Ensete, ca. 45). He has Strelitziaceae with Strelitzia, Ravenala, Phenakospermum and Heliconia; and Lowiaceae with Orchidantha. We find that although there are such differing opinions as to the

Musaceae all agree that the genera mentioned are related—segregate families being retained within the same order (Zingiberales). It should be noted also that most modern authors—Good, Hutchinson, Airy Shaw—and some not mentioned above such as Thorne, Cronquist and Takhtajan, have a greatly restricted Musaceae. At the order level we shall consider but two examples: the Rosales and the Tubiflorae.

(a) Rosales Here I shall compare and contrast the systems of Rendle (1938), Hutchinson (1959) and Bessey (1915). Rendle, who omits many small families, names 12, and describes the order as `A very natural group, the families in which are connected by transitional forms.' Hutchinson puts some of Rendle's families on his `herbaceous' side: the others in his `woody' series; with the following results. On the ` herbaceous' side: Crassulaceae (I), Cephalotaceae (2) and Saxifragaceae (3, in part) are in his Saxifragales (derived from Ranales). Podostemaceae (6) and Hydrostachyaceae (7) form his Podostemales (derived from Saxifragales). On the `woody' side: Connaraceae (1I) is in Dilleniales (derived from Magnoliales). Pittosporaceae (5) is in Pittosporales (from Dilleniales through Bixales). Rosaceae (Io) is the only family of Rendle's order to appear in H.'s Rosales (which he derives from Dilleniales)1 But H. adds Dichapetal-

CHAOS IN TAXONOMY

33

aceae and Calycanthaceae; the former not mentioned by R., the latter in his Rangles. Leguminosae (12) becomes Leguminales (derived from Rosales and consisting of Caesalpiniaceae, Mimosaceae and Papilionaceae). Saxifragaceae (3, part) and Cunoniaceae (4) are in Cunoniales (derived from Rosales) as Grossulariaceae, Philadelphaceae, Escalloniaceae, Pterostemonaceae, Baueraceae and Cunoniaceae! Hamamelidaceae (8) and Platanaceae (9) are in Hamamelidales (also from Rosales). We see that Rendle's `very natural group' is distributed over 8 orders! Bessey was sometimes a splitter as to families but a lumper at the order level. His Rosales included Crassulaceae, Cephalotaceae, Saxifragaceae (with Hydrangeaceae and Grossulariaceae as segregates), Cunoniaceae, Pittosporaceae, Hamamelidaceae, Platanaceae, Rosaceae (with Malaceae and Prunaceae as segregates), Connaraceae and Leguminosae (but as Mimosaceae, Cassiaceae and Fabaceae). This is close to Rendle's order so far but B. includes five families not mentioned by R.Brunelliaceae, Bruniaceae, Myrothamnaceae, Crossosomataceae and Eucommiaceae—as well as Casuarinaceae (R.'s Casuarinales), and Droseraceae (in R.'s Sarraceniales). These `extra' families are placed by Hutchinson in Dilleniales (Brunelliaceae and Crossosomataceae), Hamamelidales (Bruniaceae and Myrothamnaceae), Casuarinales (Casuarinaceae), Urticales (Eucommiaceae), and Sarraceniales (Droseraceae).

(b) Tubiflorae I have already written to some extent upon this subject (Gibbs, 1962), but in that paper I considered only the systems of Engler and Diels (in Syll. XII, 1936) and Hutchinson (1959), concluding that the chemical evidence available favoured the former rather than the latter. Let us first of all look at the later versions of these schemes—Melchior (in Syll.xü, 1964) and Hutchinson (1969). They are not greatly altered. Melchior divides his order into 6 sub-orders and 26 families (add -aceae). Here is his system with Hutchinson's placings. Convolvulineae 1. Polemoni. (Polemoni. in Polemoni.; Cobae. segregated and widely separated). 2. Fouquieri. (in Tamaric.) 3. Convolvul. (split. Cuscut. in Polemoni.; Convolvul. in Solan.) 2

GC()

34

CHEMOTAXONOMY OF FLOWERING PLANTS

Boraginineae 4. Hydrophyll. (in Polemoni.) 5. Boragin. (split: Boragin. in Boragin.; Ehreti. in Verben.) 6. Lenno. (in Eric.) Verbenineae 7. Verben. (split: Verben., Stilb., and Chloanth. in Verben.) 8. Callitrich. (in Onagr.) 9. Labiatae (as Lami. in Lami.) Solanineae io. Nolan. (in Solan.) ii. Solan. (split: Solan. in Solan.; Salpiglossid. in Person.) x2. Duckeodendr. (incl. in Ehreti.) 13. Buddlej. (as Buddlei. in Logani.) 14. Scrophulari. (split: Scrophulari. in Person.; Selagin. in Lami.) 15. Globulari. (in Lami.) 16. Bignoni. (in Bignoni.) 17. Pedali. (in Bignoni.) x8. Martyni. (in Bignoni.) 19. Henriquezi. (incl. in Rubi. in Rubi.) 2o. Acanth. (in Person.) 2I. Gesneri. (in Person.) 22. Columelli. (in Person.) 23. Orobanch. (in Person.) 24. Lentibulari. (in Person.) Myoporineae 25. Myopor. (in Lami.) Phrymineae 26. Phrym. (as Phrymat. in Verben.) We see that families thought by Melchior to be sufficiently near each other to be placed in a single order are distributed by Hutchinson over 12 widely spread orders! We summarize: Lignosae Magnoli. -+ Dilleni. a Bix. - Pittospor. -> Capparid. Tamaric. (2. Fouquieri.) Magnoli. -> The. Eric. (6. Lenno.) Magnoli. a Logan. (is. Buddlei.)-)- Rubi. (i7. Henriquezi. in Rubi.)

CHAOS IN TAXONOMY 35 Magnoli. a Logani. a Verben. (7. Verben. as V., Stilb., and Chloanth.; 5. Boragin. in pt and 12. Duckeodendr. as Ehreti.; z6. Phrymat.) Magnoli. a Logani. a Bignoni. (1. Polemoni. in pt as Cobae.; 16. Bignoni.; 19. Pedali.; and 2o. Martyni.) Herbaceae Ran. a Caryophyll. a Onagr. (8. Callitrich.) Ran. a Caryophyll. a Saxifrag. a Gerani. a Polemoni. (I. Polemoni. in pt; 3. Convolvul. in pt as Cuscut.; and 4. Hydrophyll.) a Boragin. (5. Boragin. in pt) a Lami. (9. Labiatae as Lami.; 15. Globulari.; 25. Myopor.; r4. Scrophulari. in pt. as Selagin.) Ran. a Caryophyll. a Saxifrag. a Solan. (to. Nolan.; ii. Solan. in pt; 3. Convolvul. in pt) a Person. (14. Scrophulari. in pt; ix. Solan. in pt as Salpiglossid.; 18. Acanth.; 21. Gesneri.; 22. Columelli. ; 23. Orobanch.; and 24. Lentibulari.). It is true that Hutchinson's system is an extreme one. What do 3 modern authors—Thorne (1968), Cronquist (1968) and Takhtajan (1969)—make of the families of Melchior's Tubiflorae ? (I shall use the numbers I have assigned to M.'s families.) Thorne has: Superorder Malviiflorae Solan. xi (including Io and 12); 1; 2; and 3. Superorder Rosiflorae Ros. 22 (in Saxifrag.) Superorder Gentianiflorae Gentian. 13 (in Logani.); 17 (in Rubi.) Bignoni. 14 (including 15); 16; 18; 19; 20; 21; 23; 24; and 25 Superorder Lamiiflorae Lami. 4; 5; 6; 7 including z6; 8; 9 as Lami. He spreads M.'s families over 5 orders in 4 superorders. Three of his orders have sizeable chunks of M.'s Tubiflorae. Cronquist has: Subclass IV. Dilleniidae Viol. 2 Subclass V. Rosidae Ros. 22 Subclass VI. Asteridae Polemoni. I; 3; 4; 6; ro; II Lami. 5; 7; 8; 9; 26 Scrophulari. (Person.) 13; 14; 15; 16; 18; 19 (incl. zo); 21; 23; 24; 25 2-2

36 CHEMOTAXONOMY OF FLOWERING PLANTS Rubi. 17 (in Rubi.) The little family Duckeodendraceae (12) is not mentioned. Again M.'s families are spread over several superorders (or subclasses) and orders. One order—Scrophulariales (Personales)—is almost exactly Thorne's Bignoniales, and accounts for nearly half of M.'s families. All but 2 of M.'s families are in the superorder (subclass) Asteridae, but this is not matched in Thorne's system. Takhtajan has: Superorder V. Dillenianae Tamaric. 2 Superorder XIV. Lamianae Gentian. 17 (in Rubi. ?) Polemoni. 1; 3 ; 4; 5; 6 Scrophulari Io; II; 13; 14; 15; 16; 18; 19; 20; 2I; 22; 23; 24; 25 Lauri. 7; 8; 9 (as Lauri.); 26 Duckeodendron (12 in M. ) is mentioned but not placed. Here we have almost all of M.'s families in one superorder, and 14 of them in the Scrophulariales—almost identical with Cronquist's order of that name, and with Thorne's Bignoniales—a real measure of agreement! We could extend this discussion almost indefinitely, but enough has been said to show how confused the situation is. Let me recall in closing this section that I once started, on a page measuring about 8 in. x 1 o in., to make a chart of the taxonomy of the Sapindales. Before long I stuck on a second sheet, then a third, fourth, and so on. When I had several square feet of chart I gave up!

RESTRICTION OF DISTRIBUTION OF CONSTITUENTS TO VARIOUS CATEGORIES OF PLANTS INTRODUCTION If one is to use comparative chemistry to distinguish between various categories of organisms one must establish facts of restriction—and this is by no means easy. A vast amount of tedious spadework must be done before one can say with any degree of confidence that a substance occurs only in such and such a group. Let us show how dangerous it is to jump to conclusions. As long ago as 1954 Peters and his co-workers reported on the occurrence of monofluoro-acetic acid and a fluoro-fatty-acid in the seeds of Dichapetalum toxicarium. Leaves of D. cymosum also have the former. We might well have supposed that these remarkable fluoro-acids were peculiar to the Dichapetalaceae (4-51200-250), or to Dichapetalum (15o-225), or even to a few species of Dichapetalum; and it is odd that no one, I think, has examined other members of the family. More recently it has been shown that monofluoro-acetic acid occurs also in the poisonous Gidgie (Acacia georginae), in a second legume (Gastrolobium grandiflorum), and in Palicourea marcgravii (Rubiaceae)! At one time biflavonyls were thought to be restricted to the gymnosperms. Then one of them was found in Casuarina, and this was hailed by some as `proof' that Casuarina is near to the gymnosperms, as has been suggested. Today we know that biflavonyls occur in Viburnum (Caprifoliaceae), Garcinia (Guttiferae), Xanthorrhoea (a monocot.!), and other flowering plants. Some `vital' substances probably occur in all Iiving organisms—the protein amino-acids and some fatty-acids, for example. Others such as the photosynthetic pigments may be in most plants. Let us deal with a few examples of restricted distribution, remembering the cautionary-tale examples above. 1. Plants, but not animals The photosynthetic pigments—chlorophylls and carotenoids—occur in all (?) true plants, except where lost secondarily, as in some saprophytic and parasitic flowering plants. They are normally absent from the fungi, and from animals. There are some substances, probably, that are normal to animals, but not to plants, but I have no knowledge of them. 1371

38 CHEMOTAXONOMY OF FLOWERING PLANTS

2. Higher plants, but not lower ones Pectins are very common, possibly universal in the higher plants. I believe they are absent from seaweeds, being replaced there by alginic acid. I don't have chapter and verse for this statement, however. Phenol glucosylation has been studied by a number of workers including Pridham (1964), who points out: `It would appear from the results in Table i [listing 23 angiosperms, 5 gymnosperms, 3 ferns, i i mosses, 1 liverwort, to algae, and 2 fungi] that a marked ability to glucosylate phenols is characteristic of the majority of higher plants, but that this reaction is absent or occurs at a very slow rate in Bryophytes and Thallophytes.' Lignin may be restricted to vascular plants, though substances resembling lignin occur in mosses. 3. Angiosperms, but not gymnosperms, and vice versa Raphides, while not universal in the angiosperms, are widely spread in the group, being present in many monocotyledons and in several families of dicotyledons. I believe them to be completely absent from gymnosperms. The cyclitol sequoitol (sequoyitol) was said by Plouvier (196o) to be confined to the gymnosperms; to be very widely spread in that group; and to prove them to be monophyletic. It has been reported (1963), however, to be formed from meso-inositol in leaves of Trifolium incarnatum. But does it occur normally in any angiosperm ? Rubber is virtually restricted to the angiosperms (and in those very nearly to the dicotyledons), but it has been reported from a few gymnosperms. The chemistries of angiosperms and gymnosperms are so similar that one is convinced of a relationship, but the nature of this relationship is not clear. 4. Dicotyledons, but not monocotyledons, and vice versa I used to think that rubber in the angiosperms was confined to the dicotyledons, where it is certainly widely spread. Lindley, as long ago as 1830, said that ' Limnocharis yields milk in abundance'—but does that contain rubber ? More recently rubber has been obtained, I think, from the banana. Are lignans absent from monocotyledons ? I have records of them from at least 26 families of dicotyledons, from Magnoliaceae to Umbelliferae and Compositae, but not a single record from a monocotyledon.

RESTRICTION TO VARIOUS CATEGORIES OF PLANTS

39

Plouvier and Favre-Bonvin (1971) say that iridoids and seco-iridoids are restricted to the dicotyledons. I have no record of them from the monocotyledons, but I have obtained positive reactions using the Ehrlich Test for aucubin-type glycosides, with 4 species of Aponogeton. Does this genus, to confound Plouvier and Favre-Bonvin, have iridoids ? Some groups of alkaloids have never been found in monocotyledons, but these are of very restricted distribution in the dicotyledons. We are looking for substances characteristic of one group but not the other, and they are hard to find. 5. Restriction to orders It is hard to think of examples for this section. Macrozamin may be restricted to the Cycadales (gymnosperms). Betalains occur only (?) in the Centrospermae and in Cactaceae and Didiereaceae (which some would include in the Centrospermae). Some sesquiterpenes are confined to the Compositae, which some would consider to constitute an order with one family. But these substances are restricted in their distribution within the Compositae, they are not characteristic of the family (order) as a whole. Derivatives of ellagic acid are widely spread in the Myrtales (table 49) and some of them are known only from families belonging to that order. Our knowledge of their distribution is still so sketchy, however, that while we can say that the order is noteworthy for the occurrence of these compounds, we cannot say that any one of them is restricted to it. Are we on safer grounds with the Malvales ? In this order cyclopropenyl fatty-acids are known to occur in Tiliaceae, Malvaceae, Bombacaceae and Sterculiaceae, at least. I have no record of them from outside the order. 6. Restriction to families It should be increasingly easy, one would think, to find examples of restricted distribution as one considers progressively smaller groups, but we have very few cases of substances that are certainly, or even probably, restricted to individual families. The alkaloid protopine comes near to this. I believe it has been found in every member of the Papaveraceae that has been examined for it. It has been reported, however, to occur elsewhere, and one report, at least—occurrence in Nandina (Berberidaceae)—seems to be accepted. Several alkaloids occur in Stemona and have not been found elsewhere, but have they been looked for in the other genera—Croomia and Stichoneuron—which some, at least, would include in the Ste-

monaceae ?

40 CHEMOTAXONOMY OF FLOWERING PLANTS

The Flacourtiaceae is noteworthy for the presence in the seed-fats of many of its members of fatty-acids of the chaulmoogric series. These are not known from any other source. But some members (tribes ?) of the family may not have them—so we may be dealing here with restriction to parts of a family. 7. Restriction to sub-families We may introduce a new type of restriction here: restriction within a given family of a substance which does, however, occur also elsewhere. Is the occurrence in the Rosaceae of ellagic acid an example of this ? It is reported from the Rosoideae, but not from the other sub-families of that family, I believe. It does, of course, occur widely in the flowering plants. Plumbagin is reported to occur in Droseraceae, Ebenaceae, Apocynaceae and perhaps Rubiaceae, as well as in the Plumbaginaceae. In the last it seems to be confined to one of the two sub-families (p. 1545). The amino-acid canavanine is restricted, so far as I know, to the Leguminosae, and in that family to the Faboideae. It is not universal in that sub-family, as the following figures, now probably out of date, indicate (bracketed figures show numbers of genera in the tribes; fractions show genera/species tested). I. Mimosoideae. Ingeae (io): absent from 2/2; Acacieae (I) : absent from 1/2; Eumimoseae (4); absent from 2/2; Adenanthereae (io): absent from 2/4; Piptadenieae (6): absent from I/I ; Parkieae (2): absent from 1/2. II. Caesalpinioideae. Dimorphandreae (4): absent from 1/I; Cynometreae (I I): absent from I/1; Amherstieae (25): absent from 6/6; Bauhinieae (3): absent from 2/5; Cassieae (13): absent from 2/5; Kramerieae (1) : no record; Eucaesalpinieae (17) : absent from 4/4; Sclerobieae: no record; Tounateae (Swartzieae) (7): absent from 1/1. III. Faboideae. Sophoreae (33): absent from 5/7, no record of presence; Podalyrieae (27): absent from 5/5; no record of presence; Genisteae (43): absent from 10/25, present in I/1; Trifolieae (6): present in s12o; Loteae (8): present in 5/12; Galegeae (65): absent from 10/23, present in 19/41; Hedysareae (48): absent from 13/26, present in 9/20; Dalbergieae (27): absent from 2/3, present in I/I; Vicieae (6): absent from 5-6/8-16, present in 1/5 ; Phaseoleae (47) : absent from 14/38, present in 5/II. 8. Restriction to tribes An examination of the figures for distribution of canavanine given above will reveal that it has not been found in the tribes Sophoreae

RESTRICTION TO VARIOUS CATEGORIES OF PLANTS 4I

and Podalyrieae of the sub-family Faboideae. In the Genisteae only one member (Bossiaea foliosa) of more than two dozen examined is reported to have canavanine. One wonders if this is correct. One might wonder, assuming it to be correct, if Bossiaea is properly placed. I have not tried to check opinion on these points. There are, I am sure, some good examples of restriction of substances to tribes, but I have not noted them for this section. 9. Restriction at the genus level I pointed out in a previous paper (1945, p. 79) that the family Flacourtiaceae provides an interesting example of this. In the tribe Oncobeae the genera Caloncoba, Lindackeria, Mayna and Carpotroche have optically active fatty-acids of the chaulmoogric series. The genus Oncoba, until split by Gilg, included Caloncoba. Now Oncoba spinosa, at least, lacks these optically active fatty-acids, differing clearly in this respect from Caloncoba echinata, glauca and welwitschii, all of which have been shown to have them. Gilg did not know of this chemical difference when he split Oncoba. Aristolochia (350-500) of the family Aristolochiaceae, has several substances—aristidinic acid (in I sp.) ; aristinic acid (1) ; aristolic acid (I) ; aristolochic acids I (13), II (I), III (I), IIIa (1), IV (I), and IVa (I); aristolochine (8); and aristolone (1)—all but one of which have not been reported, I think, from other members of the family. Bragantia wallichii is said to have aristolochic acid I. But our sampling of the family is woefully small. An amino-acid, y-hydroxy-arginine, which had previously been found in sea animals was detected by Bell and Tirimanna (1963) in all of the 17 species of Vicia which they examined. Does this differentiate Vicia from Lathyrus? If Itea (15-2o) be included in the Saxifragaceae then the occurrence in at least 3 of its species of allitol may be a generic character. It is said to be absent from Escallonia and Brexia, at least; and I have no records of it from elsewhere in the family. to. Restriction at the species level Examples here would seem to be legion, but in the great majority of cases they are probably due to our ignorance, the substances in question occurring in other species of the genera concerned. Some of the more interesting alkaloid-yielding genera seem to have different alkaloids in each species, but closer examination often shows this to be misleading. An interesting cautionary example is the distribution of the naphtha-

42 CHEMOTAXONOMY OF FLOWERING PLANTS

quinone lomatiol in the genus Lomatia (io) of the Proteaceae. According to Thomson (1957) lomatiol was known from around the seeds of Australian species, but not from around those of S. American species. My own tests, however, strongly suggest that it may occur in leaves and bark of both Australian and S. American species (p. 1569 and table 58). It then becomes a generic character. II. Restriction at the infra-specific level Detailed investigations have sometimes revealed chemical differences between plants that are considered to be members of the same species. It has been suggested that when there are no obvious morphological differences to distinguish these plants as subspecies, varieties, or forms, that they be called `chemovars'. We shall discuss a single case. In 1922 Penfold found the essential oil from the leaves of Backhousia myrtifolia growing in New South Wales to have 75-8o% elemicin. In 1953 Penfold, McKern and Spies analysed oils from four individuals from Fraser Island, Queensland. One had about 72% elemicin, two had 77-78% isoelemicin, and the fourth had about 81% isoeugenol methyl ether! A third paper, by Hellyer, McKern and Willis, appeared in 1955. The authors had analysed oils from 18 individuals from S.E. Queensland. Six proved to be of the elemicin (` type') form and had little or no isoelemicin; four had isoelemicin as the chief constituent; one had methyl eugenol in preponderance; and the remaining seven had much isoeugenol methyl ether, with small amounts of isoelemicin.

RESTRICTION OF DISTRIBUTION OF CONSTITUENTS WITHIN THE INDIVIDUAL PLANT We have considered above the restriction of distribution of substances in different taxonomic categories. Here we shall deal briefly with restriction within the individual plant. When studying small organisms it is possible to grind, chop, mince or pound one or more of them and to deal with the resultant material as a whole. This is, of course, the simplest possibility, though it may result in a great dilution of a substance which occurs only in a small part of each organism. When dealing with the higher plants one is obliged at times to use only a leaf (or even a part of a leaf), or a shoot, or an inflorescence, or fruit, or seed. If the choice is one's own one uses the portion most likely to have the substance one is looking for. Young shoots, for example, more often yield HCN than do older parts of the plant. We shall discuss briefly a few examples of restricted distribution. We have referred above to lomatiol which occurs around the seeds of some species of Lomatia. Knowing this one might look for it around the seeds of other species of the genus and of other genera of the Proteaceae. It seems likely, however, that lomatiol or a nearly related naphthaquinone occurs also in the leaves and bark of Lomatia: it may not be as restricted as we had supposed. Some acetylenic compounds are restricted to certain organs. Pittosporum buchanani, according to Bohlmann et al. (Polyacetylenv. 15o, 1968), has at least 4 acetylene compounds in its roots, but none in its above-ground parts. Latex provides us with some good examples. Latex ducts may occur only in certain organs, and the latex contains substances not found elsewhere in the plant. The rubber of Hevea is an example. In guayule (Parthenium argentatum), however, rubber occurs in cells in virtually all parts of the plant. Extraction methods on a commercial scale are necessarily quite different for the two plants. Metcalfe says that in Decaisnea fargesii laticifers occur only in the fruits! In Papaver somniferum latex tubes with alkaloids occur in all parts of the plant except the seeds, and these alone are free of alkaloids. Plagiopteron, says Metcalfe, is the only genus of the Flacourtiaceae with laticifers, and these contain a rubber-like substance. Airy Shaw (in W. 1966) has a separate family—Plagiopteraceae—for it. It has been placed by others in Olacaceae, and in Tiliaceae. Obviously it would repay detailed chemical investigation. Cyanogenic glycosides may be restricted in their distribution. I have already mentioned their occurrence in young shoots. Seedlings of Borago officinalis yield HCN: mature plants do not. Guerin found HCN 1 43 1

Ø

CHEMOTAXONOMY OF FLOWERING PLANTS

in cotyledons of the seedlings of some legumes, but not in shoots of older plants. I have confirmed some of his findings. Smith and White obtained HCN from the inflorescence of Grevillea banksii, but not from the leafy shoot. With G. sericea I got the reverse result; but with Lomatia tinctoria I got HCN from the inflorescence, not from the shoot! There are some obvious possibilities for experimental work here, and some interesting observations are accumulating. One thinks of grafting work on members of the Solanaceae to determine the sites of formation of alkaloids. A note by Kaul and Staba (1965) reports the formation of visnagin by suspension cultures of Ammi visnaga. They say that digitalis glycosides have been produced by tissue cultures of Digitalis, nicotine by Nicotiana cultures, tropane alkaloids by Datura, reserpine by Alstonia constricta, and vinca alkaloids by Catharanthus roseus. Suhadolnik (1964 or 1965) grew `callous tissue' from germinated seeds of Hippeastrum vittatum. He did not find hippeastrine and lycorine in the tissue culture, though they were present in the seeds. Some of the discordant results in the literature may be due to faulty timing. We have noted that HCN may in some cases be found in juvenile, but not in mature plants. A very interesting type of timing has been studied in aroids by Smith and Meeuse (1966). They point out that the often unpleasant odour of the spadix may arise rather suddenly and persist for but a few hours. It is known that this coincides with, or follows, a period of great metabolic activity, accompanied by an increase in temperature. Percival (1965) says that within the opening spathe of Arum maculatum, for example, there may be an increase in temperature of as much as 13 °C! This rise in temperature may be in part responsible for the volatilization of the odoriferous constituents. In the spadix of Sauromatum there was a zo-fold increase in the free amino-acids from the day before to the day after anthesis. It is well known that the fatty-acids of the storage fats of mature seeds may be different from those of the unripe seeds. A whole set of highly correlated chemical changes occurs in the ripening of such fruits as bananas. Free acids decrease, esters are formed, pectic substances change, starch yields to sugars, the pigments change, tannins disappear or more probably are adsorbed. Some plants have quite different youth and adult foliage, a phenomenon surprisingly prominent in New Zealand. The eucalypts of Australia provide examples. Hillis (1966) has found significant differences in composition between the youth and adult leaves of Eucalyptus accedens, dives and ligustrina. We have not referred specifically to restriction to individual cells of the plant, but this is well known to the anatomist and cytologist. Myrosin-cells, raphide-sacs, `tanniniferous cells', come to mind; and of course only certain cells are lignified.

EXCRETION BY PLANTS Plants in general, unlike animals, have no apparent excretory systems. Carus (1872) points out that this was recognized by Aristotle, who thought that ascidians are plant-like because they lack an excretory system: 'Auch die Ascidien, sagt Aristoteles, kann man mit Recht, pflanzlich nennen, da sie, wie die Pflanzen, keine Ausscheidung (Excremente) von sich geben.' Yet plants, like animals, have metabolic wastes—and these are sometimes of chemotaxonomic interest. Volatile wastes—carbon dioxide from respiration, oxygen from photosynthesis—escape to the atmosphere, largely through the stomata. Many aromatic plants are continually losing volatile organic substances to the atmosphere, and with modern techniques the mixtures can be analysed. Are these, too, to be classified as `waste' materials, or do they have their roles in Nature ? There is no doubt that strongly aromatic plants are often distasteful to animals, the odoriferous constituents in and/or on the plants discouraging attacks by predators. Escape to the atmosphere might then be considered to be accidental, or unavoidable, but there is some evidence that washing of these aromatics into the soil may be important, too (see below). The amounts lost to the atmosphere are astonishingly large. One is familiar with the fact that plants may scent the countryside. We mention this and quote from Rasmussen and Went (1964) when discussing the monoterpenes (p. 772). Muller, Muller and Haines (1964) noted apparent inhibition of growth of seedlings by aromatic shrubs in California. This was observed in the field—see the cover of Science for 31 January 1964—and was supported by laboratory experiments: `Root growth of Cucumis and Avena seedlings is inhibited by volatile materials produced by leaves of Salvia leucophylla, S. apiana and Artemisia californica. The toxic substance may be deposited when dew condenses on affected seedlings in the field.' More recently Muller (197o) has discussed the role of allelopathythe control of growth, health, behaviour and population biology of organisms by chemicals produced by other organisms—on the evolution of vegetation. Even more recently Whittaker and Feeny (1971) have published a review paper—Allelochemics: chemical interactions between species—which shows how fascinatingly complex the subject is. They say: `Phenolic acids released by the grass Aristida oligantha (and other old-field species) inhibit the nitrogen-fixing bacteria and blue-green algae of the soil. Low concentrations of available nitrogen in the soil, 1 45 1

46 CHEMOTAXONOMY OF FLOWERING PLANTS

to which the Aristida itself is tolerant, slow the invasion and replacement of this grass community by other species.' Other substances which may be involved in similar situations include fiavonoids, terpenoids, steroids, alkaloids and organic cyanides. Routes of release include fog-drip, rainwash, volatilization from leaves, excretion from roots, and decay. Substances which may be toxic to the plant producing them may be rendered non-toxic by combination with sugars, or by deposition in dead tissues—as in bark. Predators of some kinds are discouraged by the presence of hypericin, but one species of beetle, say Whittaker and Feeny: `has further turned the evolutionary scales on the plants by using the repellant as a cue to locate its food. The beetles explore leaf-surfaces with their tarsal chemoreceptors until hypericin, present on the leaf-surface, triggers feeding.' The mustard-oils, so characteristic of the Cruciferae, protect the plants against many predators, but some insects feed only on crucifers. An interesting development is that insects may retain toxins which they have obtained from plants, and be themselves toxic to others! We are wandering a little from the subject of excretion by plants, but we cannot forbear to mention phytoalexins which include: `phenolic compounds that are present in the skin of the protected organ as a first defense, and are produced in quantity in the deeper tissues surrounding a fungal penetration through the skin, as a second defense'. Examples of these compounds are orchinol of orchid tubers, and chlorogenic and caffeic acids produced by potatoes. The phenomenon of guttation may be mentioned briefly here. Quite large quantities of liquid are exuded under suitable conditions by many plants. Ivanoff (1963) says that this was first recorded by Munting just 300 years ago. The exudates include water as the chief constituent, inorganic salts, glutamine, etc. Modern techniques might well reveal interesting differences in composition of exudates from different species. Guttation takes place from stomata or from hydathodes. Excretion in other ways may be discussed here. The meal or farina on the leaves and stems of many species of Primula consists largely of flavone and related substances. It is secreted by glandular hairs. Blasdale (1947) has an interesting paper on this subject. He says: Of the 500 or more species and subspecies of the genus Primula, at least one half bear minute glandular hairs which secrete a white or yellow powder, commonly designated as farina. With the exception of the closely related genus Dionysia I know of no other genus of

EXCRETION BY PLANTS

47

flowering plants whose species yield similar secretions. Certain species of at least two fern genera, Pitty[r]ogramma and Notholaena, bear similar hairs producing similar products. Farina formation is of taxonomic importance in defining the genus [Primula] and the various sections into which it has been divided. Blasdale says further that the farina is powdery rather than `wax-like', as sometimes described. He did, however, find some wax-like material (which he did not identify) mixed with the flavonoid constituents. More than a score of the species he studied had flavone as a major constituent of the farina; P. denticulata had dihydroxy-flavone; P. verticillata had 5-hydroxy-flavone (reported by others from P. imperialis var. gracilis); while P. florindae had yet another flavonoid. Some few species bear quite different substances. Thus the skin-irritating material of the notorious P. obconica is said to be primin '. Blasdale saw no advantage to the species of Primula bearing farina : In the absence of proof that farina is of use to the plant it becomes necessary to add these secretions to the long list of organic compounds synthesized by plants which are believed to be by-products incidental to the complex chemical reactions which take place in plant cells. They may be detrimental to the life and growth of plant cells just as the oleoresins secreted by coniferous plants are detrimental. If so, the secreting hairs may be considered part of a mechanism designed to eliminate such secretions from living tissues. In view of the complex relations between organisms that we have discussed above we may wonder if farina is, indeed, simply a waste product. Wax is transported from the epidermal cells to the leaf surface through micro-channels, says Hall (1967). We shall see that the waxes of different species differ in their major constituents. Excretion from roots into the soil is hard to study. It is by no means certain that analyses under controlled conditions, as in water-culture, give an accurate picture of what happens under field conditions. Sir E. John Russell in his The world of the soil (1957) writes: Some plants can, however, excrete substances that protect them against attacks by parasitic fungi. Varieties of flax resistant to Wilt disease owe their immunity to the hydrocyanic acid which their roots secrete and which poisons the Fusarium and Helminthosporium fungi that cause the disease, but stimulates the Trichoderma that also represses these fungi. Susceptible varieties of flax on the other hand

48

CHEMOTAXONOMY OF FLOWERING PLANTS

do not excrete hydrocyanic acid and their roots become surrounded by a mixed population of fungi including those causing the disease. Sir John notes that things do not always work out to the advantage of the higher plant. The potato, for example, secretes substances which cause spores of wart disease to germinate, and cysts of eelworms to develop. These predators then attack the potato.

ODORIFEROUS CONSTITUENTS OF PLANTS The human nose, though far less sensitive than the noses of some animals, can still detect odoriferous materials in great dilution. Thus we find many plants have been named for their odours. Those smelling of onions or garlic (Allium), Dysoxylum alliaceum; of carraway (Carvum), Lippia carviodora, whose leaf-oil has 6o% d-carvone; of Citrus, Darwinia citriodora, Eucalyptus citriodora, Lippia citriodora. Sometimes the odoriferous constituents are known to us. Foetid odours, for example, are noted in the names Coprosma foetidissima, of which Briggs says: `The disgustingly foetid odour of this plant has been shown by Sutherland (1946) to be due to traces of methyl mercaptan' and Paederia foetida, which also has a methyl mercaptan. There are cases in which odour may reinforce impressions of relationship. Some families have quite characteristic smells. Many leguminous fruits, for example, have very similar odours. We find in LeMaout, Decaisne and Hooker (1873): `Saurureae [our Saururaceae] possess a somewhat acrid aroma, which confirms their affinity with Piperaceae.' I have myself noted that Hedyosmum (Chloranthaceae, also supposedly near Piperaceae) has a peppery smell. Goris and Mascre (1909) observed that crushed roots of species of Primula have characteristic odours—anise, coriander, methyl salicylate (compare Betula spp. in this connection, but it is the bark that one sniffs). I do not think that this has been followed up chemotaxonomically. Saghir and others have investigated the odoriferous constituents of Allium species. In 1966 they concluded: Although in the classification of the alliums the use of morphological data is basic, information on odor may provide a valuable additional taxonomic character that will help in clarifying the systematics of this intricate genus. Inasmuch, however, as a classification based entirely on chemical characters would not only place clearly unrelated species such as A. cepa and A. validum together but separate otherwise very similar taxa like A. campanulatum and A. membranaceum, it is clear that chemical evidence must be used only in conjunction with all other pertinent evidence in determining relationships. Some of the sulphur-compounds responsible for the odours were identified: Allyl disulfide definitely has a garlic odor. Propyl disulfide ... has the odor we associate with the common onion, and methyl disulfide the odor of cooked cabbage. 49 1

50 CHEMOTAXONOMY OF FLOWERING PLANTS

I have often wondered what is responsible for the characteristic smell, rather like celery, of the greengrocer's shop. Apparently phthalides contribute to the odour of celery, and so, perhaps, to that of the shop. The odours of flowers may be transitory or very persistent. We note elsewhere some recent work on aroids and on orchids. A thesis by Hills (1968) may be quoted briefly here. He worked on the orchidaceous genus Catasetum and concluded that each species sampled that is known to have a species-specific pollinator also has a specific fragrance, and that: `a study of the fragrances produced by the flowers of Catasetum is important to the taxonomy and ecology of the genus and of other genera of orchids that depend on specific attraction of euglossine bees as pollinators'. About forty compounds are produced by Catasetum flowers and twelve of these were identified: a-pinene, ß pinene, myrcene, i,8-cineole, linalool, methyl benzoate, benzyl acetate, d-carvone, methyl salicylate, z-phenyl ethyl acetate, z-phenyl ethanol and methyl cinnamate. Harper, Bate-Smith and Land have produced a book on odours— Odour description and odour classification (1968). I have not seen it.

CHEMICAL EVOLUTION IN PLANTS We may well believe that all evolution involves chemical changes and that the `characters' that we use in taxonomy are the outward and visible signs of inward chemical characters: changing or evolving as the chemistry changes. Luten (1964), in an interesting article on taxonomy in biology and chemistry, wrote: `Certainly, as plants have become diversified, both in kind and in internal function, they have used older building blocks to assemble new chemical structures which can only be regarded as more complex.' We should have put that somewhat differently, for evolution, as we well know, is not always towards the more complex. There can be reduction (not in the chemical sense!) and simplification: loss as well as gain (see below). There can be divergent, parallel and convergent evolution; and these are often difficult to distinguish. Let us examine one example. The betalains, which seem to act as if alternative to anthocyanins in plants, appear to be confined to the Centrospermae (or Caryophyllales), the Didiereaceae, and the Cactaceae—all of which are grouped together by some taxonomists. But the Caryophyllaceae, often regarded as the type family of the order, lacks betalains: it has anthocyanins instead. How can we explain this ? Reznik (1957), who has discussed the problem, saw three possibilities: (a) The Caryophyllaceae belongs to the order, but diverged somewhat from the line within which, at a later date, arose the ability to make betalains. (b) The family belongs to the order, and did at one time produce betalains, but subsequently lost the ability to do so. (c) The family does not belong to the order, having diverged from the ancestral stock before it produced the Centrospermae. We can wonder similarly about the anthocyanins. Did the Centrospermae, unlike other plants, have both betalains and anthocyanins ? And did the Caryophyllaceae lose the one and keep the other, while the remaining families did the reverse ? I am indebted to my old friend Mirov for reminding me of an interesting aspect of our work. I had asked him if his work on terpenoid substances in relation to the taxonomy of Pinus received support from the work of Erdtman on heartwood constituents of the same genus. He replied that there was not complete agreement but that that was to be expected since the `evolution' of heartwood constituents might proceed quite independently of that of the terpenoid substances. Of course one then 1 sI ]

52 CHEMOTAXONOMY OF FLOWERING PLANTS

asks which of these two groups of compounds reflects better the taxonomy of the genus. Harborne has given much attention to the evolution of fiavonoids in plants. The following notes are derived from his chapter in Comparative phytochemistry (ed. Swain, 1966). In his first paragraph he agrees with me that much remains to be done: `The drawback is that total ascertainment has only been achieved so far in one or two small plant groups so that the present contribution of flavonoids to taxonomy is slight. Many more surveys at the generic and family level are required before chemical information of this type can be incorporated with confidence into plant classification.' He says that the anthocyanins isolated from mosses and ferns are biogenetically primitive in that they lack the 3-hydroxyl group of the common anthocyanins and are derivatives of apigeninidin or of luteolinidin; and that the occurrence of the biogenetically simple chakones, dihydrochalcones and flavanones in ferns suggest that they are primitive characters in plants. Harborne makes one statement which I might query. He says (italics mine): The flavonoids of the monocotyledons are more interesting from another point of view, that of parallel evolution. If, as is generally accepted, the mono and dicotyledons arose separately from a common seed-bearing stock, then many chemical modifications in flavonoid synthesis must have arisen independently in the two groups of plants.' I query the `general acceptance', not the parallel evolution. After some detailed considerations Harborne draws up a table based mainly on present ideas of evolutionary status... and on biogenetic considerations'. According to this 3-deoxyanthocyanidins; flavonols; leucoanthocyanidins; chalcones, flavanones, and dihydrochalcones; and C-substitution are primitive characters'. `Advanced characters' resulting from gain mutations include complex 0-glycosylation; 6- or 8hydroxylation; 0-methylation; and oxidation of chalcones to aurones. `Advanced characters' resulting from loss mutations are replacement of flavonols by flavones; elimination of leucoanthocyanidins; and elimination of trihydroxylation. A great deal that might be included in this section is to be found in the symposium volume Phytochemical phylogeny, edited by Harborne (197o). I was flattered some years ago to be asked to contribute a paper to the volume of the Journal of the Linnean Society of London (1958) marking the centenary of the presentation to the Society of the Darwin— Wallace papers on evolution. It seemed appropriate to make it a paper on chemical evolution in plants. I found only a limited amount of material on this subject, and had to say `Organic evolution, and with it

CHEMICAL EVOLUTION IN PLANTS

53

biochemical evolution, are now generally accepted as facts, but we know all too little of the biochemical facts.' This might be repeated today, but we have made some progress, and many more investigators are energetically digging out more facts so that speculation may be based on a wider foundation. I should like to be alive to read what will be written when the Darwin—Wallace bicentenary is celebrated!

TESTS USED BY THE AUTHOR INTRODUCTION When confronted with the vast assemblage of higher plants one is intimidated by the problems involved in the investigation for taxonomic purposes of their comparative chemistry. Very early in the present work it became evident that one must choose in one's own research between an intensive study of a few plants and an extensive investigation of all that could be made available. Obviously the chemist, rather than the botanist, is better qualified to pursue the intensive course, and it is clear in the pages of this book that I have collected much information from the work of chemists. I felt myself, as a botanist, better fitted to pursue the more extensive course, and I have endeavoured during a quarter of a century to stick to this and not to be tempted into more intensive studies of small groups. In following this course I have had to adopt (and adapt) simple tests which could be performed rapidly upon large numbers of specimens. The notes which follow describe the routine tests that I (and my students and assistants) have employed. As the work has developed it has become obvious that some of the tests overlap and that some are doubly or trebly useful, indicating two or three groups of chemical constituents. This will be made clear, I hope, in the notes below. i. Raphides This is an observation rather than a test, and it is usually made upon the control sections when carrying out the syringin test. In some cases, however, where the material does not lend itself to the use of the syringin test, we still look for raphides. These needle-like crystals, and their usefulness in taxonomy, are discussed at some length in our discussion of the history of chemotaxonomy. See also Gibbs (1963, PP. 51-5). It is obvious that we are indebted to the plant anatomists for much information on the distribution of raphides in plants unavailable to us. Care must be taken, however, in accepting statements in early papers as to the occurrence of raphides. Many observers called unoriented acicular crystals raphides'. Today we restrict the term to bundles of needleshaped crystals arranged parallel to each other and enclosed in special `raphide-sacs'. See individual groups for further discussion. [ 54 1

TESTS USED BY THE AUTHOR

55

The Cigarette and Hot-Water Tests Some years ago we came across a paper by Dykyj-Sajfertova (1958) describing two very simple tests that seemed to be of taxonomic interest. These we have designated the Cigarette Test (Cig. Test) and the HotWater Test (H.-W. Test). We may describe them and their use as follows: 2.

Cig. Test. A lighted cigarette is pressed gently against the back of a mature leaf for about 3 seconds. A strongly positive reaction (I of Dykyj-Sajfertova) is the development almost at once of a brown to black ring around the heated area. A slower and weaker reaction is designated by II, a very slow (3o minutes) or doubtful reaction by III, and a negative reaction by IV. In some young leaves (noted by us) and in leaves with acid cellsaps (as noted by Dykyj-Sajfertova), a yellow colour may develop around the heated spot. This was called by her the oxalis-reaction (O.R.) because first observed in species of Oxalis. H.-W. Test. In this test a mature leaf is dipped part-way into water at about 85 °C and held steadily there for about 5 seconds (we increase the time a little for thick and/or leathery leaves). A strongly positive reaction (I) is the development almost at once of a brown or black band at the juncture of dipped and undipped areas. The dipped part may subsequently darken patchily or entirely. A slower, weaker reaction is dubbed II, a doubtful one III, and a negative one IV. Yellowing is again an oxalis-reaction. Dykyj-Sajfertova tested in all about moo species. She found that some families, such as the Compositae, seemed always to be I for both tests. Others, such as the Campanulaceae, seemed always to be IV. Yet others seemed to be mixed, some members giving positive and some negative reactions, or very weak ones. We have adopted the Cig. Test and the H.-W. Test as standard and have applied them to many plants. In general our results parallel those of Dykyj-Sajfertova, though we have found some exceptions. We have tested many plants not included in her list. What are we testing for in these simple experiments ? It seems that the heat-treatment in each case disorganizes the tissues and brings enzymes into contact with their substrates. More specifically we suppose that polyphenolases react with suitable substrates to produce darkcoloured substances. It seems likely that different materials may be involved in different families. We have noted, for example, that members of the Boraginaceae give a brown (often bright brown) colour, while those of the Aquifoliaceae and Araliaceae give a strikingly black reaction.

56 CHEMOTAXONOMY OF FLOWERING PLANTS

In a few cases there may be consistent differences between subfamilies or between closely related families. Thus we have found the Gentianaceae (s.s.) to be negative; the Menyanthaceae to be positive. Occasionally, we have noted differences between species of the same genus. In the Australian Anthocercis, for example, I obtained a strikingly positive H.-W. reaction with A. littorea from near Perth, and a negative reaction with A. viscosa from Albany. A brief note on the oxalis-reaction is in order here. This may be consistent in some groups. My student Elizabeth Shaw (see Shaw and Gibbs, 1961, and her thesis, unpublished) found that mature leaves of members of the Hamamelidaceae all (?) give a marked oxalis-reaction. This may be one of the `characters' of the family. Incidentally we have not checked the acidity of the cell-saps of the Hamamelidaceae, and we have obtained no information on this point from the literature. 3. The HC1/Methanol (' Isenberg—Buchanan') Test In 1945 Isenberg and Buchanan reported: `Tests by the authors with 277 species in 56 families have shown that methanol containing a small amount of hydrochloric acid gives a purple coloration when mixed cold with the shavings of some species and not with others. The method gives promise of making it possible to identify the woods of certain species that cannot be separated on the basis of structure alone.' Isenberg and Buchanan did not know the substances responsible for the purple coloration (a positive reaction) and we still are uncertain. Adler (1951) concluded that they are catechol tannins'. The very high correlation between a positive result from this test and a positive leucoanthocyanin reaction (below) makes it likely that leucoanthocyanins are involved. We have standardized the HCIIMethanol Test as follows: A small amount of sapwood from a fresh twig (about pencil-size if possible but even smaller if no older material is available) is sliced with a pencil sharpener, or cut into small chips, and just covered in a stoppered test-tube with a few ml. of the HCI/Methanol mixture (I000 ml. methanol: 25 ml. conc. HC1). The tube is allowed to stand, with occasional shaking, for some hours. A deep magenta colour in the wood (4 in Isenberg and Buchanan's scale) is a strongly positive result; 3, 2, and I are progressively weaker reactions; and o a negative result in which the wood shows no magenta colour whatever. We have noted that the supernatant liquid may also be coloured, and not always the same as the wood. In practice we decant and record the colours of liquid and of wood, using Ridgway's Color Standards and Nomenclature (1912). Roughly speaking positive results in the wood are

TESTS USED BY THE AUTHOR

57

often those of plate xxvi in Ridgway, 4 being `dull magenta purple', 3 `magenta', 2 `liseran purple', i `rose-purple' or `pale rose-purple'. Negative results are usually those of plate xxx of Ridgway, paler tints being `marguerite yellow', `ivory yellow', or `cartridge buff'. We have used this test on most of the woody species available to us. It soon became clear that some families are consistently positive to the test; others as consistently negative. As described in earlier papers (Gibbs, 1954 1958, 1962) we have established a series which is HC1/ Methanol positive and another that is negative. The former includes the Dilleniaceae, Actinidiaceae, Bixaceae, Theaceae, Clethraceae, Ericaceae, Pyrolaceae, Epacridaceae, Empetraceae, and Cyrillaceae; the latter includes the Aquifoliaceae, Salvadoraceae, Oleaceae, Loganiaceae, woody Boraginaceae, and the families of the Tubiflorae. Taxonomists will recognize these as comprising two series in each of which the families are considered to be related one to another. When one carries out many such tests one runs sooner or later into exceptional cases which often prove to be of great interest. We may deal briefly here with one example. In Jamaica I tested Euphorbia nudiflora and, to my surprise, got a bright orangey rather than a magenta reaction (` deep chrome' and `cadmium yellow' of Ridgway's plate HI in 2 tests). E. heterophylla and its var. graminifolia were then found to give similar results (` capucine orange', plate IH, for both). It transpired that these plants are very nearly related and that the familiar poinsettia (E. pulcherrima) belongs to the same group of species. It, too, gave a bright orangey colour (`bittersweet orange' of plate ix). Further research showed: (a) That many other members of the Euphorbiaceae, including some species of Euphorbia less closely related to E. nudiflora, give typical negative reactions with no orange colour, while some members of the family —which is certainly a heterogeneous group—give positive (magenta) reactions. (b) That the orange colour is very stable, remaining virtually unchanged for weeks, even with frequent changes of the HC1/Methanol mixture. (c) That I had obtained a similar orange colour (`mikado orange', plate ni) years ago with Oxyanthus tubiflorus (Rubiaceae) from the Royal Botanic Garden, Edinburgh. A second species (0. natalensis) from the same garden, was then tested and gave `cadmium orange' (plate Iii). No other rubiaceous plant—the family is mixed in its reaction to the HCl/ Methanol test—has given anything but a normal positive or negative result. A colleague of mine decided to study the chemistry of this `off-beat' reaction. He and a graduate student were defeated: they failed even to extract the orange material (Gibbs, Edward, and Ferland, 1967).

58 CHEMOTAXONOMY OF FLOWERING PLANTS

And there, for the moment, the matter rests. It looks very much as if the same stable substance occurs in a closely knit group of Euphorbia species and in at least two species of Oxyanthus! I might well have considered the few species of Euphorbia to be unique if I had not tested Oxyanthus. We must be cautious indeed before we can describe a chemical character as `peculiar' to a single group. 4. HCN (Test A) More than a dozen cyanogenic glycosides are known to occur in plants (p. 632). When any one of these is hydrolysed it yields free HCN which may be detected very easily. We have, from the beginnings of our researches in chemotaxonomy, used a simple test which we have designated HCN (Test A), bearing in mind that we might at any time use other tests (B, C, D, etc.). This simple test is carried out as follows: A small amount of plant material (1-2 gm., or even much less) is pounded in a mortar with a few drops of water, a tiny pinch of emulsin, and a few drops of chloroform. The resulting `mush' is transferred at once to a glass-stoppered test-tube. The stopper has a piece of picric acid paper (filter paper dipped into a saturated aqueous solution of picric acid and then dried) fastened to its underside with melted paraffin wax. Just before insertion the paper is dipped into io% sodium carbonate solution and gently blotted. If much HCN is released by the action of the emulsin on the glycoside in the plant material the sodium picrate turns from pale yellow to rust-red within minutes. If very little HCN is released it may require one or more days before there is obvious change. We usually leave the tubes for a week and I have some evidence that an even longer period is desirable in some cases. In our earliest experiments we used split rubber bungs to hold the sodium picrate paper. We sometimes got positive results when we didn't expect them and experiments showed that the bungs might release (absorbed ?) HCN even though they had been washed after use with truly cyanogenic material. We strongly suspect that some `records' in the literature have been obtained by similar faulty techniques. We have never obtained positive results (using our present technique) from any member of the Lauraceae, for example, though others claim to have done so. One must be cautious, however, for I have argued against the occurrence of HCN in the Cucurbitaceae (Gibbs, 1965). At that time I had tested 24 species belonging to 17 genera of the family without getting anything but negative results. Then, in November of 1967, material of Xerosicyos became available. X. perreiri gave a moderately strong positive

TESTS USED BY THE AUTHOR

59

reaction and X. manguyi a negative one! But I have not found HCN in other cucurbits which have been claimed to be cyanogenic by other workers. Plants that form cyanogenic glycosides may have them in all parts, but more often than not the glycosides are restricted to certain organs, making it worthwhile to examine various parts if they are available (Gibbs, 1965). Usually we test young leafy shoots, but sometimes inflorescences have been found to be cyanogenic when leafy shoots are not. Thus we found that shoots of Lomatia tinctoria gave negative tests while the inflorescences yielded a positive result. We found the shoot of L. silaifolia to be negative, while several authors found the inflorescence to be positive for HCN. Smith and White got similar results with Grevillea banksii; we got the reverse with G. sericea! An interesting state of affairs is found in Lotus and its segregates. Guerin (1929) reports that seeds of Dorycnium species are negative to the test, while seedlings are positive and we agree. We have found older leafy shoots of two species to be negative. In Tetragonolobus bijiora and probably in at least two other species there is a similar state of affairs. While we use fresh material wherever possible there are times when small fragments of herbarium specimens are all that are available to us. A negative test from such material may be inconclusive, but a positive test is accepted as proof that the original plant had cyanogenic glycosides. See cyanogenic glycosides (p. 629) for further discussion. Are there substances other than HCN which might emanate from plant material and might turn sodium picrate paper rust-red ? We know of none. We have, however, obtained somewhat atypical results in some cases, the paper becoming rather a dull brown. Some species of Viburnum (Caprifoli.), Velleia spathulata (Goodeni.), Mutisia coccinea (Comp.), and Casearia nitida (Flacourti.) have given such results. No explanation of this is offered, but it is a pretty problem for someone. The reader will find many references in this book to HCN as a chemotaxonomic character. See particularly Passifloraceae, Malesherbiaceae, Turneraceae, Flacourtiaceae, Leguminosae. In tables 1 to 3 I record my own results and, for comparison, those of others. A few comments upon the tables are in order: (a) It would appear at first sight that I have made more tests for HCN than have all others put together! This is misleading for at least two reasons. In the first place, though I have tried hard to collect all the information available, I must have missed many records. In the second place some of the papers consulted record only the plants giving positive results. (b) I do seem to have a better coverage of families than have others.

6o CHEMOTAXONOMY OF FLOWERING PLANTS TABLE I.

Summary of Occurrence of HCN in Dicotyledons Others

Gibbs HCN (Test A) Families (genera/species) Acanth. (250/2600) Acer. (2-3/152) Achari. (3/3) Achato. (z/8) Actinidi. (3/320) Adox. (I/1) Aextoxic. (I/I) Aizo.(131/250o) Akani. (1/1) Alangi. (x-2/18) Alseuosmi. (3/11) Amaranth. (60/900) Amborell. (I/I) Anacardi. (79/6o0) Ancistro. (I/18) Annon. (120/2100) Apocyn. (200/2000) Aquifoli. (3/450) Arali. (7o/7oo) Aristol. (7/60o) Asclepi. (250/200o) Austrobail. (x/2) Balanop. (x/9) Balanoph. (18/Ioo) Balsamin. (3/475) Basell. (4/20) Batid. (1 /2) Begoni. (5/82o) Berber. (14/650) Betul. (6/10o) Bignon. (I2o/800) Bix. (1/1) Bombac. (28/zoo) Borag. (100/2000) Bretschn. (x/1) Brunelli. (x/35) Brum. (12/75) Brunoni. (I/I) Buddlej. (19/160) Burser. (x8/600) Bux. (6/6o) Byblid. (x/2) Cact. (200/2000)

,

, +

?

,

-

, +

?

I/I

3/3 —

— —

30/59 3/I0

3/3 —

— —

1 /5

— —

— —

2/2 1/I

— —

— —

I/1 I/1

— — —

— 1/I —

24/27 — 1/I

— — —

— — —

4/5 I/I —

— — —

— — —

8/17 — 8/9

2/5 — 4/6

x/1 — —

3/3 — 3/3

I/I 1/I x/11 — — 1/I — — — — — — — 2/2 — — — — I/I —

— — — 1/I — — — — — — — — — — — — — — x/I —

I/1 9/Io 1/3 4/6 1/4 12/13 — — 1/IS 2/5 2-3/2-3 1 /2 1/9 6/13 3/5 19/20 I/I 2/2 21 /39 —

4/7 6/6 — 2/2 — 2/2 — — — x/1 — — — 2/2 — 3/3 — 2/2 3/3 —

— — — 1/2 — — — — — — — — — — — I/I — — 1/1 —

— 6/7 2/2 5/6 2/2 6/8 — — — — — — 3/5 5/25 2/2 — — 8/8 —













— — — — — 1/5

— — — — — —

x/I 4/8 — 4/8

— — I/2 — — —

— — — — — —

— 1/3 I/1 3/5 — —

Some dull.

1/I 1 9/34

2 Herbarium material.

TESTS USED BY THE AUTHOR 61 TABLE I. (cont.) Gibbs HCN (Test A) Families (genera/species)

Callitrich. (1/35) — Calycanth. (2/9) 2/4 — Calycer. (6/6o) Campan. (70/20oo) 1/4 Canal'. (6/20) I/1 Cappar. (46/800) 3/4 Caprifol. (1 5/400) 2/51 Cardiopter. (1/3) Caric. (4/45) — Caryocar. (2/25) — Caryoph. (8o/z000) — Casuar. (1/45) — — Celastr. (6o/85o) Cephalot. (x/x) — Ceratoph. (1/4-6) — Cercidi. (I/I-2) — Chenopod. (100/1500)— Chloranth. (5/70) Chrysobal. (x2/300) — Cist. (8/175) — — Clethr. (I/30) — Cneor. (2/3) Cochlosp. (2/20) Columelli. (I/4) — Combret. (18/500) Comp. (920/19000) 2/43 Connar. (24/350) — Convolv. (51/1600) Coriari. (I/12) — Corn. (1 2/95) — — Corynocarp. (I/5) Crassul. (3o/1400) 7/II — Crossosom. (2/3) 2/2 Crucif. (350/300o) Crypteroni. (1/4) I/I Cucurb. (Ioo/850) Cunoni. (25/350) I/I Cynomori. (I/1) — Cyril'. (3/ 14) Daphniph. (1/35) — — Datisc. (3/4) — Davidi. (I/I) ' Some dull. 3 I/3 dull.

?

+

Others

-

?

+

— — — — — 3/3 2/2

1/1-2 — — 214 1/x — 15/23 I/I — I/I 2/2 2/2 7/22 2/4

— — — — — 2/4

— — — — — — — — —

2/2 I/I 2/22 — 1 3/1 9 — I/I — 6/9 I/I I/I — I/I — I/1 — 7/14 5/8-9

— — — — — — — — 1/2

— — — —

I/I 3/9 2/3 1/I

— I/2

— —

1/I 42/49

2/2 z6/53

I/I 4/4

x/I 49/69

I/14 — — — — — 2/2

3/5 1/2 5/12 I/1 1 8 /35 I/2 6/8

3/7 —

I/I —

-

-

— 3/4-5 — 1 3/17

I/I — — 2/2

3/5 I/1 3/18 — 2/4 — 75/ 2202

— —

18/28 3/4

5/5 —



3/3 4/5

— — — —

1/I 1/I 2/2 1/I

— — —

— — —

— — —

4 Dull?

'Absent' — — —

4/6 — 8/15 ix /8o

4/4 I/I 4/6

I/I

9/14 1 /4

I/I I/I

2 Herbarium material. s Honeyman (mostly seed).

62 CHEMOTAXONOMY OF FLOWERING PLANTS TABLE I

(cont.) Others

Gibbs HCN (Test A) Families (genera/species)

,

, +

?



, +

?

Davidsoni. (I/I)





I/I

I/I



Degeneri. (I/I)

I/I











Desfont. (1/5)





I/I









Dialypet. (I/I)



I/I I







Diapensi. (6/18)



2/2







Dichapet. (4/250) Didiere. (4/ 11)







I/24







3/3









4/ 13

2/2



1/3

Didymel. (I/2) Dilleni. (10/350) Dioncoph. (3/3) Dipentod. (I/I) —

8/I0





I/I

Diptero. (22/400)





I/I

I/I





Droser. (4/93)

2 /34



1 /4

3/7





Dysphani. (I/5-6)







1/3





Eben. (4/450)



1/1

3/6

1/3



I/I

Elaeagn. (3/65)





3/6



1/5

Elaeoc. (I0/400)

I/I



5/6





1/I

Empetr. (3/9)





3/3



1/I

i/1

Epacrid. (30/400)

3/3



8/18



I/I

9/19

Eric. (82/2500)

2/2

2/2

20/35

2/2



15/1124

Erythrox. (4/2oo)





1/2

1/I



1/I

Eucommi. (I/I)





1/I





I/I

Eucryphi. (I/5)



I/1

I/2





-

Euphorb. (290/7500)

6/6

I/I

21/35

28/5/

2/2

12/16

Eupomati. (I/2)



I/I

I/I







Euptele. (I/2)





1/I







Fag. (7-8/600)





5/6





3/3

Flacour. (86/1300)

I/I

2/2

9/112

4/4

4/6

Fouquieri. (I/54)





I/I

9/15 —





Dipsac. (10/270)

Duckeoden. (I/I)

Elatin (2/39-45)

Frankeni. (4/5o)





1/32







Garry. (I/15)





I/6







Geissolom. (I/I)













Genti. (70/1100)

3/3

I/I

7/12



I/I

2/2

Gerani. (11/780)





3/7



3/3

Gesner. (140/1800)





8/8

— —



1/I

Globulari. (2/27)





1/3







Gomorteg. (I/I)











2 Some from herbarium material. I Herbarium material. 3 Queried by Hegnauer. + 2/2 dull. s About 8o from seeds of Rhododendron spp.

TESTS USED BY THE AUTHOR 63

TABLE I

(cont.)

Gibbs HCN (Test A) Families (genera/species) Gooden. (14/320) Grubbi. (1/5) Guttif. (49/90o) Gyrostem. (5/l6) Haloragid. (8/160) Hamamel. (z6/110) Henriquez. (2/13) Hernandi. (4/65) Himantand. (1/2-3) Hippocast. (z/15) Hippocrat. (18/300) Hippurid. (I/I) Hoplestig. (1/2) Hydnor. (z/,8) Hydroph. (20/270) Hydrostach. (1/30) Icacin. (45/400) Illici. (1/42) Jugland. (8/75) Juliani. (z/5) Krameri. (I /20) Lab. (200/3200) Lactorid. (I/1) Lardizab. (8/3o) Laur. (31/2250) Lecyth. (24/450) Lee. (I/7o) Legum.(600/13000) Leitneri. (I/I) Lenno. (3/4) Lentib. (5/30o) Limnanth. (2/8) Lin. (23/500) Lissocarp. (1/2) Loss. (15/250) Logani. (18/50o) Loranth. (40/1400) Lythr. (22/500)2 Magnoli. (x0/215) Malesherb. (1/25) Malpighi. (65/800) Maly. (85/1500) Marcgrav. (5/120)

,

Others /

+ 2/2



6/x2

1/1



3/5

— 1/1 3/7 —

— — — —

4/12 — 1 /2 12/20

3/3 1/1 3/3 —

— 1/i — —

2/4 I/1 2/3 9/18





I/I







— — —

— — —

1/4 1/I I/1

— — —

— — —

— — —



2/2

3/4





1/1

1/2 — I/I

— —

1/2 3/4

— —

— —

4/1 3

3/3

I/I

39/86

3/4



1 3/17

— — — 1/I 2/4 —

3/3 11 /13 2/2 1/I 33/64 I/I



— — — 2/26 —

4/4 3/3 x/2 51/121

1/I 3/6 — 61/119

— — 1/3

— —

2/4 2/2 2/3

— 1/15

— — —

I/I I/4

— — — — 1/2 I/I1 — — —

— I/1 — — —

5/I11 3/3 I/I 5/7 4/8

— I/I — 1/I 1/z

— I/I 1/1 — —

3/4 2/2 1/2 I/I —

2/3 —

2/4 1 7/23 i/I

— 4/6 —

— — —

— 6/9 —

Some from herbarium material.

— — 7/7 —

2 Hegnauer.

64 CHEMOTAXONOMY OF FLOWERING PLANTS

TABLE I

(cont.)

Gibbs HCN (Test A) Families (genera/species)

,

+

Martyni. (5/16) — Medusagyn. (1/I) Medusandr. (z/6) Melastom. (200/4000) 2/2 Meli. (50/1400) — Melianth. (3/38) Menisper. (67/425) Menyanth. (5/4o) — Misodendr. (1/II) Mollugin. (i4/95) Monimi. (34/450) — Mor. (61/1550) I/I Moring. (I/Io) — Myop. (5/180) 2/2 Myric. (3/56) — Myrist. (I2/15o) — Myrothamn. (1/2) Myrsin. (33/1000) — — Myrt. (100/3000) Nepenth. (I/79) — Neurad. (3/10) Nolan. (2/83) — — Nyctag. (3o/3o0) Nymphae. (8/65-8o) — Nyss. (2/9) — Ochn. (28/400) — Olac. (27/230) I/I Ole. (27/600) — Olini. (1/8) — Onagr. (2o/65o) — Opili. (7/60) Oroban. (13/150) — Oxalid. (8/95o) — Paeoni. (I/33) — Pand. (I/I) Papav. (47/700) 3/3 Passifl. (12/600) 4/20 Pedali. (i6/55) — Penae. (s121) Pentaphrag. (1/25) Pentaphylac. (1/3) — Peridisc. (2/2) Phrym. (I/I-4) —

?

Others

I +

?





I-2/I-2 —





— I/I —

1/3 5/5 — 4/4 —

— — —



8/8 2/2 3/4 5/6 2/2



— 2/3 — i/1

— — — — I/I — —

1/I 6/6 8/Io I/I 2/I0 2/3 I/I

i/i — 7/17 i/i I/I — —

— — — I/I — —

2/2 3/5 — 2/2 1/2 —

— 1/I —

6/9 12/14 1/2

— 3/6 —

— 1/I —

14/24



— — — — — — 2/4 — —

1/3 4/8 6/6 1/, 3/4 I/I Io/15 — 7/9

— I/I — — — 2/3 — — 3/4

— — — — ,/, I/1 — I/2 —

I/I 2/2 2/3 — I/I I/I 6/12 — 4/6

— — —

3/3 3/6 1/2

— 3/4 —

— — —

I/I I/I I/I

— — —

11/13

I/Ia 2/2

4/4 5/28 —

— — —

13/42k

I/I —













i/1





I/I

Mostly Honeyman (seeds).

I/I

2 Poor material.

TESTS USED BY THE AUTHOR 65 TABLE I (cont.) Gibbs HCN (Test A) Families (genera/species) Phytol. (17/I2o) Picroden. (I/3) Piper. (II/1400) Pittosp. (9/240) Plantagin. (3/265) Platan. (1/6-7) Plumbag. (10/350) Podostem. (43/2oo) Polemon. (18/320) Polygal. (13/800) Polygon. (40/800) Portul. (19/500) Primul. (28/800) Prote. (62/1400) Punic. (I/2) Pyrol. (16/75) Quiin. (3/37) RaØesi. (9/55) Ranunc. (5o/2000) Resed. (6/7o) Rhamn. (58/900) Rhizoph. (,6/I2o) Rhoiptele. (I/1) Roridul. (1/2) Ros. (100/3000) Rubi. (475/6500) Rut. (15o/1600) Sabi. (4/9o) Salic. (2/350) Salvad. (3/I2) Santal. (35/400) Sapin. (140/1500) Sapot. (50/800) Sarcolaen. (8/33) Sarcosp. (I/8) Sargentod. (I/I) Sarraceni. (3/16) Saurur. (4/5) Saxifr. (8o/120o) Schisandr. (2/47) Scroph. (200/3000) Scyphosteg. (1/I) Scytopet. (5/3 2) I Dull( 3

Others

+ — — — — — 1/2 —

I/1 — — — — — I/I

517 I/I 3/II 7/9 1/8 — 5/10

— — I/4 — — 1/4 —

— — — — — — —

1/2 I/2 6/10 1/3 — I/I

— — — — — 8/Io — 2/21 —

I/I — — 1/1 — 2/2 — I/21 —

6/9 2/4 9/14. 5/7 1,/16 12/27 1/I I/I 1/,2

— — 3/3

— — —

7/17 2/2 —

5/9 — —

15/23 — 2/3 — — I/I — I/, 2/2

— — 5/5 — 1/,

I/I

-

— 1I/18 — — —

— — — — —

I/I 2/4 5/5 1/I 2/3 11 /34 — — -

16/28 3/5 9/I1

5/31 — I/I

— — —

7/12 1 /4 5/10

4/4 1/I — — ,/11 I/I — — —

22/32 25/29 12/16 I/1 2/3 — 4/4 4/5 4/4

33/144 8/10 4/12 — I/I — — ,I/,5 4/7

2/4 ,/, — — — — — — I/I

20/47 9/12 18/25 — — — 6/7 8/x6 I/I

— — 1/1 — —

I/2 2/2 21/3o 2/4 25/43

— — 5/x6 — 2/5

— — 3/3 — 2/4

— — 21 /78 1 /I 9/9

1 Herbarium material. GCO

66

CHEMOTAXONOMY OF FLOWERING PLANTS

TABLE

i (cont.)

Gibbs HCN (Test A)

Others

Families (genera/species) Simaroub. (24/100) Solan. (85/2300) Sonnerati. (2/7) Sphaerosep. (2/14) Sphenocle. (1/I-2) Stachyur. (I/5-6) Stackhous. (3/22) Staphyle. (7/50) Stercul. (70/1000) Strasburg. (I/1) Stylidi. (6/140) Styrac. (11/150) Symploc. (1/350) Tamaric. (4/100) Tetracent. (1/I) The. (35/600) Theligon. (I/3) Theophr. (4/110) Thymel. (48/650) Tili. (47-48/400) Tovari. (1/2) Trap. (1/3-II) Tremand. (3/3o) Trigoni. (4/35) Trimeni. (2/7) Trochod. (1II) Tropaeol. (z/8o) Turner. (8/x 20) Ulm. (15/15o) 'Umbel'. (3oo/3000) Urtic. (42/700) Valeri. (13/360) Verb. (Ioo/260o) Viol. (16/850) Vit. (12/700) Vochysi. (6/2oo) Winter. (6/95) Zygoph. (30/250)

— —



2/3 13/18

— 6/7

— i/I

— 8/17

— — — -— — — — — — — — —

— — — —

— — I/2 I/1 1/2 IO/II — r/2 I/I 1/i 2/3 1/1 7/101

— — — — — 5/8 — — — — — — —

— — — — — — — — — — — — —

— — — —

— — — 1/1 — 2/2 —

— — — — — —

3/3-4 5/5 7/7 — 1/I 1/3 —

— 1 /1 6/8 — — — —

— — — — — — —

— 3/6 3/5 I/2 — I/I —

— — 3/ro — — — — — — — — I/1 —

— — — 1/1 — — — — 1/I — — — —

I/I I/1 1/21 5/9 • 13/18 9/12 3/3 21/46 5/181 5/9 — I/I 2/2

— — z/5 2/3 2/3 3/3 — 6/8 — 2/4 — 1/3 —

— — — 1 /2 — — — — I/2 — — — —

— 1/3 — 6/7 25/29 4/5 1/1 5/I2 3/12 4/6 — — 3/5

— — — — — —

I Some from herbarium material.

I/i

4/6 — 1/2 I/I — i/I — —

TESTS USED BY THE AUTHOR 67 TABLE 2.

Summary of Occurrence of HCN in Monocotyledons Gibbs HCN (Test A)

Families (genera/species) Agav. (18/560) Alism. (10/70) Amaryll. (65/860) Aponoget. (1/40) Arac.(Iio/,800) Bromel. (46/1700) Burmann. (22/130) Butom. (4/13) Cann. (I/3o-6o) Centrolep. (6/38) Commel. (40/575) Corsi. (2/9) Cyanastr. (1/5) Cyclanth. (II/18o) Cyper. (70 /3700) Discore. (1o/65o) Eriocaul. (13/I175) Flagellar. (2/6) Geosirid. (1/1) Gram. (700/8000) Haemod. (zz/12o) Hydrochar. (15/x0o) Hypox. (5/ 140) Irid. (70/15oo) Junc. (8/3oo) Juncag. (4/18) Lemn. (4/25) Lili. (220/3500) Lowi. (I/4-5) Marant. (32/350) Mayac. (x/9-lo) Mus. (6/220) Naiad. (1/35) Orch. (650/20000) Palm. (236/3400) Pandan. (3/88o) Philydr. (4/5) Ponteder. (7/30) Potamoget. (5/1o5) Rapate. (16/8o) Restion. (28/400) Scheuchzer. (I/1) Spargani. (1/zo) * Mostly seeds.

Others

+ — — 3/3 — 7/8 —

— — 1/1 — — —

9/9 2/3 7/8 1/2 16/18 9/II

1/1 — — — 17/5o —

— — — — — —

1/I 14/18 —

— —

— —

2/2 I/I

— I/I

— —

I/I —

I/1 — — — — — — —

— — — — — —

9/II — I/I 2/2 9/15 2/3 I/I —

2/2 — — I/I 3/5 I/1 — I/I

— — — — — — — —

I/I — — — 9/34' — —

3/3 — I/I — 1/I — 1/6 — 2/3 — I/1 — —

— — — — I/I — — — — ---

53/106 — — — — 1/2 2/3 — 3/5 — 2/2 — 2/2

4/5 — — — — — — — — — — — —

7/9 I/I 3/3 I/1 4/6 2/5 —



16/16 4/4 5/6 2/3 7/7 2/4 1/2 2/2 33/42 I/1 2/3 1/1 3/5

— —

37/45 II/13 2/2

— 12/12 I/I

— — —

3/5 — —

— —

3/3 1/2

2/2 —

— —

— I/I

— — —

2/2 — 1/2

— 1/1 —

— — —

I/I — —

— — — I/I' — — — 1/1 —



2

2/2 2 /3

I/1

13/13

— — — —

Identification doubtful—should be checked. 3-2

68 CHEMOTAXONOMY OF FLOWERING PLANTS TABLE 2 (cont.) Others

Gibbs HCN (Test A) Families (genera/species)

Stemon. (3/3o) Tacc. (2/3o) Thurni. (1/3) Triur. (7/80) Typh. (I/15) Vellozi. (3/19o) Xanthorr. (8/5o) Xyrid. (4/270) Zannichell. (5/2o) Zingib. (49/1500)

— — —



1i — — — — —

— — —

I/I

— — —

JR

1/1 I/I six 2/3 — — 4/4

— —

— — —



— — — 2/2

I/I

— — — — — —

2/3

— I/I

TABLE 3. Occurrence of HCN in angiosperms Gibbs HCN (Test A)

?



No information

232

2I 55 66

1 43 IIo8 1794

70 — —

93 399 818

8 52 63

62 694 1359

129 — —

1I-12 23 3o

0 2 2

31 218 284

10 -

19 Io8 200

0 4 5

13 71 III

21 — —

}

Dicotyledons Families 292 Genera 9,400 Species 166,000 Monocotyledons Families 53 Genera 2,500 Species 53,000

Others

58 135

+

?



No information

(c) Others would seem to have obtained a higher proportion of positive results than I have. There are several things that may qualify this. In the first place, as pointed out above, there is a tendency to record positive but not negative results. This is true also of records of substances other than HCN. In the second place the positive lists of others are swollen by records from legumes and grasses—plants of economic importance—which I have studied only to a very limited extent. In the third place—and Hegnauer is in agreement with me on this—a significant proportion of the positive records in the literature are of doubtful value because of faulty techniques. In the fourth place the records of others almost certainly include the results of repeated tests upon plants

TESTS USED BY THE AUTHOR 69

which may have HCN only at certain times, or under certain conditions, or in certain organs. This is probably only a minor factor. (d) Even though large numbers of tests for HCN have been made, the coverage is still woefully poor. What do we know, for example, of the Balanophoraceae (i8/ioo), of the Connaraceae (24/350), of the Dipterocarpaceae (22/400, where I have one negative record and others one positive one), or of the Hippocrateaceae (18/300, where I have one negative record) ? I have no information at all, from my own tests and those of others, for 65 families of dicotyledons and 8 of monocotyledons! (e) Despite these difficulties we do know enough about the distribution of HCN to use it tentatively when considering taxonomic problems. This will be clear, I hope, in the treatments of individual families and other groups. 5. Juglone Tests A—C (see also Quinones and Coumarins) Early in the present series of investigations we became interested in the relationships of the Juglandaceae. The occurrence of juglone, a naphthoquinone, in that family was supposed to be indicated by the following test, which we have designated Juglone Test A: A little (1-2 gm.) of finely chopped fresh plant material (often bark, but leaves, roots, etc. may also be tested) is steeped with occasional shaking in a few ml. of chloroform for several hours. The chloroform extract is filtered off, evaporated just to dryness over a water-bath, and the residue is taken up in a few ml. of ether. An equal volume of dilute ammonia (i vol. conc. ammonia: 9 vols. water) is added and the mixture shaken gently. An immediate purple colour in the ammonia layer is considered to be a positive reaction for juglone. Actually it may result, too, from the presence of some other naphthoquinones. No purple, or the appearance of other colours than purple in the ammonia layer, is considered to be a negative reaction for juglone. Lawsone, another naphthoquinone, gives an orange reaction. Juglone Test B We noted that while some plants give no colour in the ammonia layer in Juglone Test A, others give a strong yellow colour. This may be due to flavonoid substances. The colour is recorded. In testing an extract from the bark of Myrica cerifera, which had given a negative reaction in Juglone Test A, we noticed that a deep bluish green colour slowly developed from above down, as if something were slowly diffusing from the ether layer and reacting with the ammonia. The colour was relatively

70 CHEMOTAXONOMY OF FLOWERING PLANTS

stable, remaining unchanged for several days. Further tests showed that Myrica pensylvanica also gives a blue-green colour, and we wondered if all members of the Myricaceae would behave in the same way. When Comptonia was tested, however, we failed to get the colour. See, however, notes under Betulaceae, Fagaceae, Garryaceae. We now leave for some days all tubes in which a negative Juglone Test A has been obtained. Any colours given immediately or developing later are recorded as Juglone Test B (though we are not, of course, testing in this way for juglone). Juglone Test C While carrying out Juglone Test A we have noted in many cases fluorescence in the ammonia layer. This was first observed in testing bark of Brunfelsia undulata. Such fluorescence is probably due to aesculin or similar coumarins. Even where no fluorescence is visible in daylight a strong fluorescence may be seen in ultra-violet light. We now regularly look for such fluorescence, using long-wave ultra-violet light (L.w. and record it for convenience as Juglone Test C, though again we are not recording anything concerned with juglone. Quite by chance we compared the fluorescence under L.W. UVL with that under short-wave uaL. It is clear that the long-wave light is the one that should be used. Little fluorescence is visible with the shortwave lamp. 6. Leucoanthocyanin Test A (L.A. (Test A)) Some years ago Bate-Smith showed the author a simple test for leucoanthocyanins which is carried out by heating fresh plant material in 2N-hydrochloric acid. The development of a red colour which will pass into isoamyl alcohol is a positive reaction. In this test anthocyanidins are formed from the leucoanthocyanins (p. 554). Bate-Smith pointed out that the distribution of leucoanthocyanins is closely bound up with taxonomy, so we enthusiastically adopted his test and dubbed it for our purposes Leucoanthocyanin Test A (L.A. (Test A)). We carry it out as follows: Glass-stoppered test-tubes (ca. i6o x i6 mm.) are marked at 5 ml. and to ml. levels. About o-5 gm. of finely chopped fresh plant material (usually leaves) is placed in a tube, covered with 5 ml. of approx. 2N-hydrochloric acid, and the tube is placed in a boiling water-bath for 20 minutes. It is then cooled, 5 ml. of isoamyl alcohol are added, and then shaken. On separation of the layers the upper (isoamyl) layer may be red (usually near `carmine' of plate I in Ridgway)—a positive

TESTS USED BY THE AUTHOR

71

reaction—or some other colour (usually not far from `olive yellow' of plate xxx in Ridgway)—a negative reaction. With very few exceptions our results have paralleled those of BateSmith as recorded in the literature. He found that in some cases a darkening of the mixture occurred during heating which made this test of doubtful or no value for leucoanthocyanins. We find that such darkening is almost invariably associated with the presence of aucubin-type glycosides (q.v.) in the plant material, and this reaction is a very useful indicator for this group of compounds. See also Ehrlich Test A. We have noted above that the HCl/Methanol Test (which is carried out on shavings of sapwood) is very frequently correlated with a positive Leucoanthocyanin Test A (which is usually carried out on leaf material). This leads us to suppose that we may be testing for leucoanthocyanins in both cases. This is not necessarily invalidated by the few exceptions that we have found, since it is quite possible to have leucoanthocyanins in the leaves but not in the wood of a given plant, or vice versa. We shall see that there is reason also to believe that the magenta colour obtained in many cases when carrying our Ehrlich Test A (below) is due to the presence of leucoanthocyanins; as may be, too, the red colour developing in Syringin Test A (below). We seem to have here again a useful overlapping of our tests. 7. Syringin Test A The glycoside syringin (p. 119) seems to have been detected in relatively few plants. It is more or less general in the Oleaceae, and is said to occur also in Caprifoliaceae, Leguminosae (very rarely), and Loranthaceae. Tunmann (1931) says that when fresh sections of plant material are mounted in 5o% aqueous sulphuric acid the development of a blue colour indicates the presence of syringin. We have adopted this test, calling it Syringin Test A, and we carry it out as follows : Freshly hand-cut sections (usually of stem material) are mounted in a drop or two of aqueous sulphuric acid (1 pt. of conc. acid :1 pt. of water) and examined under the microscope. A positive reaction is recorded when a clear bluish colour develops in wood and/or bastfibres. A doubtfully positive reaction is noted if the lignified tissues become green. A negative reaction is one in which wood and fibres are yellow (or yellow and partially red, see below). A blue colour does not, of course, prove beyond doubt that syringin is present, since other substances might react similarly, but we know of none that do, and one of my students has detected syringin chromatographically in material giving a positive Syringin Test A (below).

72 CHEMOTAXONOMY OF FLOWERING PLANTS

Families in which we have obtained positive results include: Oleaceae many. Staphyleaceae Staphylea (3 spp.), Turpinia (I): the only members available to us so far. Crossosomataceae 2 spp. of Crossosoma, the only genus. Elizabeth Shaw, one of my students, has detected syringin chromatographically in Crossosoma californicum (unpublished). An interesting observation is that of the frequent development of a red colour in lignified tissues. This is closely correlated with positive reactions with the HC1/Methanol reagent (above), and is an example of the useful overlapping of some of our tests. In this case we can do a bit of `extrapolation', arguing as follows: Many plants are not sufficiently woody for us to carry out an HC1/Methanol Test, or only young material of a plant that does become woody is available to us. If sections of such material when mounted in sulphuric acid develop a red colour in the small amount of lignified tissue present we may argue with a fair degree of safety that they `would' give a positive HC1/Methanol reaction if they were sufficiently woody! Another interesting observation is that some plant material subjected to this test may darken or develop a pink to purple colour, particularly in the cortex. We have found that this is often (always ?) correlated with the presence of aucubin or related substances, and it points to the desirability of carrying out an Ehrlich Test (below). Finally, it should be noted that we always mount `control' sections in water for comparison with the treated material. We routinely check these control sections for presence or absence of raphides (above). 8. The Ehrlich Test It was, I believe, my former student and colleague, G. H. N. Towers, who introduced me to the Ehrlich reagent. I have modified but slightly the test as shown to me and carry it out as follows: A small amount (o•1 gm. or so) of freshly chopped plant material (usually leaves) is dropped into i-2 ml. of boiling 5o% aqueous ethanol and the mixture is heated in a water-bath until only a few drops of liquid remain. Three drops of liquid are transferred on a glass rod to a marked ro cm. filter-paper and the 3 spots are built up by further additions as evaporation proceeds. The filter-paper is then hung in a current of air until the spots are quite dry. Usually they are almost colourless: if not the colours are noted.

TESTS USED BY THE AUTHOR

73

To spot r (`Ehrlich') is added one drop of the complete Ehrlich reagent (p-dimethylaminobenzaldehyde r gm.; conc. HC1 5 ml. ; 95% ethanol Zoo ml.). To spot 2 (` control') is added one drop of acid alcohol (conc. HC1 5 ml.; 95% ethanol zoo ml.). To spot 3 (` NH3') no addition is made at this stage. Again the filterpaper is allowed to dry and any changes in colour are recorded under `Ehrlich, cold'. The paper is now placed in an oven at roo°C for r minute and any changes are recorded under `Ehrlich, hot'. Finally a drop of dilute ammonia is added to spot 3 and the colour is noted. The results obtained from this test may be summarized as follows: Spot r (`Ehrlich'), cold: a bright blue spot is considered to be positive and indicates the presence of aucubin or of similar substances. A grey or brown spot may also indicate aucubin-like substances. A magenta spot is given (almost ?) without exception by plant materials that give a positive (red) colour in L.A. (Test A) for leucoanthocyanins. Even if aucubin-like substances are present one can usually note this reaction, the spot being purplish with a bluey halo. Spot 2 (`control'), cold: usually little change is noted. Spot r (`Ehrlich'), hot: sometimes a blue spot already noted in the cold darkens somewhat. If a magenta colour has appeared in the cold it usually darkens. Spot z (`control'), hot: if a magenta colour develops in Spot r, then Spot 2 is usually orange-brown. Spot 3 (` NH3') may show little colour; may be bright yellow (flavonoids ?); rarely orange or orange-red (could this indicate aurones ?) see Nuytsia floribunda, Elaeocarpus; very rarelygreen: see Sobralia lindleyana. 9. The Aurone Test A (NH3) It has long been known that some yellow flowers if exposed to ammonia become orange-red to red. This generally (always ?) indicates the presence of aurone(s). I carry out this very simple test as follows: A few ml. of dilute aqueous ammonia are placed in a glass-stoppered test-tube. A loose plug of tissue paper or cotton-wool is wedged just above the liquid. A yellow flower (or part of a flower) is dropped on to the plug and the tube is stoppered. Any colour changes as the ammonia vapour penetrates the tissues of the flower are noted. A negative result is indicated when no trace of red or orange-red develops (though the yellow colour may deepen).

74 CHEMOTAXONOMY OF FLOWERING PLANTS A doubtful result is recorded when reddish-brown to brown coloration develops slowly. A positive result is recorded when an unmistakable orange-red or red colour develops quickly. A partial list of results from this test follows (numbers in brackets indicate numbers of species tested) : (a) Negative Nyctagin. Mirabilis (I); Aizo. Aridaria (i), Carpanthea (i), Rhombophyllum (2). Ranuncul. several; Berberid. Berberis (2). Dilleni. Hibbertia (3), Wormia (i); Guttif. Hypericum (4, but see under `doubtful'). Papaver. (several, but see under `doubtful'); Capparid. Cleome (i); Crucif. several. Crassul. Greenovia (I), Sedum (1); Pittospor. Billardiera (2) ; Ros. Fragaria, Kerria, Potentilla (some, see `doubtful' list); Legum. (many, but see `doubtful' list). Limnanth. Limnanthes (i); Oxalid. Oxalis (i); Tropaeol. Tropaeohimn (1); Zygophyll. Tribulus (I); Lin. Linum (1), Reinwardtia (I) ; Euphorbi. Euphorbia (1), Dalechampia (1). Rut. Ruta (i); Cneor. Cneorum (i); Malpighi. Galphimia (I), see also `doubtful' list. Balsamin. Impatiens (2). Tili. Tilia (i); Maly. Althaea (i), Gossypium (i), Pavonia (I); Sterculi. Hermannia (t), Waltheria (i). Viol. Viola (2); Turner. Turnera (I); Cist. Helianthemum (i), see also `doubtful' list; Loas. Cajophora (i), Mentzelia (2); Begoni. Begonia (I). Cucurbit. several. Lythr. Nesaea (i); Onagr. Kneiffia (I), Oenothera (4). Umbell. Foeniculum (i ), Pastinaca (1). Primul. Lysimachia (2), Primula (2). Ole. Forsythia (1). Gentian. Chlora (I), but the stamens turned red!, Lisianthus (i); Apocyn. Allamanda (i); Asclepiad. Asclepias (i); Rubi. Galium (r), Ixora (i). Boragin. Cerinthe (I), Lithospermum (1); Verben. Lantana (i) ; Labi. (several, but see ` doubtful' list) ; Solan. Atropa (i ), Hyoscyamus (1), Lycopersicum (i ), Nicotiana (2), Solanum (1), Streptosolen (i) ; Buddlej. Buddleja (i); Scrophulari. (several, but see also `positive' list); Bignoni. Tabebuia (i ), Tecoma (I); Acanth. several; Gesneri. Besleria (1), Gesneria (i) ; Orobanch. Orobanche (1).

TESTS USED BY THE AUTHOR

75

Dipsac. Cephalaria (1). Goodeni. Goodenia (I), Velleia (t); Comp. Chrysanthemum (i ), Helianthus, but see also `doubtful' list, Tagetes (i), etc., but see also `positive' list. Lili. Alstroemeria (1), Asphodeline (t), Erythronium (t), Tulipa (1), Uvularia (2); Amaryllid. Clivia (1) ; Irid. Crocus (t), Freesia (t). Bromeli. Vriesia (1). Orchid. Calanthe (t), Cypripedium (1), Oncidium (b) Doubtful Guttiferae Hypericum (1). Papaver. Meconopsis (1), Papaver (t). Ros. Agrimonia (t), Geum (z), Potentilla (6); Legum. Lotus (r). Malpighi. Stigmaphyllon ( t). Cist. Helianthemum (z or 3). Labi. Scutellaria (1); Scrophulari. Linaria (z). Comp. Helianthus (1). Lili. Aloe (t). (c) Positive Scrophulari. Antirrhinum (t), Calceolaria (2 ?), Linaria (z). Comp. Bidens (z), Coreopsis (6), Wedelia (t), etc. (table it). 1o. The Mäule Test In 1900 Mäule treated wood sections with dilute aqueous potassium permanganate, then (after washing) with dilute hydrochloric acid, and finally (after washing once more) with ammonia. He observed a rose-red colour (a positive reaction) in some cases, but not (a negative reaction) in others. Later workers found that in general lignified tissues of angiosperms are positive while those of gymnosperms are negative to this test. I have adopted the Mäule test and have used it on a very large number of specimens. It is carried out by me as follows: Hand sections (or sometimes sections cut about 45 mp. thick on a sliding microtome) of preferably fresh stem-material are soaked in freshly prepared 1% aqueous potassium permanganate for about zo minutes. They are rinsed and placed in dilute (ca. 20%) aqueous hydrochloric acid for r o minutes. They are rinsed, mounted in a drop or two of dilute aqueous ammonia, and observed under the microscope. A positive reaction is the almost immediate development in lignified tissues (wood, bast fibres, sub-epidermal fibres, even stomata in a few cases) of a bright rose-red colour. A negative reaction is the development of a brownish, rather indeterminate colour.

76 CHEMOTAXONOMY OF FLOWERING PLANTS

Although used by many workers, some of whom found that angiosperms in general, Podocarpus (a gymnosperm), and a few other nonangiospermous plants give positive reactions, the chemistry of the test was for long imperfectly known. It obviously involved a chlorination of the lignins (treatment with chlorine instead of permanganate followed by hydrochloric acid can be employed). In the early 194os, however, Hibbert and his students were obtaining vanillin (fig. 143) and syringaldehyde (fig. 143) from lignins subjected to alkaline oxidation. When Hibbert told the present writer that he obtained both syringaldehyde and vanillin from the wood of maple, but vanillin only from spruce, it occurred to him that here might be the explanation' of the Mäule reaction—that only lignins yielding syringaldehyde would give the rose-red colour. This proved to be the case (Creighton, Gibbs, and Hibbert, 1944; Towers and Gibbs, 1953; Gibbs, 1958). My 1958 paper lists results obtained up to that time. The following notes supplement that paper. Dicotyledons (292 families) Positive reaction, 223 families. Negative or doubtful reaction, 8 families (Podostem., Limnanth.?, Elatin.?, Trap., Hippurid., Lenno. (poor herbarium material), Callitrich., Adox.). It will be noted that these are mostly lightly lignified plants. I am sure that most if not all of them do produce some syringaldehyde. No information, 61 families, many of them tiny splinter families which I am prepared to bet will be found to yield syringaldehyde. Didymel. Rhoiptele. Dipentodont., Misodendr. Medusandr. Gyrostemon., Achatocarp., Mollugin., Dysphani. Himantandr., Eupomati., Trimen., Amborell., Gomorteg. Sargentodox., Ceratophyll. Lactorid. Hydnor. Eucryphi., Medusagyn., Dioncophyll., Strasburgeri., Ancistroclad. Cephalot., Davidsoni., Byblid., Roridul., Neurad., Krameri. Hydrostachy. Daphniphyll. Akani., Trigom. Bretschneider., Aextoxic. Pand., Cardiopterid. Sarcolaen., Scytopetal.

TESTS USED BY THE AUTHOR

77

Geissolomat. Peridisc., Scyphostegi., Malesherbi., Achari., Sphaerosepal. Crypteroni., Sonnerati., Olini., Theligon., Cynonurri. Alangi. Sarcospermat., Lissocarp., Hoplestigmat. Nolan., Duckeodendr., Henriquezi., Pedali. Sphenocle., Pentaphragmat., Brunoni. Monocotyledons (53 families) Positive reaction, 36 families. Negative or doubtful reaction, 6 families (Aponogeton., Hydrocharit.?, Lemn., Mayac.?, Pontederi., Potamogeton.). It will be noted that these are largely aquatic plants. Some, at least, of them do yield a little syringaldehyde. The Mäule Test is not sufficiently sensitive, it seems, in such cases. No information, r i families (Scheuchzeri., Zannichelli., Najad., Triurid., Geosirid., Burmanni., Corsi., Philydr., Thurni., Rapate., Lowi.). Again, I predict that some or all of these will be found to yield positive results. Most angiospermous woods yield a ratio of syringaldehyde: vanillin of about 3: i. Towers and I got some evidence that primitive angiosperms yield a lower ratio. We found a rough relationship between intensity of the Mäule reaction and the syringaldehyde: vanillin ratio. More work in this field might give interesting results. It is clear, in conclusion, that essentially all angiosperms are likely to give positive Mäule reactions. We had thought that some groups might differ significantly from others in this respect. Our tests have been sufficiently numerous, however, to make it extremely unlikely that such differences will be found. xi. Tannin Test A I cannot remember with certainty where and when I got news of this simple test, but it was almost certainly in a thesis by Miss Harney on species of Lotus. It involves the well-known reaction of tannins and/or tannin-like materials, with iron salts to give purple, blue, greenish, greyish, or brownish colours. I carry it out as follows: The plant material (usually a fresh, mature leaf) is washed thoroughly. A small filter-paper (Whatman No. i) which has been dipped into fresh 2.5% aqueous ferric ammonium citrate is blotted gently and folded around the leaf. The resulting `sandwich' is squeezed with rib-nosed pliers, the

78 CHEMOTAXONOMY OF FLOWERING PLANTS

paper is then opened and compared during the following few minutes with a control in which water rather than ferric ammonium citrate has been employed. In some cases a green patch (from chlorophyll) is seen, or there may be little or no colour—a negative result. In other cases a rapid development of a purplish-blue colour results. In yet other cases a grey to brown colour is seen. A rough scale is employed: + + +, a very strong reaction; + +, a strong reaction; +, a definite, but weak reaction; - ?, probably negative; -ve, certainly negative. In a few cases other colours may develop. It is by no means certain that all the blues to browns observed are due to tannins. It is very probable that these other colours are due to other substances. We record them when observed. We have found this test, which I have used widely since November 1964, to be a useful one chemotaxonomically. Some families consistently give strongly positive results: others are as consistently negative: while some are `mixed' in their reactions. It is, as with other characters used in taxonomy, important to use comparable material. The amount of tannin varies widely in leaves of different ages, or in healthy and diseased specimens. It is important, too, when comparing our results with those of others, as set out in our tables, to remember that our results are (with rare exceptions) from leaves only. The results of others may include tests on bark (often), roots, and other organs. Saponin Test A (and additional tests) It has, of course, long been known that saponins (and perhaps some other plant constituents) in aqueous solutions give stable foams when such solutions are shaken. The literature is full of references to 'saponins' detected by shaking a plant extract and observing a stable foam, and many of these are without doubt quite reliable. I hesitated to use the foaming test until I could find a standardized version of it. This I got from a paper by Amarasingham et al. (1964) who in turn had got it from Arthur (1954). As finally adopted (November 1964) it is carried out as follows : I2.

A small amount of fresh plant material (almost always leaves) is finely chopped, placed in a small glass-stoppered test-tube marked at 5 ml. and io ml., and water is added to the 5 ml. mark. The contents are then boiled for I minute, cooled, shaken vigorously and set aside for 5 minutes. A stable foam 2 cm. or more in depth is considered to be positive

TESTS USED BY THE AUTHOR

79

for saponin. A lesser amount of foam remaining after the 5-minute interval is considered to be doubtful, and no foam to be negative for saponin. In comparing our results with those of others (as recorded in our tables) it must be remembered that theirs may stem from haemolysis tests and/or isolation of saponins, and that they may have used bark, roots, seeds, etc. as raw material. It seemed to be wasteful to discard the tubes after observation so I have often added dilute ammonia (1: io conc. ammonia:water) to the 10 ml. mark and observed any changes in colour and/or odour during 2 or 3 days (with occasional shaking while exposed to the air). I list this as `Saponin Test B (NH3)' though it is not actually a further test for saponin. Results are recorded as follows: No change in colour, `o'. A deep yellow colour at once, `flavonoids ?'. A slight darkening during 2-3 days (`yellow ochre' to 'ochraceous orange', of plate xv in Ridgway), `I'. A deeper colour (`tawny' to `hazel' of plate xrv), `2'. A yet deeper colour (about `liver brown' of plate xiv), `3'. A still deeper colour (deeper than `liver brown'), `4'. Occasionally the development of a foul odour is recorded. The tubes are also examined (in recent tests) under L.w. vvL, and fluorescence or lack of it is recorded. This may reveal the presence or absence of coumarins (compare the Juglone Tests). We have found a close but not absolute correlation with positive tests for tannins. The test is chemotaxonomically useful. Members of the Tubiflorae, for example, tend to give o or more rarely i or 2 colours. Members of the Proteaceae when tested have all given 3 or 4 colours. Members of the Myrtaceae (rich in tannin) have given 3 or 4 colours.

CONCLUSION Chemotaxonomy has many critics. Dyed-in-the-wool taxonomists have thought its claims extravagant, and they have had some justification. Many chemists have made rash taxonomic judgments that have shocked botanists, but that is happening less frequently today. The critics have seized upon examples of apparently sporadic occurrence of constituents and of chemical variability and have tended to dismiss comparative chemistry as useless; but that, too, is happening less frequently today. More and more the taxonomists are using chemical characters, as they use morphological and other ones, in their efforts to arrive at a true picture of relationships. This book has at least one merit, and one not to be belittled. It points out, again and again, the many gaps, some little, some vast, in our knowledge of comparative chemistry. The filling of all these gaps will never be completed, but with the development of sophisticated, rapid methods for detection of many plant constituents they can be narrowed. It is to be hoped that workers will be found to speed the process. It requires the co-operation of many from outside the laboratory, however, for one of our prime needs is the provision of living material of the hundreds of particularly interesting plants that are presently unavailable to us. I have often said, halfseriously, that if I had the disposal of a large sum of money I should use it to finance expeditions to find, collect, and bring into our botanical gardens these tantalizing species. There is an urgency about this. Conservationists and others are alarmed at the rapid disappearance of habitats that harbour rare plants and animals. It will soon be too late to close some of the gaps that I mention in the pages above and that follow. Who knows what plants of potential medical or other value, quite apart from their scientific interest, have already gone the way of the dodo ?

[So]

PLANT CONSTITUENTS

PLANT CONSTITUENTS INTRODUCTION Plants produce a bewildering number and kinds of substances, and just as there is no perfect taxonomic system for plants so there is no perfect taxonomy of their constituents. Many able chemists have worked on the problem. They have devised systems of nomenclature, and have tried to enforce some of them, but with only partial success. And nomenclature, of course, is only of limited use. It has been suggested that the biosynthetic approach is the proper one—as amino-acid sequence determinations have been put forward as the ultimate answer to the problems of the taxonomy and phylogeny of living organisms—but we know little as yet about the biosynthesis of most substances and progress is slow, so we cannot wait for a biosynthetic classification. Then, too, such a classification would have its problems, comparable with those of ordinary taxonomy. How would one classify a substance produced in different organisms by different paths ? How would one distinguish with certainty the primitive from the degenerate ? It will be obvious in the section on constituents which follows that I have opted for an alphabetical arrangement of groups of substances, but that in many cases I have had to decide rather arbitrarily the composition of the groups. I have a group of acetylenic compounds, for example, but I have put the recently discovered acetylenic amino-acids with the other amino-adds, and the acetylenic fatty acids with the other fatty acids, rather than in this group. Perhaps the short list at the end of this introduction will help. It will be obvious, too, that my distribution lists are not up to date in many cases. It has been quite impossible to enter recent data which have come to me since the writing of this book was started. In some cases, however, I have been able to include some of the more recent work in the section on orders. Acetylenic compounds, excluding acetylenic amino-acids and fatty acids. Alcohols, including aliphatic, aromatic, and phenolic alcohols, and phenolic esters and ethers; but excluding phenolic glycosides (see under glycosides), terpenoid alcohols (see under terpenoids), and acetylenic alcohols (see under acetylenic compounds). Aldehydes, excluding terpenoid aldehydes and aldehydes which are naphthalene derivatives. [ 83 ]

84 CHEMOTAXONOMY OF FLOWERING PLANTS

Alkaloids. Amides, excluding amides of amino-acids (q.v.) and purine bases (see

alkaloids). Amines and some betaines, but see also alkaloids. Amino-acids, peptides, and proteins (including enzymes). Amino-sugars. Betalains (betacyanins and betaxanthins). Carbohydrates, excluding amino-sugars (above). Carboxylic acids, excluding amino-acids (above) and obviously terpenoid

acids. Coumarins, including furo-, chromano-, and benzo-coumarins, and

isocoumarins. Cyclitols, including quinic and shikimic acids. Depsides and depsidones. ; v-Diphenyl-alkanes. Elements. Fats and fatty acids. Flavonoids. Furan derivatives. Glycosides, including aucubin-type, cyanogenic and phenolic glycosides ; glycolipids; and indoxyl glycosides. Excluding alkaloidal, anthraquinone, cardiac, coumarin, diterpenoid, flavonoid, and isothiocyanate glycosides; and saponins. Gums, mucilages, and resins. Hydrocarbons, excluding acetylenic members, terpenoid hydrocarbons, and naphthalene derivatives. Irritant plants, placed here for convenience, including stinging plants, those causing dermatitis, and the irritant plants of the Anacardiaceae, Proteaceae, etc. Ketones, excluding monoterpenoid and acetylenic ketones, keto-sugars and fatty acids, furan derivatives, chalcones and other flavonoids, and the

quinones. Lactones, excluding a pyrones, alkaloids which are lactones, sesquiterpene lactones, etc. Lignans. Lignins. Melanins. Naphthalene and some of its derivatives, excluding naphthaquinones and some sesquiterpenes. Pyrones, excluding coumarins, isocoumarins, furocoumarins, etc. See also

flavonoids. Quinones. Steroids, excluding steroidal alkaloids.

PLANT CONSTITUENTS 85

Sulfur compounds, excluding sulfur-containing amino-acids, coenzymes, vitamins and acetylenic compounds. Tannins. Terpenoids. Waxes.

ACETYLENIC COMPOUNDS GENERAL Our knowledge of acetylenic compounds occurring in plants has increased at an astonishing speed. Johnson (1965) says: `In 194.8, a review of acetylenic acids and derivatives could list only three or four naturally occurring compounds; today, several hundred are known...The simplest polyacetylenic compounds are those derived from fungi and micro-organisms. Most of the group belong to the C9 or C10 series, with a small number of C8 compounds and a few other structures longer than C10.' Many acetylenes are elaborated by higher plants, and these are of considerable taxonomic interest. We are indebted to Bohlmann and his colleagues, who have published more than 15o papers on `Polyacetylenverbindungen' to date, and to Sørensen and his colleagues, for much of our information. We shall not discuss in detail here the chemotaxonomy of these substances, but one or two points may be noted. (a) The Compositae are remarkably rich in acetylenes, as the following lists show. They seem to be in most (all ?) tribes of the Asteroideae (Tubulifiorae) but to be very rare in the Cichorioideae (Liguliflorae). (b) The Umbelliferae have many acetylenes; the Araliaceae have some. In view of this it would be of great interest to know if they occur in the other families—Cornaceae, Alangiaceae, Garryaceae, Nyssaceae and Davidiaceae—that are associated with them by so many botanists as an order Apiales (Umbellales, Umbelliflorae). (c) The recent discovery by Sung, Fowden, Millington and Sheppard (1969) of three acetylenic amino-adds in the seeds of Euphoria (Sapindaceae) interestingly extends our knowledge of acetylenes. We have included these acids with the other amino-acids. (d) The discovery by Bohlmann et al. (1968) of acetylenes in Pittosporum buchanani raises interesting speculations. (e) The acetylenic fatty adds have distributions of chemotaxonomic importance. We discuss this elsewhere (p. 1701).

86

CHEMOTAXONOMY OF FLOWERING PLANTS

The Biogenesis of Natural Acetylenes This is the title of a recent review by Bu'lock (in Swain, 1966), who says that he deals with the biogenic aspect `in the belief that an understanding of biosynthetic mechanisms is crucial to our understanding of natural products in general and of chemotaxonomy in particular'. While little is yet established beyond all doubt it seems that most natural acetylenes can be derived by reduction from suitably unsaturated carboxylic acids. Thus petroselinic and tariric, oleic and stearolic, and linoleic and crepenynic acids respectively `should' be biogenetically related (fig. I). Of these pairs petroselinic acid has been found in Picrasma and tariric acid in Picramnia spp., members of the Simaroubaceae. They have not (?) been found together. It is known that oleic acid, stearolic acid (and other related acetylenes) do occur together in the Santalaceae. Interestingly it seems that the usual conversion of oleic acid to linoleic acid is lacking in this family. The third pair, linoleic and crepenynic acids, also are known to occur together. Some acetylenic substances are epoxides, but epoxides in general are supposed to arise as in fig. I a and are not, therefore, confined to plants which produce acetylenes. Cyclopropenes might arise from acetylenes and the latter might, therefore, be looked for in the Malvales. Actually sterculynic acid (fig. I) which does occur in the Malvales, is both a cyclopropene and (still) an acetylene! Thiophenes, on the other hand, are supposed to arise as in fig. I b and `should' occur, if this be so, only in acetylene-producing plants. This assumes that they can arise by but a single route. If the parent acetylene had only two triple bonds the resulting thiophene would no longer be an acetylene, and there are some such thiophenes (p. 766). Classification I do not have sufficient knowledge of acetylenes to classify them from a chemotaxonomic viewpoint. There are so many of them, however, that I have tried to break them down into more manageable groups. I have come up with the following admittedly imperfect arrangement: I. `Straight-chain' or `ordinary' acetylenes—the largest group, with about 15o members. II. Thiophene derivatives—with about 45 members. III. Other sulfur-containing acetylenes—with 8 members. IV. Acetylenes with one or more phenyl groups—with about 25 members.

ACETYLENIC COMPOUNDS 87

CH3.(CH2 )10.CH=CH.(CH2)4. COOH

Petroselinic Acid

CH3.(CH 2 )10. C = C . (C H2)4 . COON

Tariric Acid

CH3.(CH 2 )7.CH=CH.(CH2)7.000H

Oleic Acid

CH3.(CH2 )7. C EC. (CH2)7.000H

Stearolic Acid

CH3.(CH 2 )4. CH=CH.CH2.CH=CH.(CH2)7C0011 CH3(CH2)4. C=C.CH2.CH=CH.(CH2)7.COOH

HH

HH

-C=C-

-C - C 0

a. Origin of epoxides

Linoleic Acid Crepenynic Acid

+H2S

5

b. Origin of thiophenes

HC=C .(CH2)7. C\ C.(CH2)6.000H C H2 Sterculynic Acid

Fig. i. The biogenesis of natural acetylenes.

V. Acetylenes with furyl groups—with about a dozen members. VI. Acetylenes with pyran rings—with about half a dozen members. VII. Acetylenes containing nitrogen—with about half a dozen members. VIII. Other acetylenes—including enol-ether spiroketals (many) and a single isocoumarin. Names I have used some common names that occur frequently in the literature. The more scientific names have given me great trouble. Different authors use different systems and are by no means consistent. I have tried to be consistent, but some of my names are probably not acceptable to chemists.

88

CHEMOTAXONOMY OF FLOWERING PLANTS

I `STRAIGHT-CHAIN' OR `ORDINARY' ACETYLENES GENERAL This large group of acetylenes is distributed over the Compositae (about 95), Umbelliferae (about 45), Araliaceae (3), Pittosporaceae (4), Lauraceae (z), and Gramineae (i). See families for further discussion. List and Occurrence Aethusanol-A (Trideca-2,8-dien-4,6-diyn-io-ol) Umbell. Aethusa cynapium (plt) Aethusanol-A acetate Umbell. Aethusa cynapium (plt) Aethusanol-B (Trideca-2,8, ro-trien-4,6-diyn- I -ol) Umbell. Aethusa cynapium (plt) Aethusanol-B acetate Umbell. Aethusa cynapium (plt) Aethusin (Trideca-2t,8t,Iot-trien-4,6-diyne) Umbell. Aethusa cynapium (plt), Peucedanum (Tommasinia) verticillare Aethusin-epoxide (Trideca-2,8-dien-Io,Ii-epoxy-4,6-diyne) Umbell. Aethusa cynapium (plt) Artemisia-alcohol (Tetradec-8t-en-2,4,6-triyn-12-ol) Comp. Anacyclus pyrethrum (ab.gd ; t?); Anthemis ruthenica (rt), saguramica (rt) Artemisia-ketone (Tetradec-8t-en-2,4,6-triyn-ra-one) Comp. Anacyclus pyrethrum (ab.gd), radiatus; Anthemis ruthenica (rt), saguramica (rt); Artemisia vulgaris (rt) ; Cotula coronopifolia (rt) Cicutol (Heptadeca-8,io,r2-trien-4,6-diyn-I-ol) Umbell. Cicuta victorinii, virosa Cicutoxin (Heptadeca-8t,Iot,izt-trien-4,6-diyn-I,r4-diol; CH3CH2CH2CHOH. (CH=CH)3(C-C)2CH2CH2 . CH2OH) Umbell. Cicuta victorinii, virosa Cota-epoxide (Trideca-Io,rz-dien-8,9-epoxy-2,4,6-triyne) Comp. Artemisia cota (rt) Deca-2,6,8-trien-4-yn-I-al Comp. Grindelia robusta, squarrosa D eca-2,6, 8-trien-4-yn- r -ol Comp. Grindelia robusta, squarrosa Deca-2,6,8-trien-4-yn-I-ol acetate Comp. Grindelia robusta, squarrosa

ACETYLENIC COMPOUNDS 89

Dec-8t-en-4,6-diyn-I,3-diol Comp. Carthamus coeruleus (rt) Dec-8t-en-4,6-diyn-r,3-diol diacetate Comp. Carthamus coeruleus (rt), tinctorius (ab.gd) Dec-8c-en-4,6-diyn-I-ol acetate Comp. Chrysanthemum maximum (ab.gd) Dehydro-falcarinol (Heptadeca-1,9,16-trien-4,6-diyn-3-01) Comp. Artemisia atrata (rt) Dehydro-falcarinolone (Heptadeca-I,9,16-trien-4,6-diyn-8-o1-3-one) Comp. Artemisia crithmifolia (lvs) Dehydro-falcarinone (Heptadeca-I,9, r 6-trien-4,6-diyn-3-one) Comp. Artemisia (3), Cotula (3 or 4), Eriocephalus (I), Galinsoga (1), Helianthus (5), Iva (I), Lagascea (I), Tithonia (I), Tridax (i) cis-Dehydro-matricaria ester (Dec-2c-en-4,6,8-triyn-oic acid methyl ester) Comp. Achillea (5 of io tested in section ptarmica; 5/8 in millefolium; 2/7 in filipendulanae; 1/4 in santolinaidae), Anthemis (3), Artemisia vulgaris (rt), Chamaemelum nobile (rt), Chrysanthemum serotinum (rt), Cotula (2), Flaveria repanda (rt) trans-Dehydro-matricaria ester Comp. Achillea (I/Io in section ptarmica; 8/8 in millefolium; 5/7 in filipendulanae; 1/4 in santolinaidae), Anacyclus radiatus, Anthemis (3), Artemisia (1, tr.), Chamaemelum nobile (rt), Chrysanthemum, Cotula (3), Echinops (I), Matricaria (2) cis-Dihydro-matricaria acid (CH2. CH2-.CH . (C_C)2. CH2 . CH2 . COOH) is said to be secreted by a soldier beetle which may aggregate on composites (Meinwald et al. 1968). It has not (?) been found in any composite, but its methyl ester (below) is common cis-Dihydro-matricaria ester is the methyl ester of cis-dihydro-matricaria acid (above). Comp. Amellus, Cephalophora, Felicia, Matricaria, Solidago z,3-Dihydro-oenanthetol (Heptadeca-8,Io-dien-4,6-diyn-r-ol (t, t?)) Umbell. Oenanthe crocata (ab.gd ; t, t), Opopanax chironium (ab.gd) 2,3-Dihydro-oenanthetol acetate Umbell. Oenanthe crocata (ab.gd), Opopanax chironium (ab.gd) 2,3-Dihydro-oenanthotoxin (Heptadeca-8t,rot-dien-4,6-diyn-I,r4-diol) Umbell. Oenanthe crocata (ab.gd, rt) Dodeca-1,1 I-dien-3,5,7,9-tetrayne (CH2=CH. (C=C)4. CH=CH2) Comp. Carthamus, Cnicus, Coreopsis, Silybum Umbell. Carum carvi, Opopanax chironium (rt) Dodec-4-en-6,8, Io-triyn-I-ol Comp. Sanvitalia procumbens (rt)

90 CHEMOTAXONOMY OF FLOWERING PLANTS

Falcarin-diol (Heptadeca-r,9c-dien-4,6-diyn-3,8-diol Umbell. Apium graveolens (rt) Falcarin-dione (Heptadeca-i,gc-dien-4,6-diyn-3,8-dione) Umbell. Carum carvi (rt), Oenanthe pimpinelloides, Opopanax chironium (rt), Sium sisarum Falcarinol (Heptadeca-I,9c-dien-4,6-diyn-3-ol; Carotatoxin; Panaxynol) has a most interesting distribution. Pittospor. Pittosporum buchanani (rt) Arali. Panax schinseng Umbell. Daucus carota, Falcaria vulgaris (rt), Petroselinum sativum (rt) Falcarinolone? Falcarinone (Heptadeca-I,9c-dien-4,6-diyn-3-one; CH3. (CH2)6 . CH= CH.CH2(C-C)2. CO. CH=CH2) Arali. Hedera helix Umbell. Apium graveolens (rt), Carum carvi, Falcaria vulgaris (rt), Oenanthe pimpinelloides, Opopanax chironium (rt), Petroselinum sativum (rt), Sium sisarum Comp. Galinsoga parviflora Falcarinone-8-ol Umbell. Apium graveolens (rt) Heptadeca-2,8-dien,4,6-diyn-I,Io-diol Umbell. Opopanax chironium (ab. gd) Heptadeca-r,8c-dien-I1,13-diyne Comp. Chrysanthemum frutescens (rt) Heptadeca-2t,gc-dien-4,6-diyne Umbell. Oenanthe crocata (rt) Heptadeca-8t,rot-dien-4,6-diyn-I,14-diol-r-acetate Umbell. Oenanthe crocata (rt) Heptadeca-z,9-dien-4,6-diyn-I-ol(t,c ?) Umbell. Opopanax chironium (ab.gd) Heptadeca-I,9t-dien-II,13-diyn-8-ol Comp. Serratula gmelini (rt) Heptadeca-zt,8t-dien-4,6-diyn-I o-ol-I-al Umbell. Oenanthe crocata (rt) Heptadeca-8t,Iot-dien-4,6-diyn-i-ol-14-one Umbell. Oenanthe crocata (it) Heptadeca-I,9c-dien-4,6-diyn-8-o1-3-one —is this falcarinolone (above) ? Arali. Aralia nudicaulis Umbell. Carum carvi, Oenanthe pimpinelloides, Sium sisarum Heptadeca-2t,8t-dien-4,6-diyn-14-one Umbell. Oenanthe crocata (rt)

ACETYLENIC COMPOUNDS 91

Heptadeca-8t, i ot-dien-4,6-diyn-14-one Umbell. Oenanthe crocata (rt) Heptadeca-1,15c-dien-8,9-epoxy-11,13-diyn-ro-ol Comp. Anthemis rudolfiana (rt) Heptadeca-I,9t-dien-11,13,15-triyne Comp. Artemisia Heptadeca-1,9t-dien-11,13,15-triyn-8-ol Comp. Artemisia selengensis (rt) Heptadeca-2,8,10,16-tetraen-4,6-diyne Comp. Artemisia, Centaurea ruthenica and other spp. Heptadeca-2t,8t, Iot,16t-tetraen-4,6-diyn-I-al Comp. Carduus collinus, Tridax trilobata (ab.gd ; also has z-cis-) Heptadeca-2,8,10,16-tetraen-4,6-diyn-I-ol Comp. Coreopsis gigantea, Isostigma peucedanifolium, Tridax trilobata (ab.gd ; 2t,8t,rot,i6t) Heptadeca-1,6t,8t, rot-tetraen-4-yn-3-one Umbell. Falcaria vulgaris (rt) Heptadeca-zt,8t, r ot-trien-4,6-diyne Umbell. Oenanthe crocata (ab.gd, rt) Heptadeca-2c,9c, i 6-trien-4,6-diyne Comp. Chrysanthemum frutescens (rt), maximum (ab.gd) and other spp.; Silybum marianum Heptadeca-zt,8t, Iot-trien-4,6-diyn-I, l4-diol-I -acetate Umbell. Oenanthe crocata (rt) Heptadeca-r,8, I o-trien-4,6-diyn-3-ol Umbell. Opopanax chironium (ab.gd) Heptadeca-2c,8,Io-trien-4,6-diyn-I-ol is the cis- isomer of oenanthetol. Comp. Cotula plumosa (ab.gd) Heptadeca-2c,9c, r6-trien-4,6-diyn-r-ol Comp. Anthemis tinctoria var. (rt) Heptadeca-2,8,16-trien-4,6-diyn-ro-ol Comp. Anthemis cupaniana (Cousinia hystrix?) (rts, much), Jurineamollis(rt), Serratulagmelini (rt ; zc, 8t), Silybum marianum ? (zc, 8c) Heptadeca-2t,8t,Iot-trien-4,6-diyn-14-o1 Umbell. Oenanthe crocata (rt) Heptadeca-2t,8t, r ot-trien-4,6-diyn-r-ol-14-one Umbell. Oenanthe crocata (rt) Heptadeca-8,ro,16-trien-2,4,6-triyne—the 8t,xot form is centaur. X3. Comp. Artemisia (t, t?); Centaurea cyanus, vulgaris (both have t, t and t, c ?) Heptadeca-8t, rot, i 6-trien-2,4,6-triyn-I2-ol Comp. Artemisia selengensis (rt)

92 CHEMOTAXONOMY OF FLOWERING PLANTS

Heptadec-8t-en-4,6-diyn-I,Io-diol Umbell. Opopanax chironium (ab.gd) Heptadec-8t-en-4,6-diyn-I,to-diol-i-acetate Umbell. Oenanthe crocata (rt) Heptadec-9c-en-4,6-diyn-I-ol Umbell. Oenanthe crocata (rt) Heptadec-8t-en-4,6-diyn-I-01-14-one Umbell. Oenanthe crocata (rt) Heptadec-9-en-4,6-diyn-I-o1-3-one Umbell. Falcaria vulgaris (it) [I(Hept-6-enyl)-deca-2t,8c-dien-4,6-diynylJ-L-rhamnose occurs with other rhamnosides in: Comp. Jurinea cyanoides (rt), mollis (rt); Serratula gmelini (rt) Hexadeca-6,8,12,14-tetraen-Io-yn-I-ol Comp. Dahlia merckii Hexadeca-8t, I ot,15t-trien-2,4,6-triyne Comp. Chrysanthemum cis-8-Hydroxy-lachnophyllum ester–angelic acid ester Comp. Aster novi-belgii Lachnophyllol (Dec-2-en-4,6-diyn-I-ol) Comp. Cotula filicula Lachnophyllol acetate Comp. Cotula filicula cis-Lachnophyllum ester (Dec-zc-en-4,6-diynoic acid methyl ester) Comp. Aster novi-belgii (c or t ?), Lachnophyllum gossypinum (and many other composites ?) trans-Lachnophyllum ester Comp. Bellis perennis cis, cis-Matricaria ester (Deca-zc,8c-dien-4,6-diynoic acid methyl ester; CH3 . CH ° CH . (C-C)2. CH ° CH . COOCH3) is the commonest of the many acetylenic compounds of composites ? Comp. Amellus (I), Anthemis (I), Aster (3), Brachycome (I), Dimorphotheca (I), Erigeron (I), Felicia (3), Gaillardia (I), Grindelia (2), Saussurea (I), Solidago (I), Townsendia (I), Tripleurospermum (Matricaria p.p.) (3). It is said to be absent from some tribes of the family. trans, cis-Matricaria ester Comp. Amellus, Matricaria trans, trans-Matricaria ester is said to occur in a polypore and in Comp. Bells perennis Matricarianal (Deca-2,8-dien-4,6-diyn-I-al) Umbell. Aethusa cynapium

ACETYLENIC COMPOUNDS

93

Matricarianol (Deca-2t,8t-dien-4,6-diyn- i -ol) Comp. Aster tripolium (but not in 6 other spp.); Erigeron (I); Grindelia arenicola, stricta (free?, and as ester) Matricarianol acetate Comp. Grindelia robusta (rt), squarrosa (rt) 2-Methoxy-tridec-12-yne (HC- C. (CH2)9 . CH(OCH3). CH3) Laur. Litsea odorifera (prob. present in ess. oil of bk) 2-Methoxy-undec- ro-yne (HC- C. (CH2)7 . CH(OCH3) . CH3) Laur. Litsea odorifera (ess. oil of bk, much; Matthews et al. 1963) Octadeca-8,10,14,16-tetraen-I2-yn-3-one-I-ol acetate Comp. Cosmos sulphureus (ab.gd) Oenanthetol (Heptadeca-2t,8t,Iot-trien-4,6-diyn-I-ol) Umbell. Oenanthe crocata (ab.gd, rt), Opopanax chironium (ab.gd) Oenanthetol acetate Umbell. Oenanthe crocata (ab.gd), Opopanax chironium (ab.gd) Oenanthetone (Heptadeca-2t,8t,Iot-trien-4,6-diyn-14-one) Umbell. Oenanthe crocata (rt), Opopanax chironium (ab.gd) Oenanthotoxin (Heptadeca-2t,8t,Iot-trien-4,6-diyn-I,I4-diol) Umbell. Oenanthe crocata (ab.gd, rt) 16-Oxo-octadeca-9,17-dien-I2,I4-diyn-I-al Umbell. Pastinaca sativa (sd-oil) Pentadeca-2t,9c-dien-4,6-diyne Pittospor. Pittosporum buchanani (rt) Pentadeca-2t,8t-dien-4,6-diyn-ro-ol Umbell. Oenanthe crocata (ab.gd, rt) Pentadeca-9,14-dien-4,6-diyn-3-one-I-ol Comp. Cotula coronopifolia (rt) Pentadeca-2,8,10,14-tetraen-4,6-diyne Comp. Cotula bipinnata (plt) Pentadeca-I,8, Io,14-tetraen-4,6-diyn-3-ol Comp. Cotula coronopifolia (ab.gd, rt) Pentadeca-2t, 8t, I ot-trien-4, 6-diyne Pittospor. Pittosporum buchanani (rt) Umbell. Oenanthe crocata (ab.gd, rt) Pentadeca-8,10,14-trien-4,6-diyn-3-ol Comp. Cotula coronopifolia (ab.gd) Pentadeca-2t,8t, Iot-trien-4,6-diyn-12-ol Umbell. Oenanthe crocata (rt) Pentadeca-I,8t, Ioc-trien-4,6-diyn-3-one Pittospor. Pittosporum buchanani (rt)

94

CHEMOTAXONOMY OF FLOWERING PLANTS

Pontica epoxide (Trideca-8,12-dien-Io,II-epoxy-2,4,6-triyne) Comp. Achillea ptarmica var. and some other spp.; Artemisia pontica (rt) and 3 other spp.; Chrysanthemum (2); Cladanthus arabicus; Tanacetum vulgare Tetradeca-4,6-dien-8,io-diyn-I,12-diol Comp. Cotula coronopifolia (ab.gd) Tetradeca-4,6-dien-8,Io-diyn-I,Iz-diol-I-acetate Comp. Cotula coronopifolia (ab.gd) Tetradeca-4,6-dien-8,10-diyn-i,12-diol-di-acetate Comp. Cotula coronopifolia (ab.gd) Tetradeca-6,12-dien-8,Io-diyn-3-ol Comp. Anthemis saguramica (rt) Tetradeca-2, 12-dien-4, 6,8, I o-tetrayne Gram. Triticum aestivum (plt) Tetradeca-4,6-dien-8, 1 0, 12-triyn-I-ol Comp. Anthemis ruthenica (rt), Chrysanthemum atratum (ab.gd) Tetradeca-4,6-dien-8,10, 12-triyn-I-ol-acetate Comp. Tanacetum vulgare (rt, little) Tetradeca-2,4,6,12-tetraen-8, Io-diynoic acid methyl ester Comp. Sanvitalia procumbens (rt) Tetradeca-4,6,10,1z-tetraen-8-yn-I-01-acetate Comp. Cotula coronopifolia (ab.gd) Tetradeca-4t,6t, I2t-trien-8, Io-diyn-I-ol Comp. Cotula coronopifolia, Dahlia (2) Tetradeca-4, 6, I z-trien-8, I o-diyn- I -ol-acetate Comp. Coreopsisgigantea; Cotula coronopifolia; Dahlia merckii (rt), scapigera Tetradeca-2, Io-13-trien-4,6,8-triyn-I-ol-acetate Comp. Carlina Tetradec-6t-en-4,5-epoxy-8,10, I2-triyn-I -ol Comp. Chrysanthemum serotinum (ab.gd) Tetradec-6t-en-8,10,12-triyn-I,5-diol Comp. Centaurea muricata (ab.gd) Tetradec-6t-en-8,10,1 z-triyn-1, 5-diol- I-acetate Comp. Centaurea muricata (ab.gd) Tetradec-5-en-8,10,1 z-triyn- I -ol-acetate Comp. Chrysanthemum serotinum (ab.gd) Trideca-8t, I z-dien-1 o, I I-epoxy-2,4,6-triyne Comp. Chrysanthemum serotinum (ab.gd, rt) Trideca-at, lot-dien-I2,I3-epoxy-4,6,8-triyne Comp. Carthamus (3), Centaurea ruthenica (lvs; t,t?) Trideca- I ot, I z-dien-z,4, 6, 8-tetrayne Comp. Rudbeckia (3)

ACPTYLPNIC COMPOUNDS

95

Trideca-z,1 z-dien-4,6,8, Io-tetrayn-i-al (CH2=CH . (C-C)4 . CH=CH. CHO) Comp. Bidens (rts of 4), Cosmos diversifolius (rt), Leptosyne calliopsides Trideca-2,12-dien-4,6,8,Io-tetrayn (CH 2=CH.(C-C)4 .CH=CH.CH3)seems to be a common acetylene. Both cis- and trans- forms occur. Comp. Bidens (5), Carthamus (rts of 3, t), Centaurea (in 48 spp., but not in 3 spp. of section Centaurium), Crupina vulgaris, Dahlia merckii? (rt), Serratula (2), and others. Bohlmann (1966) says it is in most of the Carduinae tested (Arctium, Carduus, Cirsium, Cousinia, Galactites, Jurinea, Onopordon, Saussurea, Silybum) Trideca-z,12-dien-4,6,8, Io-tetrayn-I-ol Comp. Bidens (5), Cosmos diversifolius (rt), Leptosyne calliopsides Trideca-2, I2-dien-4, 6,8, I o-tetrayn- I -ol-acetate Comp. Bidens (6), Coreopsis, Cosmos diversifolius (rt), Leptosyne calliopsides Trideca-3t, I It-dien-5,7,9-triyn-2-chloro-I-ol (CH2. CH=CH. (C=C)3. CH=CH. CHC1. CH2OH) Comp. Carthamus coeruleus (rt), tinctorius (ab.gd); Centaurea ruthenica (rt; t,t ?); Dicoma zeyheri (t,t?) Trideca-3t, I It-dien-5,7,9-triyn-2-chloro-I-ol-acetate Comp. Carthamus (3), Centaurea ruthenica (rt; t,t ?), Dicoma zeyheri (t,t ?) Trideca-3t,1 It-dien-5,7,9-triyn-I,2-diol Comp. Carthamus lanatus (ab.gd), tinctorius (ab.gd), Centaurea ruthenica (rt; t,t?) Trideca-3t, I I t-dien-5,7,9-triyn-1,z-diol-2-acetate Comp. Carthamus lanatus (ab.gd), Centaurea ruthenica (rt; t,t ?) Trideca-3t, I It-dien-5,7,g-triyn-I,2-diol-diacetate Comp. Carthamus lanatus (ab.gd), Centaurea ruthenica (rt; t,t ?) Trideca-I,3, 5, I I-tetraen-7,9-diyne Comp. Bidens ferulaefolius (lys, st.), Carthamus coeruleus (rt), Coreopsis, Cosmos (rts of 2, all -trans) Trideca-3,5, I I-trien-7,9-diyn-I,2-diol Comp. Centaurea ruthenica (rt) Trideca-3, 5, I I-trien-7,9-diyn-I,2-diol-di-acetate Comp. Centaurea ruthenica (rt) Trideca-zc, Ioc,I2-trien-4,6,8-triyn-I-al Comp. Carlina vulgaris (rt) Trideca-zt,1 ot, 12-trien-4, 6, 8-triyn- I -al Comp. Cosmos hybridus (it), sulphureus (rt)

g6 CHEMOTAXONOMY OF FLOWERING PLANTS Trideca-zc, Ioc, 12-trien-4,6,8-triyne Comp. Bidens ferulaefolius (lvs, st. ; not given as c,c), Coreopsis Trideca-zt, Iot-i 2-trien-4,6,8-triyne Comp. Carthamus (ab.gd pts of 3), Cosmos (rts of 2) Trideca-8t, I ot, I z-trien-z,4,6,triyne—not all the following are given as t,t. Comp. Achillea (26 of 29 spp. tested), Anacyclus (2), Anthemis (3), Artemisia, Bidens, Chrysanthemum, Coreopsis, Flaveria, Matricaria (Tripleurospermum) oreades (lvs, st.) Trideca-zt, Iot, I2-trien-4,6,8-triyn-I-ol Comp. Cosmos hybridus (rt), sulphureus (rt) Trideca-at, I oc,1z-trien-4,6,8-triyn- i-ol-acetate Comp. Carlina cis- and trans- Tridec-2-en-Iz,13-epoxy-4,6,8,To-tetrayne Comp. Centaurea deusta (rt) Tridec-I2-en-2,3-epoxy-4,6,8, l o-tetrayne Comp. Centaurea deusta (rt) Tridec-iot-en- I z,13-epoxy-2,4,6,8-tetrayne Comp. Carthamus tinctorius (ab.gd, rt), Centaurea ruthenica (lys; t ?) Tridec-I2-en-z,4,6,8,bo-pentayne (CH3. (C-C)3. CH=CH2) is one of the chief acetylenes of composites. I have records from: Comp. Achyrachaena (1), Ambrosia (3), Arctium, Arnica (I), Berkheya (r), Bidens (2), Buphthalmum (3), Calendula (I), Carduus, Carthamus (I), Cirsium, Cousinia (1), Cynara (1), Echinacea (2), Flaveria (I), Galactites, Guizotia (t), Helipterum (I), Hemizonia (I), Jurinea, Layia (I), Melampodium (2), Onopordon, Rudbeckia (t), Sanvitalia (t), Saussurea, Serratula (4), Silybum, Spilanthes (1), Synedrella (I), Xanthium (t) Tridec- I ot-en-2,4, 6, 8-tetrayn- 12-chloro- 13-0l Comp. Carthamus tinctoria (ab.gd) Tridec-Io-en-2,4,6,8-tetrayn-12,13-diol Comp. Centaurea ruthenica (lvs) Tridec-12,13-epoxy-z,4,6,8,1 o-pentayne Comp. Centaurea deusta (rt)

II THIOPHENE DERIVATIVES GENERAL We have seen, in discussing the biogenesis of acetylenic substances, that the thiophenes appear to arise from compounds with z or 4 acetylenic linkages following each other (fig. I).

ACETYLENIC COMPOUNDS

97

If this is the case we might expect to find both `straight chain' polyacetylenes and thiophenes in the same or in closely related plants, and at least 19 of the 3o or so genera listed below are known to have both. The thiophenes seem to be confined to the Compositae and in that great family to the following tribes of the sub-family Asteroideae (Tubuliflorae) : 4. Inuleae—Buphthalmum, Calocephalus, Tarchonanthus 5. Heliantheae—Achyrachaena, Ambrosia, Bidens, Coreopsis, Eclipta, Guizotia, Hemizonia, Layia, Melampodium, Rudbeckia, Spilanthes 6. Helenieae—Baeria, Lasthenia, Schkuhria, Tagetes 7. Anthemideae—Anacyclus, Anthemis (Chamaemelum), Artemisia, Chrysanthemum, Matricaria (Tripleurospermum), Santolina I o. Arctoteae—Berkheya I i. Cardueae (Cynareae)—Atractylus, Centaurea, Echinops, Serratula A substance having but z neighbouring acetylenic linkages would, on giving rise to a thiophene, no longer be an acetylene (fig. I). A few thiophenes—presumably of this type, and all from members of the Compositae—are listed among sulfur compounds, though they would seem to `belong' here. List and Occurrence 2-(Acetoxymethyl)-5'-(but- I -yn-3-ene- I )bithienyl-2, z' Comp. Bidens dahlioides (ab.gd); Buphthalmum grandiflorum (ab. gd), salicifolium (ab.gd) z-Acetyl-3-hydroxy-5-prop-I-ynyl-thiophene (fig. 2) Comp. Artemisia aborescens 2-Acetyl-3-methoxy-5-prop- I -ynyl-thiophene Comp. Artemisia arborescens (rt) 5-(But-4-chloro-3-hydroxy-I-ynyl-I )-bithienyl-2,z' Comp. Tagetes minuta (rt) 5-(But-3-en-3-chlor-4-acetoxy- I-ynyl)-bi-thienyl-2,2' Comp. Berkheya adlami (rt) 5-(But-3-en-I-ynyl-I)-bithienyl-2,2' (fig. 2) Comp. Berkheya adlami (rt); Echinops; Tagetes erecta, minuta z-(But-3-en-I-ynyl-I)-5-(pent-2t-en-4-yn-I-al-5)-thiophene Comp. Baeria chrysostoma, coronaria; Coreopsisgrandiflora (rt) 2-(But-3-en-I-ynyl- I)-5-(pent-2t-en-4-yn-I-of-5)-thiophene Comp. Baeria chrysostoma, coronaria; Serratula radiata (rt; t ?) 2-(But-3-en-I-ynyl-I)-5-(pent-2t-en-4-yn-I-ol-acetate-5)-thiophene Comp. Baeria chrysostoma, Serratula radiata (rt; t ?) 4

CCC)

98 CHEMOTAXONOMY OF FLOWERING PLANTS

2-(But-3-en-i-ynyl-t)-5-(pent-2t-en-4-ynyl-5)-thiophene (fig. 2) Comp. Baeria (3), Bidens (2), Centaurea (rts of 4; t ?), Guizotia oleifera (ab.gd), Lasthenia glaberrima, Serratula radiata (rt; t ?) 5-(But-4-ol- I-ynyl- I )-bithienyl-2, 2' Comp. Tagetes minuta (rt) 5-(But-4-ol- i -ynyl-4-acetate- I )-bithienyl-2, 2' Occurrence ? 5-(3 ,4-D iacetoxy-but- I -ynyl- I )-bithienyl-2, 2' Comp. Echinops sphaerocephalus (rt) 5-(3,4-Dihydroxy-but- I-ynyl-I )-bithienyl-2,2' Comp. Echinops sphaerocephalus (rt) I-(Furyl-2)-4-(5-acetoxymethyl-thienyl-2)-but-Ic-en-3-yne (fig. 2) Comp. Santolina sp. (rt) I -(Furyl-2)-4-(thienyl-2)-but- I -en-3-yne Comp. Santolina pinnata (c, and t) 5-(3-Hydroxy-4-acetoxy-but-I -ynyl)-bithienyl-2, 2' Comp. Echinops sphaerocephalus (rt) 5-(4-Hydroxy-3-acetoxy-but-I-ynyl)-bithienyl-2,2' Comp. Echinops sphaerocephalus (rt) 5-(4-Hydroxy-but- I -ynyl)-bithienyl-2,2'-acetate Comp. Tagetes erecta, minuta, patula 5-(Hydroxymethyl)-5'-(but-3-en- I -ynyl- I)-bi-thienyl-2, 2' Comp. Bidens dahlioides (ab.gd); Buphthalmum grandiflorum (ab. gd), salicifolium (ab.gd); Echinops sphaerocephalus (rt) 2-(Methyl acrylate)-5-(prop-I-ynyl-I)-thiophene Comp. Chrysanthemum 5-(Methyl)-5'-(but-3-en-I-ynyl-I )-bithienyl-2,2' Comp. Buphthalmum grandiflorum (ab.gd), salicifolium (ab.gd); Rudbeckia amplexicaulis (ab.gd) 2-(Methyl)-5-(methyl-but-a-en-y-ynoate)-thiophene Comp. Anacyclus radiatus; Anthemis nobilis (Chamaemelum nobile?) (rt; c and t), vulgaris (t) 2-(Methylpent-a-en-y-ynoate-a)-thiophene Comp. Anthemis fuscata (ab.gd) 2-(Nona-I,7-dien-3,5-diynyl-I )-thiophene Comp. Atractylus spp. 2-(Nona-3t, 5t-dien-7-ol- I -ynyl- I )-thiophene Comp. Anthemis saguramica (rt) 2-(Nona-3, 5-dien-7-one- I -ynyl- I )-thiophene Comp. Anthemis saguramica (rt; c,t and t,t) Tripleurospermum (c,t or t,t ?) 2-(Non-5t-en-7-ol- I-ynyl-I )-thiophene Comp. Anthemis saguramica (rt)

ACETYLENIC COMPOUNDS

99

OH ~S~

H3C-C_C S"COCH3

~Cc CH=CH2

5 (But-3-en-1-ynyl-l-)- bithienyl- 2,2

2-Acety1 3-hydroxy-5-prop-1-ynyl- thiophene

S

S

'C-CH3

2-(Phenyl)-5(.Fpropynyl)-thiophene

H2C =CH.0=C

S

CV:-CH = CH. CH3

2-(But-3•en 1-ynyl-1-)-5 - (pent-2t-en-4- ynyl-5)-thiophene

c

H3C.00.OH2C s C=C-C=C

HH

1 (Furyl-2)-4- (5•acetoxymethyl-thienyl-2)-but-1 c-en-3-yne

Fig. 2. Some acetylenic derivatives of thiophene.

2 (Non-3 t-en-7-one- I -ynyl-i)-thiophene Comp. Anthemis saguramica (rt), Matricaria (Tripleurospermum) inodora (it) 2-(Non-3-en- I -yn-6-o1-7-one-isovalerate- I)-thiophene Comp. Anthemis saguramica (rt) 2-(Non-3-en- I -yn-5-o1-7-one-isovalerate- I)-thiophene Comp. Anthemis saguramica (rt) 2-(Octa-3t,5t,7-trien- I -ynyl- I)-thiophene Comp. Matricaria (Tripleurospermtlm) inodora z-(Penta-I,3-diynyl-I )-5-(4-acetoxy-but-I-ynyl-I )-thiophene Comp. Echinops sphaerocephala (rt) z-(Penta-I,3-diynyl-I )-5-(but-3-en- I -ynyl- I )-thiophene Comp. Calocephalus citreus, Echinops sphaerocephalus (rt) z-(Penta-I,3-diynyl-I )-5-(3-chloro-4-acetoxy-but-I-ynyl-I)-thiophene Comp. Echinops sphaerocephalus (rt) z-(Penta-I,3-diynyl-I)-5-(3-chloro-4-hydroxy-but-I-ynyl-I )-thiophene Comp. Echinops sphaerocephalus (rt) 2-(Penta- I, 3-diynyl- I)-5-(3 , 4-diacetoxy-but- I -ynyl- I)-thiophene Comp. Echinops sphaerocephalus (rt) 4-=

I00 CHEMOTAXONOMY OF FLOWERING PLANTS

2-(Penta-I,3-diynyl-I )-5-(3,4-dihydroxy-but-I-ynyl-I)-thiophene Comp. Echinops sphaerocephalus (rt) 2-(Pent-3-en- I -yn-5-al- I )-thiophene Comp. Anthemis saguramica z-(Phenyl)-5-(a-propynyl)-thiophene (fig. 2) Comp. Coreopsis grandiflora (lvs, fl.) 2-(Prop-I -yny1- I)-5'-(acetylenyl)-bithienyl-2,2' Comp. Tagetes erecta 2-(Prop- I -ynyl- I)-5 -(hexa-3, 5-di en- I -ynyl- I )-thiophene Comp. Melampodium (rts of 2; t), Rudbeckia (rts of 5; all t ?) z-(Prop- I-ynyl- I)-5-(hex-5-en- i, 3-diynyl- I )-thiophene Comp. Achyrachaena (I), Ambrosia (3), Eclipta (2), Hemizonia (I), Iva (I), Layia (z ?), Rudbeckia (I), Schkuhria (2), Spilanthes (I ?), Tarchonanthus (I ?) 2-(Prop- I -ynyl-3-of - I)-5-(hex-5-en- i,3-diynyl- I )-thiophene Comp. Rudbeckia triloba (rt) z-(Prop-I -ynyl- I)-5'-(viny1)-bithienyl-z,z' Comp. Guizotia olezfera

III OTHER SULFUR-CONTAINING ACETYLENES GENERAL These, like the thiophene derivatives, seem to be restricted to the Compositae and in this case to a few species of Anthemis and to Chrysanthemum segetum. Is it significant that some other species of Anthemis have thiophenes, and that the mercapto-acetylenes found in Chrysanthemum have phenyl groups (p. 503) ? List and Occurrence Deca-2,4-dien-4-methylmercapto-6,8-diynoic acid methyl ester Comp. Anthemis tinctoria var. (rt; c,c and c,t) Deca-z,6-dien-7-methylmercapto-4,8-diynoic acid methyl ester Comp. Anthemis cairica (t,t), carpatica (rt; c,t and t,t), cota (t,t), ruthenica (rt; c,c and t,c), tenuifolia (t,t), tinctoria var. (rt; c,c) Deca-z,4-dien-5-methylmercapto-6,8-diynoic acid methyl ester Comp. Anthemis carpatica (rt, c,c) Deca-z,8-dien-9-methylmercapto-4,6-diynoic acid methyl ester Comp. Anthemis arvensis (c,t), carpatica (rt; c,t), cinerea (c,t), maritima (c,t), ruthenica (c,t), tinctoria (rt; c,t), triumfetta (rt; c,t)

ACETYLENIC COMPOUNDS IOI

Deca-2,4-dien-5-methylsulfone-6,8-diynoic acid methyl ester Comp. Anthemis ruthenica (rt) Deca-2,4,8-trien-5-methylmercapto-6-ynoic acid methyl ester Comp. Anthemis austriaca (rt; c,c,c and c,t,c) Deca-2,4,6-trien-5-methylmercapto-8-ynoic acid methyl ester Comp. Anthemis tinctoria var. (rt; c,c,c) Dodeca-2,Io-dien-ii-methylmercapto-4,6,8-triynoic acid methyl ester (CH3. C(SCH3)=CH . (C-C)3. CH=CH . COOCH3) Comp. Anthemis tinctoria var. (it; c,c)

IV ACETYLENES WITH ONE OR MORE PHENYL GROUPS GENERAL Acetylenes of this type seem to be confined to the Compositae and in that family to a few genera of the tribes Heliantheae and Anthemideae. List and Occurrence 7-(m-Acetoxyphenyl)-hept-2t-en-4,6-diyn-I-ol acetate Comp. Coreopsis tinctoria cv. (rt) Capillene (I -Phenyl-hex-z-en-4-yne) Comp. Artemisia capillaris (and another sp. ?) Grant. ?Agropyron (Triticum) repens. Probably not, says Sorensen (in Swain, 1963) Capillin (I-Phenyl-hexa-2,4-diyne-I-one) Comp. Artemisia capillaris, dracunculus; Chrysanthemum frutescens; Lonas annua (rt) Demethyl-frutescine (Methyl-2(penta-2',4'-diynyl-I)-6-methoxybenzoate) Comp. Chrysanthemum frutescens (rt) Demethyl-frutescinol acetate Comp. Chrysanthemum frutescens (rt) I,Io-Diphenyl-deca-2,4,6,8-tetrayne (fig. 3) Comp. Artemisia dracunculus Frutescine (Methyl-z-hexa-2',4'-diynyl-6-methoxy-benzoate; fig. 3) Comp. Chrysanthemum frutescens (rt) Frutescinol acetate Comp. Chrysanthemum frutescens (rt) Frutescinol lactone Comp. Chrysanthemum frutescens (rt)

IO2 CHEMOTAXONOMY OF FLOWERING PLANTS

0

C-

C_C-CH:CH SCH3

1-Phenyl-pent-4-en-2-yn-5-methylmercapto-1-one

H3CO

CO.00H3

CH2-(C°_C)2.CH3

Frutescine

CH2.(C°-C)4 -CH2

1,10-Di phenyl -deca-2,4,6,8-tetrayne

(C= C)3 . C H3

1-Phenyl - hepta-1,3,5 -triyne

Fig. 3. Some acetylenic compounds with phenyl groups.

Frutescinone (Methyl-z-hexa-2',4'-diynoyl-6-methoxy-benzoate) Comp. Chrysanthemum frutescens (rt) I -Phenyl-hepta- I ,3-diyn-5,6-diol Comp. Dahlia x ` Preference' (tuber) I -Phenyl-hepta- I , 3 -diyn-5, 6, 7-triol Comp. Dahlia x 'Dolce Vita' (tuber) I -Phenyl-hepta- I , 3, 5-triyn-7-ol-acetate Comp. Bidens dahlioides (ab.gd), leucanthus (ab.gd) I-Phenyl-hepta-I,3,5-triyne (fig. 3) Comp. Bidens (4), Coreopsis (at least 3) I-Phenyl-hept-5-en-I,3-diyne Comp. Coreopsis (tuber), Dahlia (tuber) I-Phenyl-hept-5-en-I,3-diyn-7-ol Comp. Bidens I -Phenyl-hept-5t-en- I, 3-diyn-7-ol-acetate Comp. Bidens pilosus (rt), tripartitus (rt); Coreopsis sp., leucanthus (rt) I-Phenyl-hexa-2,4-diyn-I-ol acetate Comp. Lonas annua I-Phenyl-hexa-2,4-diyn-I-one-6-ol Comp. Lonas annua (ab.gd) I -Phenyl-hexa-2,4-diyn- I -one-6-ol-ß-methyl-crotonic acid ester Comp. Lonas annua (ab.gd) I-Phenyl-penta-z,4-diyne (Benzyl-diacetylene) Comp. Artemisia dracunculus, Chrysanthemum segetum

ACETYLENIC COMPOUNDS I03

I -Phenyl-pent-4-en-2-yn-5-methylmercapto Comp. Chrysanthemum segetum (rt) I -Phenyl-p ent-4-en-2-yn-5-methylmercapto- I -one (4-Benzoyl-buta-Imethylmercapto-I-en-3-yne; fig. 3) Comp. Chrysanthemum segetum (rt; c and t) I-Phenyl-undeca-7,9-dien-I,3,5-triyne—there is some doubt about this. Comp. Coreopsis ?

V ACETYLENES WITH FURYL GROUPS GENERAL This is a small group essentially confined to the Compositae. One is said to occur in Eremophila (Myoporaceae), another in a legume, Vicia faba. List and Occurrence Atractylodin (I-(Furyl-2)-nona-It,7t-dien-3,5-diyne) Comp. Atractylodes sp. (rhiz.) Carlina oxide (z-(3'-Phenyl-prop-I'-ynyl) furan; fig. 4) Comp. Carlina acaulis (rt) 5-Chlormethyl-2(octa-2,4,6-triynyliden)-2,5-dihydro-furan (fig. 4) Comp. Gnaphalium obtusifolium (rt; c and t) I -(2, 3-Dihydro-furyl-z)-non- I -en-3, 5,7-triyne Comp. Chrysanthemum leucanthemum (rt) Freelingyne (fig. 4) has been called the `first example of an acetylenic terpenoid'. Myopor. Eremophila freelingii (wd-oil) I -(Furyl-2)-hexa-2, 4-diyne Occurrence ? I -(Furyl-2)-nona- I -en-3, 5, 7-triyne Comp. Chrysanthemum leucanthemum (rt) cis- and trans-5-Methoxy-2(hexa-z,4-diynylidene-I)-2,5-dihydro-furan Occurrence ? Methyl-3 [5-(hept-4c-en-2-ynoyl)-2-furyl]-trans-acrylate Legum. Vicia faba (shoot) 4-(Nona-6,8-dien-z,4-diynylidene)-butenolide Comp. Carlina vulgaris (rt) 2-(Nona-6c,8 c-dien-2,4-diynylidene)-2, 5-dihydro-furan Comp. Carlina vulgaris (rt) 2-(Non-I-en-3,5,7-triynyl-I)-z,3-dihydro-furan Comp. Chrysanthemum leucanthemum (rt)

I04 CHEMOTAXONOMY OF FLOWERING PLANTS

O" C°C.CH2 3' 1'

H3C- (C=C)3.CH''OCH2CI 5-Chlor methyl-2 (octa-2¢,6 — triynyl iden)-2,5-dihydrofuran

Carlina oxide

C3C,, C=C H

F_____.7 \C -' O ~'O H

Freelingyne



Fig. 4. Some acetylenes with furyl groups.

VI ACETYLENES WITH PYRAN RINGS GENERAL A few acetylenes are known which have pyran, or rather dihydro- or tetrahydro pyran rings. These seem to be confined to the Compositae, but although so few in number, they are recorded from Inuleae (Anaphalis, Gnaphalium); Heliantheae (Dahlia, Ichthyothere); Anthemideae (Chrysanthemum); and Cardueae (Centaurea). List and Occurrence 5-Chlor-3,4-epoxy-2(octa-2,4,6-triynyliden)-5,6-dihydro-2H-pyran Comp. Anaphalis triplinervis (rt) 5-Chlor-2(octa-2,4,6-triynyliden)-5-6-dihydro-2H-pyran (fig. 5) Comp. Anaphalis margaritacea, triplinervis (rt); Gnaphalium obtusifolium (rt) 2e and 2a-Hydroxy-6(non-It-en-3,5,7-triynyl-I)-tetrahydro-pyran Comp. Centaurea muricata (ab.gd) 3-Hydroxy-2(non- It-en-3, 5,7-triynyl- I)-tetrahydro-pyran (Ichthyothereol; fig. 5) Comp. Dahlia coccinea (lvs, fl.), Ichthyothere terminalis (lvs) z-(Non- I t-en-triynyl- I)-3-acetoxy-3 ,4, 5 , 6-tetrahydro-pyran Comp. Chrysanthemum serotinum (ab.gd, rt) 2-(Non-It-en-triynyl-I)-3-hydroxy-3,4,5,6-tetrahydro-pyran Comp. Chrysanthemum serotinum (rt)

ACETYLENIC COMPOUNDS

CH3-(CEC )3-C H

CI

t CH3-(C_C)3CH=CH

IOS

HO 23 O

5-Chloro-2 (otta-2,4,6 -triynyliden)-5,6-dihydro- 2H-pyran

3-Hydroxy-2(non-it-en-35,7- triynyl )- tetrahydro-pyran

Fig. 5. Acetylenes with pyran rings.

VII ACETYLENES CONTAINING NITROGEN GENERAL A few acetylenes—mostly amides—are known which contain one or more nitrogen atoms. These, like so many acetylene compounds, have been recorded only from the Compositae and in that family only from Heliantheae and Anthemideae. List and Occurrence Dodeca-zc,4t-dien-8,io-diyn-i-oic acid-i-isobutylamide Comp. Echinacea angustifolia (rt), purpurea (rt) Hexadeca-7,14-dien-r0,Iz-diyn-I-ol-azobenzol-carbonic acid ester Comp. Dahlia merckii Hexadeca-7, 12,14-trien- I o-yn- I -ol-azobenzol-carbonic acid ester Comp. Dahlia merckii Tetradeca-zt,4t-dien-8, Io-diyn-I-oic acid- i-isobutylamide (Anacycline) Comp. Anacyclus pyrethrum (rt) Undeca,2,4-dien-8, Io-diyn-r-oic acid-i-isobutylamide Comp. Chrysanthemum frutescens (t,t); Echinacea angustifolia (rt; c,t), purpurea (rt; c,t)

VIII OTHER ACETYLENES A group of enolether-spiroketals (fig. 6)—for most of which I have no names—have been found in Chrysanthemum (many in 40 spp.!), Artemisia (several in at least I sp.), and Matricaria (at least r in at least 2 spp.). These are all members of the Anthemideae. A single isocoumarin acetylene—capillarin (fig. 6)—is also to be found in two spp. of Artemisia.

I06 CHEMOTAXONOMY OF FLOWERING PLANTS

CH3 -(C_C)2 . CH U

I

0

An enolether-spiroketal

Capillarin

Fig. 6. Uncommon acetylenes.

I ALCOHOLS GENERAL We have included here the following `groups' of alcohols and derivatives: I. Aliphatic I. Monohydric: a. Normal saturated; b. Other saturated; c. Unsaturated. 2. Dihydric. 3. Trihydric and up (Aliphatic Polyols): a. Trihydric; b. Tetrahydric; c. Pentahydric; d. Hexahydric; e. Heptahydric. II. Aromatic (some are phenols) III. Phenols IV. Phenolic esters and ethers We have excluded phenolic glycosides (p. 635), terpenoid alcohols, acetylenic alcohols, the alcohols of the Anacardiaceae, etc.

I . I . a Normal aliphatic alcohols GENERAL A series of alcohols (C„H2n+1OH) beginning with methyl (CH3OH) and ethyl (CH 3. CH 2OH) alcohols is known from plant sources. The lower members of the series occur chiefly as esters of very varied kinds, some of which are prominent in the odoriferous mixtures of plants. The higher members of the series, with C20 to C34, occur as waxes (esters with

fatty acids). An examination of the following list will show that I have little information of chemotaxonomic value. We have all too few records for most of these alcohols. It is evident, however, that the even C-number alcohols are much commoner in plants than are those with odd C-

ALCOHOLS I07

numbers. It is clear, too, that some plants appear to use higher Cnumber alcohols than do others (Table 4). This is in line with observations on hydrocarbons (figs. 135 and 136). List and Occurrence Methyl alcohol (Methanol; Wood alcohol; CH3OH; fig. 7) occurs usually as esters. Is it free in any of the following ? Urtic. Boehmeria The. Thea (Camellia) Maly. Gossypium Umbell. Anthriscus, Heracleum, Pastinaca Verben. Vitex Ethyl alcohol (Ethanol; CH3. CH2OH) occurs free and as esters Fag. Castanea sativa (wd) Ros. Fragaria (frt), Rubus idaeus (frt) Rut. Citrus (frt) Myrt. Eucalyptus spp. (ess. oil) Umbell. Anthriscus cerefolium (frt), Heracleum giganteum (frt), Pastinaca sativa (frt) Solan. Nicotiana tabacum (lys) Propyl alcohol (Propan-i-ol; CH3. CH2 . CH2OH) occurs only secondarily ? Butyl alcohol (Butan-t-ol; CH3. (CH2)2 . CH2OH) occurs chiefly as esters Lab. Mentha arvensis v. piperascens (ess. oil; free ?) Amyl alcohol (Pentan-i-ol; CH3.(CH2)3 .CH2OH) occurs only (?) as esters Hexyl alcohol (Hexan-i-ol; CH3. (CH2)4 . CH2O14) occurs free and as esters Laur. Litsea zeylanica (lvs; ess. oil) The. Thea (tea; ess. oil) Ros. Fragaria (frt) Gerani. Pelargonium (ess. oil) Lab. Lavandula spita (ess. oil), vera (ess. oil); Salvia spinosa (ess. oil) Heptyl alcohol (Heptan-I-ol; CI-I3.(CH2)5.CH2OH) Laur. Litsea zeylanica (lys; ess. oil) Lill. Hyacinthus (fl. oil?) Octyl alcohol (Octan-I -ol ; CH3.(CH2)6 .CH2OH) occurs free and as esters The. Thea (tea; leaf-oil) Rut. Citrus bigaradia (oil), paradisi (frt-oil)

Io8 CHEMOTAXONOMY OF FLOWERING PLANTS

Umbell. Heracleum giganteum (villosum) (frt, free and as ester), sphondylium (frt, as ester); Pastinaca sativa (frt, as ester) Nonyl alcohol (Nonan-I-ol; CH3.(CH2)7 .CH2OH) Rut. Citrus aurantium (peel-oil); Eremocitrus glauca (leaf-oil) ? Decyl alcohol (Decan-I-ol; CH3. (CH2)s. CH2OH) Ros. Prunus amygdalus (fl.-oil) Rut. Citrus? Bux. Simmondsia californica (sd, as ester) Undecyl alcohol (Undecan-i-ol; CH3.(CH2)9 .CH2OH): no records Dodecyl alcohol (Dodecan-I-ol; Lauryl alcohol; CH3 . (CH2)10 . CH2OH) Rut. Citrus aurantifolia (oil, as ester) Rhamn. Rhamnus purshiana (bk, as ester ?) Umbell. Ligusticum acutilobum (frt, as ester) Agay. Furcraea gigantea (fl.) Tridecyl alcohol (Tridecan-i-ol; Pisangceryl alcohol; CH3 .(CH2)11. CH2OH) Mus. Musa cera (wax) Tetradecyl alcohol (Tetradecan-I-ol; Myristyl alcohol; CH3 .(CH2)12. CH2OH) Umbell. Ligusticum acutilobum (frt, as ester) Pentadecyl alcohol (Pentadecan-I-ol; CH3. (CH2)13. CH2OH): no records Hexadecyl alcohol (Hexadecan-I-ol; Cetyl alcohol; CH3 .(CH2)14. CH2OH) Loranth. Loranthus europaeus (frt ?) Umbell. Dorema ammoniacum (resin) Convolvul. Ipomoea spp. (as esters) Comp. Ambrosia artemisifolia (pollen; wax ?) Lili. Smilax spp. (rts) Gram. Sorghum? Heptadecyl alcohol (Heptadecan-I-ol; Margaryl alcohol; CH3. (CH2)15. CH2OH) : no records 0ctadecyl alcohol (Octadecan-I-ol; Stearyl alcohol; CH3 .(CH2)16. CH2OH) occurs in lichens and fungi and Piper. Piper methysticum (rt) Comp. Ambrosia artemisifolia (pollen; wax ?) Nonadecyl alcohol (Nonadecan-I-ol; CH3. (CH2)17 . CH2OH) Ros. Rubus idaeus (frt ?) Eicosyl alcohol (Eicosan-I-ol; Arachidyl alcohol; CH3.(CH2)18. CH2OH) seems to occur widely Fag. Fagus sylvatica (bk-wax) Bux. Simmondsia californica (sd-wax) Anacardi. Rhus succedanea (japan wax, free ?)

ALCOHOLS I09

Plumbagin. Plumbago rosea (rtbk ?) Comp. Artemisia vulgaris (1f-wax) Palmae. Raphia Gram. Triticum sativum (oil) Heneicosyl alcohol (Heneicosan-s-ol; CH3 .(CH2)19. CH2OH): no records Docosyl alcohol (Docosan-s-ol; CH3 .(CH2)20 .CH2OH) Bux. Simmondsia californica (sd-wax, as ester) Solan. Mandragora autumnalis (rt) Tricosyl alcohol (Tricosan-i-ol; CH3.(CH2)21 .CH2OH): no records Tetracosyl alcohol (Tetracosan-I-ol; Lignoceryl alcohol; CH3 . (CH2)22. CH2OH) Chenopodi. Spinacia oleracea (as ester ?) Maly. Gossypium (cotton) Palmae. Copernicia cerifera (carnauba-wax, as ester) Gram. Dactylis glomerata (wax) Pentacosyl alcohol (Pentacosan-s-ol; CH3. (CH2)23. CH2OH) : no records Hexacosyl alcohol (Hexacosan-I-ol; Ceryl alcohol; CH3 .(CH2)24. CH2OH) occurs free (?) and in many waxes Chenopodi. Spinacia oleracea (wax ?) Magnoli. Michelia compressa (lys) Berberid. Epimedium macranthum (lys) Aristolochi. Aristolochia indica (rt) Papaver. Papaver (?` ceryl alcohol') Crucif. Brassica oleracea (1f-wax) Ros. Malus (apple-peel; wax?) Legum. Gleditsia horrida (sd, etc.) Euphorbi. Cluytia similis (1f-wax) Anacardi. Rhus succedanea (japan wax) Rhamn. Ceanothus (` ceryl alcohol') Onagr. Chamaenerion angustifolium (plt), Epilobium obscurum (plt) Comp. Chrysanthemum cinerariaefolium (fl.-wax), Lactuca sativa (1f-oil) Palmae. Copernicia cerifera (carnauba• wax; as ester ?) Gram. Dactylis glomerata (wax), Lolium perenne (wax), Triticum sativum (wax) Heptacosyl alcohol (Heptacosan-I-ol; CH3. (CH2)25. CH2OH) Ros. Malus (apple-wax) Cucurbit. Citrullus colocynthis (frt) Octacosyl alcohol (Octacosan-s-ol; CH3.(CH2)20 .CH2OH; Cluytyl alcohol) Santal. Santalum album (If-wax) Cact. Opuntia sp. (wax)

II0 CHEMOTAXONOMY OF FLOWERING PLANTS

Crucif. Brassica (1f--wax) Ros. Malus (apple-wax) Euphorbi. Cluytia similis (free and as ester) Palmae. Copernicia cerifera (carnauba-wax), Raphia ruffia (wax) Gram. Triticum (wax) Mus. Musa sapientum (wax) Nonacosyl alcohol (Nonacosan-I-ol; CH3.(CH2)27 . CH2OH) Ros. Malus (apple-wax) Triacontyl alcohol (Triacontan-I-ol; Myricyl alcohol; Melissyl alcohol; CH3. (CH2)26 . CH2OH) occurs chiefly in waxes. It is reported from conifers and Santal. Santalum album (If-wax) Cact. Opuntia sp. (wax) Crucif. Brassica spp. (wax) Ros. Malus (apple-wax) Leg. Medicago sativa Of-wax) Euphorbia. Euphorbia antisyphilitica (candelilla wax) Anacardi. Rhus succedanea (japan wax) Eric. Arbutus unedo (leaf) Solan. Mandragora (combined) Gram. Saccharum (wax) Palmae. Copernicia cerifera (carnauba-wax; free and combined ?), Raphia (wax) Hentriacontyl alcohol (Hentriacontan-I-ol; CH3 .(CH2)29 .CH2OH): no records Dotriacontyl alcohol (Dotriacontan-i-ol; Lacceryl alcohol; CH3. (CH2)30. CH2OH) occurs in many plant waxes Eric. Arbutus unedo (leaf, free ?) Palmae. Copernicia cerifera (carnauba-wax, free and combined) Tritriacontyl alcohol (Tritriacontan-I -ol ; CH3.(CH2)31.CH2OH): no records Tetratriacontyl alcohol (Tetratriacontan-I-ol; CH3.(CH2)32 •CH2OH) Euphorbi. Euphorbia antisyphilitica (candelilla-wax) Maly. Gossypium (wax) I . 1. b Other saturated alcohols GENERAL These are few in number and seem to have no chemotaxonomic value, but several of them are known only from single sources and it is possible that increased knowledge of their occurrence will yield results useful to the chemotaxonomist. We have arranged them in alphabetical order.

ALCOHOLS III

List and Occurrence Heptacosan-14-ol (Dimyristyl-carbinol; [CH3(CH2)12]2 • CHOH) Papaver. Corydalis aurea (combined) Heptan-z-ol (Methyl-n-amyl-carbinol; I-Methyl-hexyl alcohol; CH3. (CH2)4 . C(CH3)HOH) Myrt. Eugenia caryophyllata (oil of cloves) Isoamyl alcohol (3-Methyl-butan-I -ol ; CH(CH3)2 . CH2 . CH2OH) occurs free and as esters Ros. Fragaria (frt), Rubus idaeus (frt) Gerani. Pelargonium (ess. oil) Myrt. Eucalyptus (ess. oil) Lab. Mentha piperita (oil), Lavandula (oil) Isobutyl alcohol (CH3)2CH. CH2OH Comp. Anthemis nobilis (oil) Methyl-diheneicosyl-methanol (CH3. C(C21H43)2.OH) Gerani. Erodium cicutarium d-3-Methyl-pentan-I-ol (CH3. CH2. CH(CH3) . CH2 . CH2OH) Gerani. Pelargonium (ess. oil) Lab. Mentha arvensis v. piperascens (ess. oil) Nonacosan-Io-ol (Ginnol; CH3 . (CH2)8. CH(OH). (CH2)18 . CH3) occurs in Ginkgo and other gymnosperms and Papaver. Papaver somniferum (opium) Ros. Malus (apple-wax; d-) Nonacosan-i5-ol Crucif. Brassica oleracea v. gemmifera Eric. Arbutus unedo (st-wax) Nonan-2-ol (Methyl-n-heptyl-carbinol; CH3 . (CH2)8. CH(OH). CH3) Rut. Ruta (oil; l-) Myrt. Eugenia caryophyllata (oil of cloves) Octan-z-ol (Methyl-n-hexyl-carbinol) Gerani. Pelargonium (ess. oil) d-Octan-3-ol (d-Ethyl-n-amyl-carbinol) Lab. Lavandula vera (ess. oil); Mentha arvensis v. piperascens (ess. oil), piperita, pulegium (ess. oil; free and as ester) Tricosan-I2-o1 (Diundecyl-carbinol; [CH3. (CHz)10]2 • CHOH) Comp. Artemisia vulgaris (leaf-wax) Undecan-2-ol (Methyl-n-nonyl-carbinol) Laur. Litsea odorifera (leaf-oil; l-) Rut. Ruta (oil; i-)

I12 CHEMOTAXONOMY OF FLOWERING PLANTS

II. I . c Unsaturated monohydric alcohols GENERAL We have excluded the acetylenic alcohols (see p. 85). As treated here we have a small but mixed group showing no obvious chemotaxonomic value. List and Occurrence Allyl alcohol (Prop-z-en-1-ol; CH2 =CH.CH2OH) Martyni. Martynia diandra (sd-oil) 1-n-Amyl-vinyl-carbinol (l-Oct-I-en-3-ol; CH3. (CH2)4. C(CH _ CH2) HOH) occurs in fungi, conifers and Lab. Lavandula vera (ess. oil); Mentha pulegium (ess. oil), timija (ess. oil) Bixol (4,7,10,13-Tetramethyl-tetradec-3,6,9,12-tetraen-I-ol) Bix. Bixa orellana (sd) But-2-en-I-ol (Crotyl alcohol; Crotonyl a.; CH3. CH = CH. CH2OH) Crucif. Brassica napus (sd) But-3-en-I-ol (CH2 = CH . CH2 . CH2OH) Crucif. Brassica napus (sd) I,5-Dimethyl-hex-4-en-I-ol (z-Methyl-hept-z-en-6-ol) Laur. Litsea zeylanica (leaf-oil ?) Burser. Bursera delpechiana (ess. oil ?) Docos-13-en-I-ol Bux. Simmondsia californica (sd) Eicos-1I-en-1-ol Bux. Simmondsia californica (sd) cis-Hex-3-en-I -ol (CH3. CH2. CH : CH . CH2 . CH2OH) seems to be widely spread in leaves. Karrer (1958) says: `Seither wurde dieser Alcohol aus vielen grünen Blättern, in denen er meist frei vorkommt, isoliert.' Ros. Rubus idaeus (frt) Rut. Citrus paradisi (frt) I-Methyl-dec-9-en-I-ol (l-Undec-I-en-to-ol) Laur. Litsea odorifera (lvs; ess. oil) Nona-z,6-dien-I-ol Viol. Viola odorata (lvs, fl.) Cucurbit. Cucumis sativus

ALCOHOLS I13 TABLE 4. Aliphatic alcohols of waxes of a few plants

(various authors) Number of C atoms Plants Simmondsia (liquid seed-wax) Copernicia (Carnauba-wax, leaf) Cluytia Malus (Apple-wax, fruit) Euphorbia (Candelilla-wax)

20 2I 22 23 24 25 z6 27

28 29 30 31 32

33

34

+ . + . + . + . + . + . + . . + + +++++. . +

+

I.2 Dihydric aliphatic alcohols GENERAL These are few in number. Almost all of them are a,w-diols. There is some evidence that they may prove, like the alkanes, to be of some chemotaxonomic significance. List and Occurrence Ethylene glycol (Ethane-1,2-diol; CH2OH.CH2OH; fig. 7) may be considered to be the second in the series of `sugar-alcohols'. It is surprising, in view of the ubiquity of fats which are esters of glycerol, a trihydric alcohol, that no similar esters of this dihydric alcohol seem to be known. I have no record of the occurrence of ethylene glycol in higher plants. Dodecan-I,12-diol (CH2OH.(CH2)10 . CH2OH) is known from conifers Hexadecan-i,i6-diol (CH2OH . (CH2)14 . CH2OH) is known from conifers Octadecan- i, r 8-diol (CH2OH . (CH2)16 . CH2OH) Legum. Spartium junceum (fl.) Docosan-r,22-diol (CH2OH . (CH2)20 . CH2OH) Palmae. Copernicia cerifera (carnauba-wax, free ?) Tetracosan-I,24-diol (CH2OH . (CH2)22. CH2OH) Palmae. Copernicia cerifera (carnauba-wax, free ?)

I14. CHEMOTAXONOMY OF FLOWERING PLANTS

Hexacosan-I,26-diol (CH2OH . (CH2)24. CH2OH) Legum. Spartium junceum (fl.) Palmae. Copernicia cerifera (carnauba-wax, free ?) Octacosan-I,28-diol (CH2OH . (CH2)26. CH2OH) Palmae. Copernicia cerifera (carnauba-wax) I-Methyl-propan-I,2-diol(Butan-2,3-diol; CH3. CHOW. C(CH3)HOH) is not in the above series. It is produced by micro-organisms and: Ros. Malus (ripe and over-ripe fruit)

I.3 Aliphatic polyols (Trihydric and up) GENERAL These alcohols are often called the `sugar-alcohols'. Actually methyl alcohol and ethylene glycol might be included as the first and second alcohols of the series. We have considered the `polyols' to start with glycerol. Hough and Stacey (1966), in a paper on the biosynthesis and metabolism of allitol and the sugar D-allulose in Itea, have given us a brief summary of our knowledge of some sugar alcohols. Plouvier (in Swain, 1963; and other papers) has contributed much to this knowledge.

I .3 . a Trihydric alcohols List and Occurrence Glycerol (Glycerine; fig. 7) is a constituent of fats and phosphatides and therefore presumably of universal occurrence. It occurs free (?) and/ or as glycosides in seaweeds. It is said to be free in Sterculi. Theobroma cacao (sd) Ole. Olea europaea (ripe olives) Palmae. Phoenix dactylifera (sap)

I .3 . b Tetrahydric alcohols (Tetritols) List and Occurrence Erythritol (fig. 7) occurs in algae, fungi, and lichens. It is also in: Gram. ? D-Threitol (fig. 7) is in large amount in a fungus (Armillaria mellea), but not (?) in higher plants.

ALCOI-HOLS I15

I . 3 . c Pentahydric alcohols (Pentitols) List and Occurrence Adonitol (Ribitol; fig. 7) is universally (?) present in plants as part of riboflavin. It occurs free in: Ranuncul. Adonis amurensis (to 4% of plt), vernalis (rt) Umbell. Bupleurum falcatum (rt) D-Arabitol (fig. 7) occurs in lichens but not (?) in higher plants.

I. 3 . d Hexahydric alcohols (Hexitols) List and Occurrence Allitol (fig. 7) has been investigated by Plouvier (1959), and more recently by Hough and Stacey (1966) who say: `The allitol content of Itea leaves increases considerably during photosynthesis whereas the converse is true during metabolism in the dark. Allitol is thought to function in a reserve capacity.' Saxifrag. Itea ilicifolia (]vs, st.), virginica (lvs, st.), yunnanensis (lvs, 6%); but not in Brexia and Escallonia Dulcitol (Dulcin; Dulcose; Euonymite; Galactite; Melampyrin; Melampyrite; fig. 7) has been studied by Plouvier (1949). It occurs in red algae, in fungi, and in

Laur. Cassytha Saxifrag. Brexia Celastr. at least 7 genera Hippocrate. Pristimera, Salacia, Tontelia Scrophulari. Melampyrum, Rhinanthus, Scrophularia Plouvier did not find it in: Rut., Simaroub., Meli., Rhamn., and Vit. D-Glucitol (D-Sorbitol; fig. 7) seems to have a restricted distribution. It is said to occur in algae, fungi, oak-galls and Ros. (many). Strain (1937) says: ' It thus appears that sorbitol [glucitol] may play the same role in the plants of the genus Rosacae [sic] that sugar alcohols play in the metabolism of some marine algae.' Solan. Nicotiana It has not been found in Jugland. (Juglans) ; Laur. (Umbellularia) ; Berberid. (Berberis) ; Papaver. (Eschscholtzia); Saxifrag. (Astilbe); Rut. (Citrus); Hippocastan. (Aesculus); Celastr. (Celastrus); Rhamn. (Rhamnus); Eric. (Arbutus); Solan. (Physalis); Caprifoli. (Symphoricarpos)

I16

CHEMOTAXONOMY OF FLOWERING PLANTS

CI H2OH CH,OH

CH,OH

CH,OH

CH ,OH

HCOH

HCOH

H2OH

HCOH CH,OH

Methyl alcohol CH,OH HO H I HO~H ( HOiH CH,OH

Ethylene glycol CH,OH

CH,OH HO

HOCH

HO

HCOH

CH,OI-I

CH,OH

H

HO I H

H

HO~(H

CH,OH HOCH

CH~

C H,OH Dulcitol

CH,

I

HCOF

HCOH

H~OH

HC

Hi

CH,OH

CH,OH

CH,OH

HOCH

HOCH

H OH

HOCH

HCOH

1-1,0H

CH,OH

o-Glucitol

t-iditol

CH,OH

CH,OH

HO I H

HOCH

HOH

HOCH

HiOH

HCOH

HCOH

HCOH

CH,OH o-Mannitol (Hexitol)

HCOH

HO H I HCOH

HCOH

H$OH

HOCH

CH,OH

(Hexitols)

Ö I H4OH J

HOCH

OH

HOCH

Allitol

CH,OH H OH

HCOH

HOCH CH,OH

Adonitol o-Arabltol (Pentitols)

H OH C CH,OH

Erythrltol o-Threitol (Tetritols)

Glycerol

HOCH

CH, OH HOCH

Polygalitol Styracitol (Anhydrohexicols)

CH,OH

D-Volemltol (Heptltols)

D-Persettol

Fig. 7. Aliphatic alcohols.

L-Iditol (Sorbierite; fig. 7) Ros. Sorbus aucuparia (frt) D-Mannitol (Manna sugar; Mannite; fig. 7) seems to be widely distributed. It is recorded from algae, fungi, conifers, and Salle. (Populus); Caryophyll. (Dianthus); Cact. (Opuntia); Canell. (Canella, Warburgia); Laur. (Laurus, Cinnamomum); Ranuncul. (Aconitum); Platan. (Platanus); Legum. (at least 6 genera); Elaeagn. (Hippophae); Lythr. (Lawsonia); Punic. (Punica); Umbell. (Apium, Daucus, Meum); Ole. (general); Rubi. (Basanacantha, Coffea, Genipa, Pavetta) ; Convolvul. (Ipomoea) ; Verben. (Clerodendron) ; Scrophulari. (general?); Orobanch. (Orobanche); Myopor. (Myoporum) ; Comp. (Scorzonera) ; Lili (Allium) ; Bromeli. (Ananas) ; Gram. (Agropyrum, Andropogon, Triticum); Palmae. (Phoenix); Cyper. (Carex) Two anhydro-hexitols (which have only 4 free -OH groups) are known and may be included here.

ALCOHOLS I17

Polygalitol (Acerite; Aceritol; I,5-Anhydro-n-glucitol; fig. 7) is known only (?) from: Prote. Protea (8) Polygal. Polygala spp. Acer. Acer (from acertannin) Styracitol (I,5-Anhydro-n-mannitol) is known only (?) from: Styrac. Styrax obassia (frt)

I .3 . e Heptahydric alcohols (Heptitols) D-Perseitol (n-a-Mannoheptitol; D-Manno-ngala-heptitol; fig. 7) is known only (?) from: Laur. Persea gratissima (fit) D-Volemitol (a-Sedoheptitol; fig. 7) is known from algae, fungi (Lactarius volemus), lichens, and Primul. Primula spp.

II AROMATIC ALCOHOLS GENERAL As is usually the case, we have difficulties in classification. Some of the aromatic alcohols included here, such as coniferyl alcohol and salirepol, are also phenols. Where should they go ? List and Occurrence Anethol-glycol (ß-(p-Methoxyphenyl)-a-methyl-ß-hydroxy-ethyl alcohol) Rut. Ruta montana (ess. oil) Anisalcohol (4-Methoxy-benzyl alcohol) Umbell. Pimpinella anisum (sd-oil) Orchid. Vanilla Benzyl alcohol (Phenyl-carbinol) is said to occur free and/or as esters in: Caryophyll. Dianthus Annon. Cananga odorata (fl.-oil) Legum. Acacia farnesiana (fl.-oil) Viol. Viola odorata (oil) Myrt. Eugenia caryophyllata (clove-oil) Ole. Jasminum (fl.-oil)

I18 CHEMOTAXONOMY OF FLOWERING PLANTS

CH OH

H3C-CHOH

CH2OH

CH-CH2OH

~ OH

OH

OH

OH

Salicyl

3,4-Dihydroxy

oC (p Tolyl)-

A-(p-Hydroxy-

alcohol

-benzyl-alcohol

-ethyl alcohol

phenyl) ethyl alcohol

CH2OH

CH2OH

CH2 OH

CH

CH u CH

CH

CH

CH

O OH

''OCH 3

Cinnamyl

Coniferyl

alcohol

alcohol

H3CO

OCHS

OH Syringenin

Fig. 8. Some aromatic alcohols.

Lili. Hyacinthus Agay. Polianthes tuberosa Amaryllid. Narcissus Betuligenol (y-(p-Hydroxyphenyl)-a-methyl-propyl alcohol ;l p-Hydroxyphenyl-butan-3-ol; Rhododendrol) is the aglycone of betuloside. Betul. Betula alba (bk; free?; to 25% of cork layer) Eric. Rhododendron chrysanthum (lys) Cinnamyl alcohol (fig. 8) occurs as esters in many plants. Salic. Populus balsamifera (buds, combined?) Laur. Cinnamomum zeylanicum (lys; free and combined) Lili. Hyacinthus (fl.-oil; free and combined) Xanthorrhoe. Xanthorrhoea hastilis (resin) Amaryllid. Narcissus (fl.-oil) Coniferyl alcohol (fig. 8) is the aglycone of coniferin. Is it a lignin unit ? 3,4-Dihydroxy-benzyl alcohol (fig. 8) occurs (as glycoside only ?) in: Ros. Prunus lusitanica (lys), Pyrus calleryana (lys) ß-(3,4-Dihydroxyphenyl)-ethyl alcohol is the aglycone of echinacoside. ß-Phenyl-ethyl alcohol occurs free and/or as esters in: Salic. Populus balsamifera (bud) Caryophyll. Dianthus caryophyllatus (fl.-oil)

ALCOHOLS I19

Magnoli. Michelia champaca (fl.-oil) Annon. Cananga odorata (fl.-oil) The. Thea (If-oil) Ros. Rosa (fl.-oil); Rubus idaeus (frt?) Gerani. Pelargonium (oil) Rut. Citrus (fl.-oil) Lili. Hyacinthus (fl.-oil), Lilium (fl.-oil) Amaryllid. Narcissus (fl.-oil) Y(3)-Phenyl-propyl alcohol Hamamelid. Liquidambar (storax; free and as ester) Styrac. Styrax Salicyl alcohol (Saligenin; Saligenol; fig. 8) Salic. Populus balsamifera (lvs, bk) Salirepol (Gentisic alcohol) occurs in fungi ? It is the aglycone of salireposide. Syringenin (Sinapinic alcohol; fig. 8) is the aglycone of syringin. The syringyl group occurs in lignin of angiosperms and some gymnosperms. Does syringenin occur free in woody dicotyledons ? a-(p-Tolyl)-ethyl alcohol (fig. 8) Zingiber. Curcuma longa (rhiz.-oil, 5%) ß-(p-Hydroxyphenyl)-ethyl alcohol (Tyrosol; fig. 8) Ole. Osmanthus fragrans v. auranticus (fl.)

III PHENOLS GENERAL We have placed phenols here because some of the alcohols treated in the previous section are at the same time phenols, and because the phenols themselves resemble the true tertiary alcohols. Some of the a,w-diphenyl-alkanes are phenols. While it may seem artificial to separate the phenols from the phenol ethers we have come across strange cases of distribution which would seem to support such separation. For example: Eugenol Eugenol-methyl ether Mor. Cannabis Annon. Cananga Monimi. Atherosperma Laur. Cinnamomum zeylanicum, Laur. Cinnamomum oliveri Cryptocarya, Dicypellium Piper. Piper Aristolochi. Asarum Ros. Rosa Legum. Acacia

I20 CHEMOTAXONOMY OF FLOWERING PLANTS

Myrt.

Eugenia, Pimenta (z)

Myrt. Melaleuca (2), Pimenta Lili. Hyacinthus Arac. Acorus calamus

Isoeugenol Magnoli. Michelia Annon. Cananga Myristic. Myristica Laur. Cinnamomum, Nectandra Ros. Prunus Rubi. Leptactinia

Isoeugenol-methyl ether Aristolochi. Asarum Myrt. Backhousia, Melaleuca Lab. Orthodon Gram. Cymbopogon

Hydroquinone-methyl ether Pyrol. Pyrola

Hydroquinone-dimethyl ether Lili. Hyacinthus

Only in the cases of the Lauraceae and Myrtaceae are the phenol and its phenol ether found in the same family and only in the latter family is the same species involved (Pimenta). Do these records really reflect the distributions of these compounds or have we again examples which illustrate our ignorance ? I am afraid it is the latter! List and Occurrence Allyl-catechol (Allyl-pyrocatechol; fig. 189) Piper. Piper betle (1f-oill 4.-Allyl-2,6-dimethoxy-phenol (Methoxy-eugenol) Myristic. Myristica fragrans Antiarol (I,2,3-Trimethoxy-5-hydroxy-benzene) Mor. Antiaris toxicaria (latex) Catechol 0,2,-Dihydroxy-benzene; Pyrocatechol; fig. 9) seems at first sight to be rather widely spread, usually in combination, but I have a very extensive list of reported absences Salic. Populus (free in 7 species), Salix (free) Chenopodi. Beta (some doubt of this) Guttif. Psorospermum guineense (bk, > 9%) Platan. Platanus (some doubt of this) Rut. Citrus paradisi (Ivs, frt) Vit. Ampelopsis hederacea Oils) Lili. Allium (bulb) It has not been found in Myric. (Myrica); Jugland. (Carya, Juglans); Betul. (Alnus, Betula); Fag. (Fagus, Quercus); Ulm. (Zelkova); Eucommi. (Eucommia); Mor. (Humulus, Morus); Loranth. (Viscum); Polygon. (Polygonum, Rumex); Caryophyll. (Stellaria); Magnoli. (Magnolia); Annon.

ALCOHOLS I21

(Asimina); Schisandr. (Schisandra); Calycanth. (Calycanthus); Laur. (Lindera); Euptele. (Euptelea); Cercidiphyll. (Cercidiphyllum); Ranuncul. (Galtha); Berberid. (Berberis); Lardizabal. (Akebia); Aristolochi. (Aristolochia); Actinidi. (Actinidia); Guttif. (Hypericum); Papaver. (Chelidonium, Eschscholtzia); Crucif. (Brassica); Hamamelid. (Liquidambar); Saxifrag. (Deutzia, Philadelphus); Ros. (Amygdalus, Malus, Prunus, Pyrus); Legum. (Caragana, Lupinus, Robinia, Sophora) ; Gerani. (Erodium ?) ; Tropaeol. (Tropaeolum) ; Euphorbi. (Euphorbia, Securinega); Rut. (Evodia); Simaroub. (Ailanthus); Anacardi. (Rhus); Acer. (Acer); Hippocastan. (Aesculus); Aquifoli. (Ilex); Celastr. (Euonymus); Staphyle. (Staphylea); Bux. (Buxus); Rhamn. (Rhamnus); Vit. (Vitis); Tili. (Tilia); Thymelae. (Daphne); Elaeagn. (Hippophae); Stachyur. (Stachyurus); Tamaric (Myricaria); Davidi. (Davidia); Corn. (Cornus); Arali. (Acanthopanax, Hedera) ; Umbell. (Aegopodium) ; Eric. (Erica, Gaylusaccia, Rhododendron) ; Primul. (Primula) ; Plumbagin. (Armeria); Eben. (Diospyros); Styrac. (Styrax); Ole. (Fraxinus, Syringa); Asclepiad. (Periploca); Convolvul. (Convolvulus); Lab. (Elsholtzia, Lamium); Solan. (Lycium, Solanum); Bignoni. (Catalpa); Plantagin. (Plantago); Caprifoli. (Lonicera, Sambucus); Comp. (Achillea, Taraxacum); Lili. (Asparagus); Trid. (Iris); Gram. (Phragmites); Lemn. (Lemna); Typh. (Typha) Chavibetol (fig. 189) Piper. Piper betle (1f-oil) Chavicol (r-(p-Hydroxyphcny1)-prop-2-ene; fig. 189) is the aglycone of lusitanicoside. Piper. Piper (Chavica) betle (ess. oil) Rut. Barosma venustum (lvs) Myrt. Pimenta acris (lvs), racernosa (lvs) Lab. Origanum majorana (plt) Zingiber. Zingiber officinale Creosol (Homoguaiacol; 1-Methyl-3-methoxy-4-hydroxy-benzene) Annon. Cananga odorata (fl.-oil) Umbell. Pimpinella anisuro (sd-oil) Ole. Jasminum (fl.-oil) m-Cresol (1-Methyl-3-hydroxy-benzene) The. Thea (1f-oil) Comp. Artemisia transiliensis (ess. oil) p-Cresol (1-Methyl-4-hydroxy-benzene) has been recorded from conifers and, in small amount, from The. Thea (lvs) Legum. Acacia farnesiana (fl.) Rut. Citrus (fl.)

I22 CHEMOTAXONOMY OF FLOWERING PLANTS

Umbell. Pimpinella anisum (frt) Eric. Ledum palustre v. dilatatum (1f-oil) Ole. Jasminum (fl.-oil) Comp. Gnaphalium arenarium Lili. Lilium candidum (fl.) Ethyl-guaiacol (I-Ethyl-3-methoxy-4-hydroxy-benzene) Laur. Cinnamomum camphora o-Ethyl-phenol (I-Ethyl-2-hydroxy-benzene) Anacardi. Schinus molle (oil; much) Eugenol (Allyl-guaiacol; fig. 9) occurs sometimes as acetate. Mor. Cannabis sativa Laur. Cinnamomum zeylanicum (1f-oil ?), Dicypellium caryophyllatum, Cryptocarya (Cinnamomum) massoy (bk-oil; 75%) Myrt. Eugenia caryophyllata (oil of cloves; 95%); Pimenta acris (oil), officinalis (oil) Lab. Ocimum gratissimum (If-oil; 6o%), sanctum (if-oil; 70%) Guaiacol (I-Hydroxy-2-methoxy-benzene; fig. 9) seems to be widely distributed (free ?) : Mor. Cannabis sativa Zygophyll. Guaiacum officinale (resin) Rut. Citrus (fl.-oil), Ruta montana (oil) Acer. Acer saccharum (sap) Umbell. Apium graveolens (sd-oil) Solan. Nicotiana tabacum (if-oil) Pandan. Pandanus odoratissimus (fl.-oil) Hydroquinone (I,4-Dihydroxy-benzene) occurs mostly combined. It is the aglycone of arbutin. Prote. Protea mellifera (lvs, 2-5%) Saxifrag. Bergenia ; Hydrangea ? ; but not in Escallonia, Heuchera, Philadelphus, Ribes, Rodgersia Ros. Pyrus communis (1f-bud), Rubus fruticosus (lvs) Umbell. Pimpinella anisum (sd) Eric. Arbutus unedo (Ivs), Rhododendron sp. (lvs), Vaccinium vitis-idaea (lvs, fl.) Comp. Xanthium canadense (sd) Hydroquinone-ethyl ether Illici. Illicium anisatum (frt), verum Rut. Empleurum serrulatum (If-oil) Hydroquinone-methyl ether (fig. 9) Pyrol. Pyrola secunda (lvs) Isoeugenol Magnoli. Michelia champaca (fl.-oil) Annon. Cananga odorata (fl.-oil)

ALCOHOLS I23

OH

9 OH

P-OH ?OCH3 OH

OH

Et?)

OCH3

OCH 3

Phenol Catechol Guaiacol Hydroquinone- Eugenol -methyl ether

Fig. 9. Some phenols. Myristic. Myristica fragrans (sd-oil) Laur. Cinnamomum, Nectandra puchury (sd-oil) Ros. Prunus domestica (fl.) Rubi. Leptactinia senegambica (fl.-oil) p-Isopropyl-phenol (Australol) Myrt. Eucalyptus Methoxy-hydroquinone is known only (?) as glycoside. Phenol (Hydroxy-benzene; fig. g) is reported from a conifer and Salic. Salix (bk, free ?) The. Thea (lys) Saxifrag. Ribes nigrum (shoot, free ?) Rut. Ruta montana (ess. oil) Solan. Nicotiana tabacum (lys) Comp. Artemisia annua (ess. oil) Phloroglucin (i,3,5-Trihydroxy-benzene) is often in combination. It is reported (free ?) from conifers and Caryophyll. Lychnis dioica m-Phlorol (i-Ethyl-3-hydroxy-benzene) Comp. Arnica montana (rt) Pyrogallol (I,2,3-Trihydroxy-benzene) can be obtained from many tannins. It occurs free (?) in conifers but not (?) in angiosperms. Pyrogallol-I,3-dimethyI ether Comp. Artemisia herba-alba v. densifiora (ess. oil) Pyrolagenin is the aglycone of pyrolatin. Sesamol (I-Hydroxy-3,4-methylenedioxy-benzene) Pedali. Sesamum indicum (oil) p-Vinyl-phenol is the aglycone of furcatin.

I24 CHEMOTAXONOMY OF FLOWERING PLANTS

IV PHENOLIC ESTERS AND ETHERS GENERAL Once again we find a distinction between the Magnoliales and Ranunculales (sensu Syll. 12, 1964), the former being rich in these substances, the latter virtually lacking them (if our records are representative).

List and Occurrence I-Allyl-2,3,4,5-tetramethoxy-benzene Umbell. Petroselinum sativum (oil) Anethole (fig. To) Piper. Piper peltatum Magnoli. Magnolia salicifolia (If-oil; to 73%) Illici. Illitium anisatum (little), verum (oil; to 88%) Rut. Clausena anisata (1f-oil; to 89%) Burser. Canarium commune Myrt. Backhousia anisata (1f-oil) Umbell. Foeniculum vulgare, Pimpinella arrsum (sd-oil; to 85%) Lab. Ocimum basilicum Apiole (1-Allyl-2,5-dimethoxy-3,4-methylenedioxy-benzene; fig. 189) Laur. Licaria (Misanteca) sp. (bk, wd), Ocotea sp. (bk, wd) Piper. Piper angustifolium (1f-oil) Umbell. Apium?, Crithmum maritimum (rt, ess. oil; to 6o%), Petroselinum sativum Asarone (fig. I o) Piper. Piper angustifolium (oil) Aristolochi. Asarum arifolium (rt), caudatum (rt), europaeum (rt) Umbell. Daucus carota (sd-oil) Lab. Orthodon asaroniferum (ess. oil) Arac. Acorus calamus, gramineus (rt-oil) ß-Asarone is the cis-trans- isomer of asarone. Arac. Acorus calamus (it-oil) Calamol (C6H2 . (OCH3)3. CH2 . CH=CH2) Arac. Acorus calamus (rt-oil) Coniferyl-benzoate (Lubanol-benzoate) Styrac. Styrax benzoin (gum, chief constit.) p-Coumaric acid-methyl ether is the aglycone of linocinnamarin. p-Cresol-methyl ether Annon. Cananga odorata (fl.-oil) Crocatone (5-Methoxy-3,4-methylenedioxy-propiophenone) Umbell. Oenanthe crocata

ALCOHOLS I25

Croweacin Rut. Eriostemon crowei (If-oil) Dill-apiole (I-Allyl-5,6-dimethoxy-3,4-methylenedioxy-benzene) is isomeric with apiole. Monimi. Laurelia serrata (If and st.-oil) Laur. an unnamed member (wd-oil) Piper. Piper (angulatum ?) (1f-oil) Umbell. Anethum graveolens (frt-oil), sova (frt-oil); Crithmum nzaritimum (frt-oil); Ligusticum scoticum (frt-oil) Lab. Orthodon formosanus (sd-oil ; to 65%) 3,4-Dimethoxy-cinnamic acid Scrophulari. Veronicastrum (Veronica) virginicum (rhiz.) Elemicin (fig. to) seems to be widely spread Laur. Cinnamomum glanduliferum (wd-oil) Rut. Boronia muelleri, pinnata, thujona (oils; to 90%); Zieria smithii (ess. oil) Burser. Canarium commune (resin) Myrt. Backhousia myrtifolia (ess. oil), Melaleuca bracteata (ess. oil) Lab. Orthodon elemiciniferunz Gram. Cymbopogon goeringii (ess. oil; 57%), procerus (ess. oil; 35%) Esdragol (Estragol; Isoanethole; Methyl-chavicol) Illici. Illicium Laur. Persea gratissima (bk) Ethyl-gallate Eric. Arbutus unedo Eugenol-acetyl-salicylic acid ester Myrt. Eugenia Eugenol-methyl ether Annon. Cananga odorata Monimi. Atherosperma moschatum (lvs) Laur. Cinnamomum oliveri (lvs) Piper. Piper betle (lvs) Aristolochi. Asarum canadense (rt; much), europaeum (rt; much) Ros. Rosa (fl.) Legum. Acacia farnesiana (fl.) Myrt. Melaleuca bracteata (lvs, ess. oil; to 9S%), leucadendron; Pimenta Lili. Hyacinthus (fl.) Arac. Acorus calamus (Japan) Eugenone (z,4,6-Trimethoxy-benzoyl-acetone) Myrt. Eugenia caryophyllata

I26 CHEMOTAXONOMY OF FLOWERING PLANTS

Foeniculin Illici. Illicium Umbell. Foeniculum vulgare Gentisic acid-benzyl ester Salic. Populus Hydroquinone-dimethyl ether Lili. Hyacinthus (fl.-oil) z-Hydroxy-4-methoxy-benzoic acid-methyl ether (Primula-camphor) occurs free (?) and as glycoside. Primul. Primula officinalis (rt & fl.-oil), veris (rt), viscosa (rt; as primverin) 2-Hydroxy-5-methoxy-benzoic acid-methyl ether occurs free (?) and as primulaverin. Primul. Primula acaulis (rt; as primulaverin), auricula (rt; free ?), officinalis (rt; free ?) Iso-elemicin Myristic. Myristica fragrans (sd-oil) Myrt. Backhousia myrtifolia (1f-oil) Isoeugenol-methyl ether Aristolochi. Asarum arifolium Myrt. Backhousia myrtifolia (1f-oil), Melaleuca bracteata (1foil) Lab. Orthodon methylisoeugenoliferum (sd-oil; 53%) Gram. Cymbopogon javanensis (ess. oil) Isomyristicin Myristic. Myristica Umbell. Anethum graveolens (ess. oil) Isosafrole Annon. Cananga odorata Illici. Illicium religiosum (frt) Umbell. Ligusticum acutilobum (rt-oil) Methyl gallate Anacardi. Cotinus coggygria (lvs) Myrt. Metrosideros excelsa (fl.) Methyl salicylate (Salicylic acid-methyl ester; fig. 438) occurs usually as glycoside. The following list includes records of occurrence, both free and combined, largely from the early work of van Romburgh (1899) in the tropics Betul. (Betula); Fag. (Quercus (3)); Mor. (Conocephalus, Ficus); Chenopodi. (Chenopodium); Myristic. (Myristica); Calycanth. (Calycanthus); Laur. (Lindera); Ranuncul. (Clematis); Menisperm. (Cocculus); The. (Camellia); Saxifrag. (Ribes); Ros. (Fragaria, Photinia, Prunus, Rubus); Chrysobalan. (Parinari); Legum. (at least

ALCOHOLS I27

22/44); Erythroxyl. (Erythroxylum (4)); Euphorbi. (Bridelia (2), Baccaurea, Cyclostemon (3), Macaranga); Rut. (Atalantia, Glycosmis (2), Murraya); Burser. (Garuga); Polygal. (Comesperma ericinum (rt; prob. free), Polygala (7), Xanthophyllum (2?); Sapind. (at least 5-6/7-8); Sabi. (Meliosma?); Staphyle. (Turpinia); Icacin. (Platea (2)); Rhamn. (Alphitonia, Ceanothus, Paliurus); Vit. (Vitis); Elaeocarp. (Elaeocarpus);Flacourti. (Homalium (2), Hydnocarpus (3), Ryparosa (2), Scolopia, Taraktogenos); Viol. (Alsodeia); Myrt. (Eugenia, Metrosideros); Lecythid. (Barringtonia (2)); Rhizophor. (Carallia (I)); Pyrol. (Monotropa); Eric. (Gaultheria); Epacrid. (Styphelia tubiflora (lys; prob. free)); Myrsin. (Ardisia (7)); Sapot. (Sideroxylon); Eben. (Diospyros (4), Maba (2)); Symploc. (Symplocos (2)); Ole. (Linociera (I-2), Nyctanthes); Apocyn. (Alstonia, Chilocarpus, Hunteria); Asclepiad. (Cryptolepis, Marsdenia); Rubi. (at least 10/20); Bignoni. (Bignonia (2), Nyctocalos, Tabebuia); Acanth. (Thunbergia); Caprifoli. (Viburnum); Comp. (Stifftia, Vernonia); Gram. (Dendrocalamus) Myristicin (fig. I o) may be psychotropic (Shulgin, 1966) Myristic. Myristica fragrans (sd), and other spp. ? Laur. Cinnamomum glanduliferum (wd) Umbell. Anethum graveolens (oil), Carum (Ridolfia) segetum (fl.-oil; 33%), Levisticum scoticum (rhiz.; much), Oenanthe stolonifera (frt), Pastinaca sativa (plt; little), Petroselinum sativum (ess. oil), Peucedanum graveolens (oil) Lab. Orthodon asaroniferum, grosseserratum, hirtus (little) Phaselic acid (Malic ester of caffeic acid) Legum. Phaseolus m-Phlorol-isobutyrate Comp. Arnica montana (rt) m-Phlorol-methyl ether Comp. Arnica montana (rt) Pipataline (fig. 189) Piper. Piper peepuloides (frt) Quinic acid-I,4-dip-coumarate Bromeli. Ananas Safrole (Shikimol; fig. Io) Annon. Cananga odorata Illici. Illitium parviflorum (oil; 90%), religiosum (lys) Monimi. Doryphora sassafras (bk, lys, frt ?), Nemuaron humboldtii (ess. oil; 99%) Laur. Beilsmiedia sp.; Cinnamomum (many); Ocotea cymbarum, pretiosa; Sassafras albidum Aristolochi. Asarum sp.

I28 CHEMOTAXONOMY OF FLOWERING PLANTS CH3 CH CH

CH3 CH CH

OCH3 H3CO

CH2

CH

CH

CH 612

CH2

CH2

0./

0

H3CO

I0

OCH3

H3CO

OCH3

Anethole

CH2 CH

• H3 OC H3

Asarone

Elemicin.

Myristicin

Safrole

Fig. to. Some phenolic ethers.

Sparassol (2-Hydroxy-4-methoxy-6-methyl-methyl benzoate) occurs in fungi, lichens, and Eric. Rhododendron japonicum (rtbk) I-Undecenyl-3,¢-methylenedioxy-benzene (fig. I89) Piper. Piper longum (frt)

ALDEHYDES GENERAL We have included here: I. Aliphatic aldehydes I. Saturated aliphatic aldehydes. 2. Unsaturated aliphatic aldehydes. II. Aromatic aldehydes (mostly phenolic) We have excluded terpenoid aldehydes such as citronella!, and aldehydes which are naphthalene derivatives.

I. I Saturated aliphatic aldehydes List and Occurrence Formaldehyde (Methanal; H. CHO) may occur in traces in many plants Chenopodi. Beta (lvs, rt) Lab. Monarda fzstulosa, punctata (1f-oil) Comp. Achillea millefolium (ess. oil) Acetaldehyde (Ethanal; CH3. CHO) has been reported (free ?) in many plants Betul. Carpinus betulus (lvs)

ALDEHYDES I29 Fag. Quercus (lvs) Laur. Cinnamomum camphora Crucif. Brassica Ros. Rosa canna, Pyrus germanica, Sorbus aucuparia Rut. Citrus Umbell. Carum carvi (oil), Foeniculum vulgare (oil), Pimpinella anisuro (oil) Lab. Mentha piperita (oil), Rosmarinus officinale Solan. Nicotiana tabacum (lvs) Propionaldehyde (Propanal; CH3. CH2 . CHO) has been reported from algae and a conifer, but not (?) from angiosperms. Butyraldehyde (Butanal; CH3. (CH2)2 . CHO) occurs (free ?) in Betul. Carpinus betulus (lvs) Fag. Quercus sessiliflora (lvs) Mor. Morus (lvs) Crucif. Raphanus Legum. Acacia (lvs) Myrt. Eucalyptus globulus (ess. oil), Melaleuca leucadendron (1f-oil) Lab. Lavandula delphinensis (oil), Monarda fistulosa (ess. oil) Comp. Artemisia scoparia (oil) Isobutyraldehyde (Isobutanal; (CH3)2CH.CHO) is reported from algae, conifers and Mor. Morus (lvs) Crucif. Raphanus Legum. Acacia (lvs) Solan. Datura stramonium?, Nicotiana tabacum (lvs) Valeraldehyde (Pentanal; CH3 . (CH2)3. CHO) Betul. Carpinus betulus (probably in lys) Fag. Quercus sessiliflora (lvs) Laur. Ocotea pretiosa (tr.) Myrt. Eucalyptus dives, globulus?; Melaleuca leucadendron? Isovaleraldehyde (3-Methyl-butanal; (CH3)2 . CH . CH2. CHO) is a hemiterpenoid. Fag. Quercus sessiliflora (lvs) Laur. Cinnamomum camphora Legum. Glycine max Rut. Citrus Myrt. Eucalyptus globulus and other spp. Lab. Lavandula delphinensis, Mentha piperita, Monarda fistulosa Comp. Helichrysum italicum (ess. oil) Hexanal (Caproic aldehyde; CH3. (CH2)4. CHO) is reported from conifers and Fag. Quercus sessiliflora (lvs) 5 GCO

130 CHEMOTAXONOMY OF FLOWERING PLANTS

Laur. Cinnamomum camphora Myrt. Eucalyptus globulus Heptanal (Oenanthal; CH3 . (CH2)5. CHO) Annon. Cananga odorata (fl.-oil) Lill. Hyacinthus (fl.-oil ?) Octanal (Caprylic aldehyde; CH3.(CH2)O .CHO) is reported from conifers and Rut. Citrus (at least 3 spp.), Zanthoxylum rhetsa Lab. Lavandula delphinensis Gram. Cymbopogon winterianus Nonanal (CH3 . (CH2)7 . CHO) is reported from conifers and Ros. Rosa Rut. Citrus spp., Eremocitrus glauca Gram. Cymbopogon Zingiber. Zingiber officinalis Decanal (Capric aldehyde; CH3. (CH2)8 . CHO) is said to occur in conifers and Laur. Cinnamomum camphora, micranthum (ess. oil) Legum. Acacia cavenia?, farnesiana; Cassia Rut. Citrus bigaradia (oil) Umbell. Coriandrum sativum (oil) Lab. Lavandula Irid. Iris (rt-oil) Dodecanal (Lauryl aldehyde; CH3. (CH2)10 . CHO) occurs in conifers and Rut. Citrus bigaradia, medica v. acida Tetradecanal (Myristic aldehyde; CH3. (CH2)12. CHO) is reported from a conifer and Laur. Cinnamomum sp., Ocotea usambarensis (bk-oil) Pentadecanal (CH3. (CH2)13. CHO) Laur. Cinnamomum micranthum Octadecanal (Stearyl aldehyde; CH3 . (CH2)16 . CHO) is reported from lichens and Laur. Cinnamomum sp.

I.2 Unsaturated aliphatic aldehydes List and Occurrence a-Methyl-acrolein (Artemisal; Methacrolein; CH2=C(CH3). CHO) Comp. Artemisia tridentata (1f-oil) Hex-2-en-I-al (a-Hexenal; CH3. (CH2)2. CH=CH. CHO) has been called `leaf-aldehyde'. Karrer (1958) says: `Diirfte in allen chloro-

ALDEHYDES 131

phyllhaltigen Pflanzen vorkommen u. bei der Assimilation eine Rolle spielen.' Hept-2-en-I -al (ß-Butyl-acrolein; CH3. (CH2)3. CH=CH. CHO) Legum. Glycine max? Oct-2-en-i-al (CH3. (CH2)4. CH=CH. CHO) Zingiber. Achasma walang 8-Methyl-non-2-en- i -al Umbell. Coriandrum sativum Nona-2,6-dien-i-al Viol. Viola odorata (If-oil) Cucurbit. Cucumis sativus Deca-2,4-dien-I-al (CH3. (CH2)4 . CH=CH. CH=CH. CHO) Legum. Arachis hypogaea (oil), Glycine max (oil) Dec-2-en-i-al (CH3. (CH2)6 . CH=CH. CHO) Rut. Citrus Umbell. Coriandrum sativum (ess. oil) Zingiber. Achasma walang (oil of lys and rt) Dodec-2-en-i-al (CH3 . (CH2)8 . CH=CH. CHO) has been found in a millipede and in Rut. Citrus Umbell. Daucus carota, Eryngium foetidum (ess. oil; much) Zingiber. Achasma walang, Zingiber? 2-Methyl-dodec-2-en-i-al: from an unidentified seed-oil. Trideca-2,4-dien-I-al: see immediately above. Tridec-2-en-I-al: see immediately above. II AROMATIC ALDEHYDES (MOSTLY PHENOLIC) GENERAL Our knowledge of the distribution of aromatic aldehydes is so fragmentary that we can use it but little in chemotaxonomy. It is obvious that some plants of economic value, such as Cinnamomum and Vanilla, have been studied fairly fully. Many of the occurrences recorded result, too, from the close examination of essential oils. We may note one or two points of interest. (a) The order Magnoliales is represented in the following list by Magnoliaceae, Annonaceae, Illiciaceae, Monimiaceae, and Lauraceae. The Ranunculales is without representation. (b) The occurrence of 4-methoxy-salicylic aldehyde in the order Gentianales might prove of real interest. It has been reported from Apocynaceae (1) and from Asclepiadaceae (several genera, mostly closely related). Is it elsewhere in the order ? 5-2

132 CHEMOTAXONOMY OF FLOWERING PLANTS

List and Occurrence 3-Acetyl-6-methoxy-benzaldehyde Comp. Encelia farinosa (lvs) o-Anisaldehyde (Salicyl aldehyde-methyl ether; z-Methoxy-benzaldehyde) Laur. Cinnamomum cassia p-Anisaldehyde (4-Methoxy-benzaldehyde) results often from oxidation of anethole? It is reported from algae, fungi, conifers and Magnoli. Magnolia salicifolia (1f-oil) Illici. Illicium Legum. Acacia farnesiana (fl.-oil), Mimosa? Rut. Pelea madagascariensis Burser. Protium carana Eric. Erica arborea Lab. Agastache rugosa (ess. oil) Orchid. Vanilla Asaraldehyde (z,4,5-Trimethoxy-benzaldehyde) Aristolochi. Asarum europaeum (rt-oil) Umbell. Daucus carota Arac. Acorus calamus Benzaldehyde (fig. I I) occurs in some cyanogenicglycosides. It is reported free ( ?) from conifers and Annon. Cananga odorata (fl.-oil) Ros. Rosa, Rubus idaeus (frt) Legum. Acacia farnesiana (11.-oil) Rut. Citrus, Ruta Myrt. Eucalyptus, Melaleuca leucadendron Lili. Hyacinthus (fl.-oil) Amaryllid. Narcissus (fl.-oil) Cinnamic aldehyde (fig. I I) Laur. Cinnamomum (several species; to go% of ess. oil) Legum. Cassia Myrt. Melaleuca Lab. Lavandula, Pogostemon patchouly Lily. Hyacinthus (fl.-oil) Amaryllid. Narcissus (11.-oil) Coniferyl aldehyde (Ferulic aldehyde; fig. I I) seems to be derivable from lignins. Does it occur free in woods ? 3,4-Dihydroxy-benzaldehyde (Protocatechuic aldehyde) Comp. Cichorium intybus (free in sd and sdlg; combined later) Mus. Musa (` cavendish' banana; fungistatic in green frt) m(3)-Hydroxy-benzaldehyde: occurs in salinigrin.

ALDEHYDES 133

p(4)-Hydroxy-benzaldehyde: occurs in dhurrin. It is reported free (?) from a moss and Papaver. Papaver somniferum Xanthorrhoe. Xanthorrhoea australis (resin), hastilis (resin) Gram. Andropogon Orchid. Vanilla o(z)-Methoxy-cinnamic aldehyde Laur. Cinnamomum cassia (oil of bk and lys) p(4)-Methoxy-cinnamic aldehyde Comp. Artemisia dracunculus (ess. oil) p(4)-Methoxy-salicylic aldehyde (fig. I I) Apocyn. Hanghomia marseillii (rt) Asclepiad. Chlorocodon sp. (white?) (rt), Decalepis hamiltonii (rt), Hemidesmus indicus (rt), Periploca graeca (bk), Tylophora indica (rt) Methylenedioxy-cinnamic aldehyde (Piperonyl-acrolein) 3,4Laur. Cinnamomum sp. Parvifloral (fig. II) Rut. Zanthoxylum parviflorum (wd) Phenyl-acetaldehyde Ros. Rosa Phenyl-propionaldehyde (Dihydro-cinnamic aldehyde) Laur. Cinnamomum cassia, zeylanicum Piperonal (Heliotropin; 3,4-Methylenedioxy-benzaldehyde; fig. II) Monimi. Doryphora sassafras (tr.) Laur. Cinnamomum sp. Ros. Spiraea Legum. Robinia pseudacacia (fl.-oil; `heliotropin') Viol. Viola odorata (fl.) Umbell. Eryngium poterium (ess. oil) Orchid. Vanilla (Tahiti; not others?) Salicylic aldehyde (o(z)-Hydroxy-benzaldehyde; fig. I I) is the aglycone of spiraein. It seems to be widely distributed. Laur. Cinnamomum cassia Ros. Filipendula (Spiraea) ulmaria, Prunus avium Rhamn. Ceanothus velutinus (lvs) Flacourti. Homalium tomentosum Apocyn. Rauwolfia caffra (bk) Boragin. Cordia asperrima Solan. Nicotiana tabacum (lvs) Sinapic aldehyde (fig. II) Jugland. Juglans cinerea (htwd), nigra (htwd) Fag. Quercus (htwd) Acer. Acer saccharinum (htwd)

134 CHEMOTAXONOMY OF FLOWERING PLANTS

CHO

CHO

CH

CHO i CH HO CHO

CH

OH

4 OCHS

CH3

HO

OCH3

4-methoxysalicylic —

Coniferyl

Benzal-

Cinnamic

-dehyde

aldehyde aldehyde -aldehyde

CHO

CHO

1

CHO

Parvifloral

HO

CH CH

1:; :ko oJ

H CO 3 H3CO

" OCH3 r OCH3 1 OH OH

OCH3 OH

Piperonal

Salicyclic aldehyde

Sinapic

Syring-

aldehyde

aldehyde

Vanillin

Fig. i r. Some aromatic aldehydes. Syringaldehyde (fig. I I) can be obtained from lignin of all (1) angiosperms and a few gymnosperms. 3,4,5-Trimethoxy-benzaldehyde Gram. Cymbopogon (2 spp.) Vanillin (fig. I I) can be obtained from most lignin, and secondarily from many plants. Orchid. Nigritella suaveolens (fl.), Vanilla planifolia (frt; to 3%) Veratraldehyde (3,4-Dimethoxy-benzaldehyde) Umbell. Eryngium poterium Gram. Cymbopogon javanensis

ALKALOIDS GENERAL It is hard to compile general notes for such a diverse lot of substances as the alkaloids. It is not even possible to define an alkaloid in a way that would please everyone, since some of the simpler alkaloids of one

ALKALOIDS

135

author would be excluded by another. The simple amines, for example, grade into alkaloids without an N-ring, such as the alkaloidal amines. It has been proposed to call these last proto-alkaloids'. Alston and Turner (1963) say: Among nitrogenous substances of plants there is almost a continuum from the universal products of metabolism to alkaloids in the strict sense, and of course nitrogen-containing secondary compounds exist which are not classified as alkaloids. Purine and pyrimidine bases and the amino acid, histidine, are alkaloids except by the physiological criterion. Betacyanins ...except for the absence of any obvious physiological effects, are clearly model alkaloids. Mothes (1966) has reviewed our knowledge of the biogenesis of alkaloids. Even more recently Robinson has dealt generally with our subject in his The Biochemistry of Alkaloids (1968). We have drawn heavily upon him. Many other sources have been used in compiling the following notes and the `list and occurrence' sections which follow. We may mention particularly the very useful, but deliberately uncritical, book Alkaloid-bearing Plants and their Contained Alkaloids by Willaman and Schubert (1961), which lists over 3,600 species of plants as containing 2,000 alkaloids; the now rather dated 4th edition of The Plant Alkaloids by Henry (1949) ; the long series entitled The Alkaloids: Chemistry and Physiology (vols 1, 1950; 2, 1952 ; 3, 1953; 4, 1954; edited by Manske and Holmes; and 5, 1955; 6, 1960; 7, 1960; 8, 1965; 9, 1967; 10, 1968; II, 1968; edited by Manske); and Swan's An Introduction to the Alkaloids (1967). Some surveys for distribution have been made. We may note that of Douglas and Kiang (1957), who tested 214 plants for alkaloids and found 38 strongly positive. Hegnauer (in Swain, 1963) stresses the taxonomic significance of distribution. The survey of Willaman and Li (1963) should also be mentioned, it recalls the work of McNair (1931, 1935, 1936). Efforts to relate size' of alkaloids to the type of plant (herb, shrub, tree) and to the habitat (tropical, sub-tropical, temperate) meet with little success. Wideness of distribution of individual alkaloids is also considered by Willaman and Li. They conclude that caffeine (14 families) is the most widely distributed alkaloid, followed by trigonelline (12), and nicotine (9). Less widely spread as to families but occurring in many genera and species (genera/species) are lycorine (3o/85), berberine (26/89), and protopine (25/79). I give their figures in each case. At the other end of the scale, they say, are 1,443 alkaloids known to occur in but one species! Schultes (1963) has something to say as to richness of individual families. He estimates that at least Io% of the species of the Leguminosae

136 CHEMOTAXONOMY OF FLOWERING PLANTS

and Solanaceae have alkaloids. Recent work on the Apocynaceae, he points out, has tremendously increased our knowledge of that family and he concludes that about Io% of all known alkaloids occur in it! Mothes (1966) has figures to illustrate this last point. He says that in the 5 years before he writes the known alkaloids of Vinca (including Catharanthus?) have jumped from zo to 8o and that the Apocynaceae (which includes Vinca) have more than 30o alkaloids, as many as were known from the plant kingdom 40 or So years ago! The plants of Australia and of Papua–New Guinea have been surveyed by Webb (1949 1952, 1955). As to the physical properties of alkaloids we may note that they are usually basic—hence the name alkaloid or `alkali-like', proposed by Meisner a century and a half ago—but there are exceptions. They are usually colourless solids, but some (such as berberine) are coloured, and some (such as nicotine) are liquid. Most of them are optically active, and the different active forms are usually, but not always, found in different plants. They are said to occur in the cell-sap as cations and may be associated with particular acids, but this is not always the case. They are rare in animals. Salamandra is said to have some with oxazolidine nuclei and some with a carbinolamine system. An arthropod, Glomeris marginata, secretes 1,2-dimethyl-4-quinazolone. In the plant kingdom they have been found in fungi, in Equisetum, in Lycopodium, and in the higher plants. It is difficult to say just how many families of angiosperms produce alkaloids. Some of the supposed records are highly suspect. I have hundreds of names of `alkaloids' which seem to have been recorded but once and whose existence, let alone structure, has never been confirmed. It would be idle at this time to try to generalize as to the biogenesis of alkaloids. Much is known, but much is speculative, or based on but a few examples. It is probable that some of the widely distributed alkaloids arise in different ways in different groups; in such cases they would, chemotaxonomically speaking, be different substances! Mothes (1966) recognizes this sort of difficulty. Writing of the quinoline alkaloids he says: There are a number of other quinoline alkaloids, including fabianines, furoquinolines, isopropylquinolines, acridines, etc. We cannot presume that these quinolines represent a biosynthetically uniform group. It may be that the moieties which condense with anthranilic acid or with the opened indole nucleus are of greater taxonomic significance than the N-precursor. Hegnauer (in Swain, 1963) too, in writing of the odd distribution of the quinine alkaloids, says:

ALKALOIDS 137

Although it is impossible to speculate on the origin of the quinine alkaloids in the Annonaceae and Simarubaceae without experimental facts, it appears highly probable that they are formed in quite a different way from that in Cinchona. He says that the indole ring in most cases arises from tryptophan but that in several cases (including the betanins) it arises from phenylalanine. When we do know enough of the biogenesis of alkaloids it will be possible to group them more naturally and to use the distribution of the groups as an important taxonomic character. Alkaloid biogenesis and distribution even now are of considerable use as the notes which follow will show. The grouping we have arrived at, after some abortive attempts, is as follows. We realize that it is imperfect, but we believe that a committee of alkaloid chemists would never agree on a single system, so we make no apology. Acridines

CO',) OH OH

Alkaloids of Amary l l i daceae

Lycorine

Alkaloidal Amines

Crinine

OnNH2 Benzylamine

Daphniphyllum Group

Dihydroquinclones

Meloscine

Diterpenoid Alkaloids

138 CHEMOTAXONOMY OF FLOWERING PLANTS

Imidazoles

Indole Groups

Indolizidine

Isoquinoline Groups

CO

The lunaria Group Monoterpenoid Alkaloids

Oxazoles

Actinidine

~Ji

Papaverrubines 0 0

u

The Purine Bases

Pyrazoles

ALKALOIDS

Pyridine Groups

0

Pyrido (34-c) quinolines

Pyrrol id Ines

LN J H

Pyrrolizidines

Qu inazol i nes

Quinolines

C0

Quinolizidines

c0

Steroid Alkaloids

Solanidine HO

Tropane Alkaloids

0 H3CO

Tropolones

N 1,0

H3CO H3CO I-ac Colchicine OCH3

139

140 CHEMOTAXONOMY OF FLOWERING PLANTS

ACRIDINE GROUP GENERAL Price (in M. e9' H., v.2, 1952) writes of the wide variety of alkaloidsquinoline, furano-quinoline, isoquinoline, carboline, etc.—occurring in the Rutaceae, and says: `In view of this biogenetic versatility it seems appropriate that the recently discovered group of acridine alkaloids [Hughes, Lahey, Price and Webb, 19481 should occur also in the Rutaceae. Members of this group have been found in five species, belonging to three genera, indigenous to the tropical rain forests of Northern Australia.' Price listed 1 alkaloids, 2 of which may arise during isolation. Openshaw (in M., v.9, 1967) removes dubamine, which had been included in the acridines, because it turns out to be a quinoline rather than an acridine. We are indebted to Albert (1966) for a whole volume on the acridines, but this deals with the chemistry of the group as a whole. The naturally occurring alkaloids, which are derivatives of acridone rather than of acridine (fig. 12), receive only brief mention. To the best of my knowledge these alkaloids number about a dozen; are restricted to the Rutaceae; and occur in that family in a handful of species belonging to 6 or 7 genera. According to Robinson (1968) the acridines are believed to be derived from anthranilic acid and acetate, but there is no proof of this.

List and Occurrence Acronycine (fig. 12) Rut. Acronychia bauen (bk) ; Melicope fareana Arborinine (fig. 12) Rut. Glycosmis arborea (pentaphylla) (lvs); Ravenia spectabilis (lvs) I,3-Dimethoxy-N-methyl-acridone Rut. Acronychia bauen (lvs) Evoprenine Rut. Evodia alata (bk) Evoxanthidine (Nor-evoxanthine) Rut. Evodia alata, xanthoxyloides (Ivs); Teclea grandifolia Evoxanthine (I-Methoxy-2,3-methylenedioxy-N-methyl-acridone; fig. I2) Rut. Evodia alata (lvs, bk), xanthoxyloides (lvs, bk); Teclea grandifolia (rt) Melicopicine (fig. 12) Rut. Acronychia bauen (lvs, bk); Melicope fareana (lvs, bk)

ACRIDINE GROUP 141

2

10 Acridine

0 u

H Acridone

Arborinine

0 • H3 II OCH3 OCH3 OCH3

Acronycine

Evoxanthine

Melicopicine

Fig. 1z. Acridine, acridone, and some acridine alkaloids. Melicopidine Rut. Acronychia bauen (lvs, bk); Evodia alata (bk), xanthoxyloides (lvs, bk); Melicope fareana (lvs, bk) Melicopine Rut. Acronychia acidula (bk), bauen (lvs, bk); Evodia alata, xanthoxyloides; Melicope fareana (lvs, bk) i, 2, 3-Trimethoxy-N-methyl-acridone Rut. Evodia alata (lvs) Xanthevodine (Nor-melicopidine) Rut. Acronychia bauen (lvs); Evodia xanthoxyloides (lvs) Xanthoxoline—what is this ? Rut. Evodia xanthoxyloides (lvs); Zanthoxylum (Fagara) naranjillo (lvs)

ALKALOIDAL AMINES (including the ß-Phenyl-ethylamines) GENERAL It is difficult to decide which compounds should be listed here and which with other amines (p. 36o). Karrer (1958), who excludes alkaloids as a whole from his book, does include anhaline (hordenine) and candicine. Willaman and Schubert, on the other hand, include anhaline and

142 CHEMOTAXONOMY OF FLOWERING PLANTS

candicine in their Alkaloid-bearing Plants and Their Contained Alkaloids (1961). We include the so-called alkaloidal amines and the ßphenyl-ethylamines in this section. We include ephedrine and related compounds, but exclude narceine. The 13phenyl-ethylamines and their derivatives are rather widely distributed in dicotyledons. They also occur, but more rarely, in monocotyledons. Some are to be found elsewhere—in fungi, in gymnosperms, and in animals. Is it more than chance that many of them occur in the Chenopodiaceae and Cactaceae, with at least one in the Nyctaginaceae? These families are, in the modern view, closely related. Bentley (1965) says that they are believed to arise in the sequence amino-acids -+ f3phenyl-ethylamines, and that they may then condense with aldehydes to form simple isoquinolines (as in fig. 13). Damascenine (fig. 14) may be considered to be a simple derivative of anthranilic acid (o-amino-benzoic acid) which, in animals, is a degradation product of tryptophan. In plants damascenine does not arise from tryptophan but it can be formed from anthranilic acid or shikimic acid. Unlike nicotine, which is formed in the root, and many alkaloids which are formed in leaves, damascenine is synthesized and stored in the seed. List and Occurrence Adrenaline does not, I think, occur in higher plants, but nor-adrenaline does. Aegeline Rut. Aegle marmelos o-Amino-benzoic acid (Anthranilic acid; 2-Amino-benzoic acid) occurs in bacteria, but not (?) in higher plants. o-Amino-benzoic acid-methyl ester is said to be present in small amount in many essential oils. p-Amino-benzoic acid (4-Amino-benzoic acid) occurs in fungi and bacteria, but not (?) in higher plants. Anhaline (Hordenine; ß p-Hydroxy-phenyl-ethyl-dimethylamine; fig. 14) Cact. Lophophora (Anhalonium) williamsii, Mammillaria, Trichocereus Legum. Acacia berlandieri Gram. Avena, Hordeum (2), Oryza, Panicum (2), Phalaris, Sorghum, Zea Benzylamine (Moringine; Moringinine; fig. 54) Moring. Moringa oleifera (bk)

ALKALOIDAL AMINES 143

Candicine (ß p-Hydroxy-phenylethyl-trimethyl-ammonium hydroxide) Cact. Lophophora williamsii; Trichocereus candicans and 2 other spp. Magnoli. Magnolia grandiflora (bk) Rut. Fagara (bk of 6 spp.), Phellodendron amurense Coryneine (3-Hydroxy-candicine) Cact. Stetsonia (Cereus) coryne Rut. Fagara hiemalis (bk) Damascenine (fig. 14) Ranuncul. Nigella arvensis (aristata) (sd), damascena (sd) l-Ephedrine occurs in species of Ephedra (Gnetales). In angio-sperms it has been recorded from Ranuncul. Aconitum napellus (rt) Papaver. Roemeria refracta Moring. Moringa oleifera Maly. Sida cordifolia (lys) and 3 other spp. Celastr. Catha edulis Epinine (N-methyl-3,4-dihydroxy-phenylethylamine) Legum. Cytisus Feruloputrescine (Subaphylline) Chenopodi. Salsola subaphylla Rut. Citrus paradisi (lys) Halostachine (better Halostachyine; Phenylethanol-methylamine) Chenopodi. Halostachys caspica 3-Hydroxy-tyramine (ß-3,4-dihydroxy-phenylethylamine) Nyctagin. Hermidium alipes (rt) Legum. Cytisus (Sarothamnus) scoparius Jaborandine—belongs here ? Piper. Piper jaborandi, reticulatum (lys) Rut. Pilocarpus pinnatifolius (lys, fl., frt) Jaxartine (N-Methyl-2-(4-hydroxyphenethyl)-amine) Chenopodi. Anabasis jaxartica Kuramerine is related to Kumokirine (a pyrrolizidine). Orchid. Liparis kumokiri, kurameri Macromerine (1-(3,4-Dimethoxyphenyl)-2-dimethylamino-ethanol) Cact. Coryphantha runyonii, Thelocactus micromeris (Coryphantha macromeris) Mescaline (Mezcaline: ß-3,4, 5-Trimethoxy-phenylethylamine; fig. 14) Cact. Gymnocalycium, Lophophora, Opuntia, Trichocereus Methyl-damascenine Ranuncul. Nigella? N-Acetyl-mescaline Cact. Lophophora williamsii

IØ CHEMOTAXONOMY OF FLOWERING PLANTS

N-Benzoyl-ß-phenyl-ethylamine Legum. Oxytropis muricata N-Benzoyl-tyramine Rut. Casimiroa edulis (sd) N-Methyl-anthranilic acid Rut. Citrus paradisi (frt ?) N-Methyl-anthranilic acid methyl ester Rut. Citrus spp. (ess. oil) Zingiber. Kaenapferia ethelae (rhiz. ?) N-Methyl-mescaline Cact. Lophophora williamsii N-Methyl-ß-phenyl-ethylamine Chenopodi. Arthrophytum leptocladum (lvs, st.) Legum. Acacia spp. N-Methyl-tyramine (Andirine ? ; Angeline; ß p-Hydroxy-phenylethylmethylamine; Geoffroyine; Rhatamine; Surinamine) Chenopodi. Anabasis jaxartica (plt) Cact. Lophophora williamsii Legum. Acacia berlandieri; Andira spp. ? Gram. Hordeum N,N-Dimethyl-4-methoxy-phenethylamine Rut. Toddalia (Teclea) simplicifolia Nor-adrenaline (Arterenol; Nor-epinephrine) Ros. Prunus domestica Rut. Citrus aurantium Solan. Solanum tuberosum Mus. Musa paradisraca, sapientum d-Nor-iso-ephedrine (Cathine) occurs in Ephedra and Celastr. Catha edulis 1-Octopamine (l-Nor-synephrine) occurs in the octopus and other animals. It has recently been reported from Rut. Citrus (lemon) O-Methyl-tyramine-N-methylcinnamide (Herclavine) Rut. Zanthoxylum clava-herculis Oxy-candicine Cact. Stetsonia (Cereus) coryne Oxytyramine Legum. Cytisus ß-Phenylethylamine (fig. 14) occurs in fungi and Loranth. Viscum album? Legum. Acacia (many spp., but see discussion under Leguminosae) Pseudo-ephedrine (Iso-ephedrine) is recorded fromEphedra and Taxusand Papaver. Roemeria refracta

ALKALOIDAL AMINES

HO

HOØCOOH H2

HO 0v

An amino-acid

145

+ O-4 HOØ HO" C NH2

HO

A 0-phenyl-

(Dihydroxy-

ethylamine

-phenylalånine)

-I- CHO

N

A simple isoquinoline

CH3 Acetaldehyde

Fig. i 3. Origin of fl-phenyl-ethylamines and simple isoquinolines.

QH2

CnNH2

Benzylamine f3-Phenyl-ethyl-amine

HO

NH2 HO N Tyramine

Anhaiine

OCHS

Mescaline

Damascenine

Taspine

Fig. 14. Some alkaloidal amines.

Celastr. Catha edulis Maly. Sida cordifolia Salicifoline Magnoli. Magnolia salicifolia (bk) and 5 other spp. Smirnowine Legum. Eremosparton aphyllum (st.), flaccidum; Smirnowia turkestana (lys) Smirnowinine Legum. Eremosparton aphyllum (st.), Smirnowia turkestana (lys, st.) Sphaerophysine (? Isoamyl-putrescine; Spherophytine) Legum. Eremosparton fiaccidum (lys, st.), Smirnowia turkestana (lys), Sphaerophysa salsula

146 CHEMOTAXONOMY OF FLOWERING PLANTS

l-Synephrine Rut. Citrus Taspine (fig. 14) has a structure which has been described as `unique among alkaloids'. Berberid. Leontice eversmannii Trichocereine (N,N-Dimethyl-mescaline) Cact. Trichocereus terscheckii Tyramine (ß p-hydroxyphenylethylamine; fig. 14) occurs in fungi. It is widely spread in higher plants Loranth. Phoradendron (3), Viscum album Cact. Lophophora williamsii Crucif. Capsella bursa-pastoris Legum. Acacia berlandieri, Cytisus (Sarothamnus) scoparius Gerani. Erodium cicutarium Rut. Citrus aurantium Comp. Carduus?, Silybum marianum Amaryllid. Crinum sp.

ALKALOIDAL PEPTIDES GENERAL Manske (in M., v.I o, 1968) says that the adouetines, which occur in Waltheria (Sterculi.), seem to be peptides. The alkaloids of Araliorhamnus, Ceanothus, Lasiodiscus, Scutia, and Zizyphus (all of the Rhamnaceae) also belong here. Robinson (1968) would put julocrotine here, too, but we have placed it among the pyridine alkaloids. Recent workers have reported additional alkaloidal peptides from Euphorbiaceae, Pandaceae, Rubiaceae, and Urticaceae, so they are evidently widely spread. List and Occurrence Adouetines -X, -Y, and -Z Sterculi. Waltheria indica (americana) Aralionin Rhamn. Araliorhamnus vaginata (lvs) Canthiumine yields N,N-dimethyl-L-phenylalanine, p-hydroxy-styrylamine, L-proline, and L-threo-ß phenylserine. Rubi. Canthium euryoides Ceanothin-B Rhamn. Ceanothus americana

ALKALOIDAL PEPTIDES 147

HC:CH.NH.CO.CH—{ H 3C 0

HI COC

N.

N% N
3%), Scopolia Lab. Orthosiphon Comp. Parthenium argentatum (plt) Cadaverine (1,5-Dimino-pentane; Pentamethylene diamine; NH2(CH2)5NH2) Legum. Glycine max, Pisum sativum Solan. Solanum tuberosum Arac. Arum italicum (infl.), Sauromatum guttatum (infl.) Choline (Amanitin; Bilineurin; Combretine; Neurin; Sinkalin; +

[(CH3)3N . CH2CH2OH]OH—) may be universal in plants. I have the following records: Mor. Humulus Monimi. Doryphora Ranuncul. Caltha Crucif. from sinapin? Legum. Glycine max (sd), Phaseolus, Trigonella, Vicia sativa (sd) Gerani. Erodium Combret. Combretum micranthum (lys) Ole. Olea Solan. Atropa, Scopolia, Withania somnifera (rt) Lab. Orthosiphon

362 CHEMOTAXONOMY OF FLOWERING PLANTS

Scrophulari. Digitalis (2) Valerian. Valeriana officinalis Lili. Convallaria Citrosamine (Glucosamido-glucuronido-inositol) Rut. Citrus (lys of `Dancy' tangerine) p-Coumaroyl-agmatine Gram. Hordeum vulgare (young shoots) Creatinine has been recorded from wheat, rye, clover, lucerne, potato, etc. Diethylamine ((CH3CH2)2NH) Arac. Arum italicum (infl.), Sauromatum guttatum (infl.) Dimethylamine ((CH3)2NH) occurs in fungi and Capparid. Courbonia virgata (frt) Ros. Crataegus Umbell. Heracleum sphondylium (fl.) Arac. Arum dioscoridis (infl.) ?, italicum (infl.); Dracunculus vulgaris (infl.); Sauromatum guttatum (infl.) bis-i,¢-Dimethylamino-butane ( ?Tetramethylputrescine) Solan. Hyoscyamus muticus Dimethylamino-ethanol ((CH3)2N . CH2CH2OH) occurs only (?) esterified in the alkaloids cassain, cassaidin, etc. Ergothioneine is a betaine. Euphorbi. Hevea brasiliensis (latex), benthamiana (latex), spruceana (latex) Ethanolamine (2-Amino-ethanol; Colamine; NH2 .CH2CH2OH) may be obtained by hydrolysis of cephalins from all plants ? It may occur (free ?) in Ros. Crataegus Legum. Pisum sativum Arac. Amorphophallus konjac (Hydrosme rivieri) (infl.), Sauromatum guttatum (infl.) Ethylamine (CH3CH2NH2) Ros. Crataegus oxyacantha Gerani. Erodium Cucurbit. Bryonia dioica (fl.) Caprifoli. Sambucus nigra Arac. Amorphophallus konjac (Hydrosme rivieri) (infl.); Arum italicum (infl.), maculatum (infl.); Dracunculus vulgaris (infl.); Sauromatum guttatum (infl.) Galegine ((CH3)2C=CH2NH . C(=NH)NH2) is a derivative of guanidine. Legum. Galega officinalis (lvs, sd) The. Camellia (Thea)

AMINES 363

Guanidine (HN=C(NH2)2) is said to occur in algae, fungi, and higher plants. Guanidine derivatives have been recorded from many families (Reuter, 1957-8) among the `soluble nitrogenous substances'. Chenopodi. Beta Legum. Galega officinalis, Glycine max (sd), Vicia sativa Gram. Zea Hercynine (Histidine-betaine) Euphorbi. Hevea brasiliensis (latex) i,6-Hexanediamine Arac. Arum italicum (infl.), Sauromatum guttatum (infl.) Histamine (fig. 19) is said to be associated with the burning or stinging sensation caused by many irritant plants. Werle and Raub (1948) have studied its distribution, and Werle and Zabel (1948) have investigated the distribution of histaminase. I have records of presence or absence of histamine from fungi and Urtic. Laportea gigas; Urera sp. (lvs); Urtica dioica, urens Loranth. Viscum Chenopodi. Beta vulgaris var. rapa (lys), trigyna (lvs); Chenopodium bonus-henricus (lys, fl.); Salsola kali (lys); Spinacia oleracea (fl.) Ranuncul. Delphinium sp. (fl.) Piper. not in Piper nigrum Sarraceni. Sarracenia (lvs) Nepenth. Nepenthes (lvs) Droser. Drosera (lys) Papaver. Chelidonium majus (lys); not in Corydalis glauca Crassul. not in one Saxifrag. not in one Legum. Mimosa sp. (lvs); Trifolium pratense (lys), repen (lvs)but not in Genista, Tamarindus Gerani. Erodium (1)—but not in Pelargonium (i) ? Rut. Citrus (1)—but not in Ruta (i) Aquifoli. not in one Sterculi. not in Theobroma cacao Cucurbit. Cucumis sp. Arali. not in one Primul. Cyclamen (I, lys, fl., corm, rt)—but not in Primula (i) Lab. Lamium album (lvs), Salvia Solan. Lycopersicum esculentum (sap) Orobanch. not in Orobanche (i) Lentibulari. Pinguicula (i) (lvs) Plantagin. Plantago lanceolata (Iys) Comp. Silybum marianum Arac. Amorphophallus konjac (Hydrosene rivieri) (infl.)

364 CHEMOTAXONOMY OF FLOWERING PLANTS

4-Hydroxy-galegine Legum. Galega officinalis (sd) Isoamylamine ((CH3)2CH . CH2. CH2 . NH2) is very widely distributed (McKee, 1962; Stein von Kamienski, 1957-8). I have records of it from fungi and Polygon. Polygonum cuspidatum (fl.) Berberid. Mahonia aquifolium—but not in Berberis (i) Nymphae. Nuphar luteum (fl.) Saxifrag. Chrysosplenium, Hydrangea quercifolia (fl. ?), Ribes Ros. Amelanchier rotundifolia (fl.); Aruncus sylvester (fl.); Chaenomeles (fl., 2); Cotoneaster (2); Crataegomespilus; Crataegus (12); Filipendula (2), Prunus (fl., 5 or 6); Pyracantha coccinea; Pyrus communis (piraster); Sanguisorba; Sorbaria (1, fl.); Sorbus aria, domestica?, x latifolia; Spiraea (a) Euphorbi. Mercurialis (plt, z) Rut. Phellodendron amurense (fl.) Acer. Acer pseudoplatanus Staphyle. Staphylea colchica (fl.) Cucurbit. Bryonia dioica (fl.) Onagr. Oenothera lamarckiana (fl.) Corn. Cornus sanguinea Umbell. Anthriscus (fl.); Chaerophyllum (fl.), Heracleum; Peucedanum; Pimpinella Asclepiad. Vincetoxicum officinale (fl.) Rubi. Galium (fl. of 2 or 3 spp.) Solan. Atropa belladonna (fl.); Nicotiana (lys and/or fl. of 5) Caprifoli. Sambucus nigra, Viburnum (fl. of 4) Arac. Amorphopallus konjac (Hydrosme rivieri) (infl.), Arum dioscoridis (infl.) ?, Dracunculus vulgaris (infl.), Sauromatum guttatum (infl.) Isobutylamine ((CH3)2CH . CH2NH2) occurs free (?) and as amides such as fagaramide, spilanthol, etc. Nymphae. Nuphar luteum (fl.) Berberid. Berberis vulgaris, Mahonia aquifolium Ros. Crataegus (6 spp., says McKee, 1962), Filipendula ulmaria (fl.), Pyrus communis, Rosa sp., Sorbus aucuparia (fl.) Umbell. Conium maculatum Asclepiad. Vincetoxicum officinale (fl.) Caprifoli. Sambucus nigra (sap); Viburnum lantana, prunifolia Arac. Amorphophallus konjac (Hydrosme rivieri) (infl.); Arum italicum (infl.), maculatum (infl.), nigrum, nickelii; Sauromatum guttatum Isopropylvinyl-putrescine ((CH3)2CH. CH=CH . NH(CH2)4NH2) Legum. Eremosparton fiaccidum (lvs, st.), Sphaerophysa

AMINES 365

Methylamine (Mercurialin; CH3NH2) is said to occur in seaweeds and in Chenopodi. Beta Ranuncul. Delphinium consolida (fl.), Thalictrum flavum (fl.) Nymphae. Nuphar luteum (fl.) Saxifrag. Philadelphus lemoinei (fl.) Euphorbi. Mercurialis annua (lys), perennis (lys) Staphyle. Staphylea colchica (fl.) Umbell. Chaerophyllum aromaticum (fl.), Conium maculatum (fl.), Heracleum sphondylium (fl.), Leptotaenia dissecta (rt) Asclepiad. Stapelia? Lab. Mentha Solan. Atropa belladonna (lys, fl.), Nicotiana (fis of 5) Caprifoli. Sambucus nigra (fl.), Viburnum opulus (fl.) Lili. Lilium candidum (fl.), martagon (fl.); Veratrum nigrum (fl.) Irid. Iris germanica (fl.) Arac. Acorus?; Amorphophallus konjac (Hydrosme rivieri) (infl.); Arum dioscoridis (intl.), italicum (roil.), maculatum (fl.); Dracunculus vulgaris (intl.); Sauromatum guttatum (infl.) Methylamino-ethanol (CH3NHCH2CH2OH) occurs free (?) in fungi and as esters in Erythrophleum alkaloids. N-Acetyl-histamine Chenopodi. Spinacia oleracea N-Carbamyl-putrescine (NH2CO.NH(CH2)4NH2) may be an intermediate in the formation of putrescine from agmatine by Gram. Hordeum vulgare N,N-Dimethyl-histamine Chenopodi. Spinacia oleracea ß-Phenylethylamine has been treated also as an alkaloid. Here it occurs in flowers of: Saxifrag. Philadelphus delavayi Ros. Crataegus (ca. 8), Pyrus communis, Sorbus aucuparia, Spiraea sorbifolia Corn. Cornus (2) Asclepiad. Vincetoxicum officinale i,2-Propanediamine Arac. Arum italicum (infl.), Sauromatum guttatum (infl.) Propionyl-choline Loranth. Viscum album Propylamine (CH3CH2CH2NH2) occurs in ergot and Chenopodi. Camphorosma monspeliacum Putrescine (i,4-Diamino-butane; NH2(CH2)4NH2) may be formed from agmatine by barley. It occurs in fungi and Legum. Pisum sativum

366 CHEMOTAXONOMY OF FLOWERING PLANTS

Gerani. Erodium Rut. Citrus grandis (and other spp. ?) Solan. Atropa belladonna, Datura stramonium Arac. Arum italicum (infl.), Sauromatum guttatum Sinapin is the sinapic acid ester of choline. It occurs in the glycoside sinalbin. Crucif. Draba nemorosa (free ?) Tetramethyl-ammonium hydroxide (Tetramine; (CH3)4N.OH) occurs in sea-anemone and Capparid. Courbonia pseudopetalosa, virgata (rt) Trimethylamine ((CH3)3N): secondary in many cases? It has been reported from red and brown algae and from many higher plants. Fag. Fagus Chenopodi. Beta vulgaris, Chenopodium vulvaria (lys), Rhagodia hastata Ranuncul. Clematis—not in Thalictrum Aristolochi. Aristolochia gigas, grandiflora (fl.) ? Capparid. Courbonia virgata Crassul. Cotyledon umbilicus (plt) Saxifrag. Chrysosplenium Ros. Crataegus (fls of 9 spp.); Prunus padus, serotina (fl.); Pyrus communis (fl.); Sorbaria (I, fl.); Sorbus aucuparia (fl.), latifolia; Spiraea sorbifolia (fl.) Euphorbi. Mercurialis perennis (plt) Maly. Gossypium (fl.) Corn. Cornus sanguinea (fl.) Umbell. Chaeophyllum cicutaria, Heracleum sphondylium (fl.) Menyanth. Menyanthes? Solan. Nicotiana Caprifoli. Viburnum lantanum Comp. Arnica montana, Taraxacum officinale (fl.) Lili. Hyacinthus orientalis Arac. Acorus calamus (rhiz.), Amorphophallus konjac (Hydrosme rivieri) (infl.), Dracunculus vulgaris (infl.), Sauromatum guttatum (infl.), Spathiphyllum heliconiaefolium

AMINO-ACIDS 367

AMINO-ACIDS, PEPTIDES, AND PROTEINS (including Enzymes) GENERAL We have here the same kind of problem which faces us when we consider

carbohydrates, terpenoids, and any other chemical units which may occur singly or linked in chains of from two to a few to many units. The amino-acids are very numerous and often occur singly in the plant. They may also be found linked together as peptides, two to many units being involved. Finally, chains of very many units are known as proteins and enzymes. But where is the boundary between a big peptide and a small protein? Elmore, in his Peptides and Proteins (1968), sees no boundary between them. He asks, is adrenocorticotrophic hormone (with 39 amino-acid residues) to be called a large peptide or a small protein ? And is there any real distinction to be drawn, except in function, between an `ordinary' protein and an enzyme? We shall divide our discussion here, ignoring these difficulties more or less, into three major sections dealing with: I. Amino-acids. II. Peptides. III. Proteins (including enzymes).

I AMINO-ACIDS GENERAL There is no clear distinction between some amino-acids, such as histidine, and some alkaloids; nor can we always place amides logically—some substances, such as glutamine and asparagine, are amides of amino-acids! About 20 amino-acids occur in proteins, and these have been called the `magic twenty'. Actually we are by no means certain that all of these occur in all proteins. Davies et al. (1964) include hydroxyproline and cystine in their list, making a total of 22. They say, however: `Current theories of coding can account for twenty amino-acids; hence it is necessary to assume that hydroxyproline is alternative to proline as one of the "magic twenty" and that cysteine but not cystine is coded.' Fowden (1962) points out that further amino-acids may occur in individual proteins, such as enzymes. He mentions a-amino-adipic acid, for example, as being present to the extent of o•o6% of the dry weight of the water-soluble proteins of Zea mays, and sarcosine as occurring in a peanut protein.

368 CHEMOTAXONOMY OF FLOWERING PLANTS

Most, if not all, of the `magic twenty' occur free as well as in the bound form. In addition many other amino-adds have been found in the free state, sometimes in rather large amount. Fowden (1962) has a dramatic graph to show how the adoption of chromatography as a tool has resulted in a tremendous increase in the number of non-protein amino-acids known. It would seem that our list is incomplete, but we have placed a few amino-adds elsewhere. Fowden points out that: Unlike animals, plants must synthesize all the amino-acids necessary for the formation of protein. In addition, however, they synthesize at least sixty amino-acids which, so far as is known, are not incorporated into protein. Some of these amino-acids are found in only a very few species, and many have unusual structural features not found in other natural products...the degree of uncertainty that is at present associated with the function of these compounds resembles that surrounding other types of plant products, including the alkaloids, floral pigments, essential oils, and polyphenols. Writing in 1965, Dunnill and Fowden estimated that at least loo non-protein amino-acids were known at that time from plants, occurring either free or as y-glutamyl peptides. The chemotaxonomy of amino-acids is discussed elsewhere in this book. We may note: (a) The work of Bell (1962, 1963, 1964), Bell and Tirimanna (1963), and Bell and O'Donovan (1966) on the amino-acids of Lathyrus and Vicia (both Leguminosae). (b) That of Montant (1957) on the free amino-acids of Euphorbia. (c) The distribution of djenkolic acid and N-acetyl-djenkolic acid in the subfamily Mimosoideae of the Leguminosae. (d) The occurrence of 8-acetyl-ornithine in the Papaveraceae. (e) The amino-acids of the Cucurbitaceae. (f) The cyclopropyl amino-acids of the Sapindaceae-Hippocastanaceae group. It is tempting to discuss the biosynthesis of amino-acids in higher plants, but the temptation must be resisted. The interested reader is referred to such reviews as those of Fowden (in Plant Biochemistry, edited by Bonner and Varner, 1965; and Ann. Rev. Plant Physiol. 1967). We may note, however, that a relationship between a-amino-acids and cyanogenic glycosides: RR /0 . Glucose >CH.CH(NH2).COOH-R )C.CN R has been established for linamarin, lotaustralin, prunasin, and dhurrin.

AMINO-ACIDS 369

It is interesting that free labelled HCN may be incorporated into asparagine by Vicia (some species), Lathyrus odoratus, Ecballium elaterium, and Cucumis sativus; but into y glutamyl-ß-cyano-alanine by some other Vicia species (including sativa, monantha and ferruginea). Free ß-cyano-alanine, which is neurolathyritic, occurs in V. sativa. List and Occurrence 8-Acetyl-ornithine (H3CO . NH . CH2 . CH2 . CH2 . CH(NH2) . COOH) Papaver. General ? Tyler (196o) says: `Its usefulness a sa chemotaxonomic indicator would appear to rank with protopine [an alkaloid]. Both compounds distinguish the Papaveraceae and Fumariaceae [we treat these as sub-families of the Papaveraceae] from other families but not necessarily from each other.' Unfortunately for this statement 8-acetyl-ornithine does occur elsewhere: Legum. Onobrychis viciifolia and other members of the family Gram. some members of the Festuceae (Fowden, 1958) l-Alanine (a-Amino-propionic acid; CH3 . CH(NH2) . COOH) is one of the protein' amino-acids. Many derivatives occur as `non-protein' amino-acids. ß-Alanine (ß-Amino-propionic acid) seems to be widely distributed. Crassul. Kalanchoe Legum. in root nodules, etc. Irid. Iris Gram. Agropyrum, Lolium Albiziine (3-Ureido-alanine) Legum. Mimosoideae a-Amino-y-acetylamino-butyric acid (y-Acetyl-diamino-butyric acid) Euphorbi. Euphorbia pulcherrima (latex) l-a-Amino-adipic acid (HOOC . CH2 . CH2 . CH2 . CH(NH2) . COOH) is widely distributed in the free state (Fowden, 1962). Is it involved in the synthesis of lysine? Legum. Pisum (sd) Gram. probably present in small amounts in: Avena, Brachypodium, Bromus, Dactylis, Festuca, Hordeum, Lolium, Poa, Zea /-cc-Amino-butyric acid (CH3. CH2. CH(NH2). COOH) Solan. Solanum tuberosum (lvs, but not tubers) Gram. Zea mays (lvs, free (?) and combined) y-Amino-butyric acid—writing in 1962, Fowden says that it: `...seems to be distributed universally—a plant that did not contain it would be considered odd'. It is probably produced by decarboxylation of glutamate. I have records of it from: Betul., Ulm., Chenopodi.,

370 CHEMOTAXONOMY OF FLOWERING PLANTS

Calycanth., Piper., Legum., Euphorbi., Hippocastan., Solan., Lili. (general ?), Gram., etc. 1-Amino-cyclopropane- i -carboxylic acid Ros. Malus (apple), Pyrus (pear) (unripe frt) Eric. Vaccinium vitis-idaea 2-Amino-4-hydroxyhept-6-ynoic acid Sapind. Euphoria longana (sd) 2-Amino-6-hydroxy-4-methylhex-4-enoic acid Hippocastan. Aesculus californica (sd) 2-Amino-4-hydroxymethylhex-5-ynoic acid Sapind. Euphoria longana (sd) ß-Amino-isobutyric acid (H2N . CH2 . CH(CH3) . COOH) : arises by breakdown of thymine? Irid. Iris tingitana 2-Amino-4-methylhex-4-enoic acid and its y-glutamyl peptide Hippocastan. Aesculus californica (sd) 2-Amino-4-methylhex-5-ynoic acid (fig. 87) Sapind. Euphoria longana (sd) a-Amino-y-oxalylamino-butyric acid occurs in equilibrium with aoxalylamino-ß-amino-butyric acid (Bell and O'Donovan, 1966) in Legum. Lathyrus spp. a-Amino-ß-oxalylamino-propionic acid is a neurotoxin. It occurs in equilibrium with a-oxalylamino-ß-amino-propionic acid (Bell and O'Donovan, 1966) in Legum. Lathyrus spp. a-Amino-pimelic acid (HOOC . (CH2)4 . CH(NH2). COOH) occurs in a fern and in Legum. Ceratonia siliqua (sd) a-Amino-ß-(pyrazolyl-1V)-propionic acid (ß-Pyrazol-1-yl-alanine) is formed from pyrazole and serine in cucumber seedlings. Cucurbit. see discussion under family /-Arginine (a-amino-8-guanidino-valeric acid; H2N . C(=NH) . NH . (CH2)3. CH(NH2).COOH) is a `protein' amino-acid which, according to Mothes (1961) is also `a frequent form of nitrogen-storage in underground organs and stems'. I have records of it combined and/or free from algae, gymnosperms, at least 25 families of dicotyledons, and 5 families of monocotyledons. Asparagine (H2N . CO . CH2 . CH(NH2) . COOH) is the amide of aspartine (an amino-acid). It was crystallized from juice of Asparagus in 18o6I It is a constituent of proteins and therefore universally ( ?) distributed. I have records of it from 22 families of dicotyledons and 6 families of monocotyledons. Several derivatives of asparagine are known to occur.

AMINO-ACIDS 371

l-Aspartic acid (a-Amino-succinic acid; HOOC . CH2 . CH(NH2). COOH) is one of the `magic twenty' protein amino-acids. It may also occur free in Bromeli. Aechmea purpurea rosea, Ananas comosus, Billbergia nutans (An important storage material in all—Reuter, 1957-8) Arac. It is the chief soluble nitrogenous substance in some. Azetidine-z-carboxylic acid (Homoserine lactone; fig. 87) is an iminoacid found by Fowden and Steward (1957) in many related monocotyledons, and often in considerable amount. It `...may contain as much as 5o% of the total nitrogen present in the rhizome of Solomon's seal (Polygonatum multiflorum)'. Writing in 1962 Fowden says: `azetidine-2-carboxylic acid occurs in a high proportion of liliaceous species [including our Agavaceae] but has not been detected in members of other plant families except in a few species of Amaryllidaceae [species which we include in Liliaceae] ...'. Lili. Bowiea volubilis (st.), Camassia sp. (sd), Convallaria majalis (lvs, sd), Danae racemosa (sd), Fritillaria imperialis (sd), Gasteria verrucosa (lvs), Hosta glauca (sd), Liriope muscari (lvs, sd), Littonia modesta (sd), Mai anthemum canadense (lvs, sd), Milla biflora (sd), Polygonatum sp. (lvs), Rohdea japonica (lvs), Ruscus aculeatus (` lvs'), Scilla hohenackeri (sd), Smilacina racemosa (sd) Agay. Dracaena deremensis (lvs), fragrans (lvs), godseffiana (lvs), sanderiana (lvs) Amaryllid. ? Canaline (a-Amino-y-O-hydroxylamino-butyric acid; H2N .0. CH2 . CH2. CH(NH2) . COOH) is formed enzymatically from canavanine. Does it occur free in any amount ? Canavanine (cc-Amino-y-hydroxyguanidino-butyric acid; H2N . C(=NH) . NH . O . CH2. CH2 . CH(NH2) . COOH) is known only from the Leguminosae and in that great family only from the Faboideae. cis-a-(Carboxycyclopropyl)-glycine Hippocastan. Aesculus parviflora (sd) trans-a-(Carboxycyclopropyl)-glycine Sapind. Blighia sapida (sd) m-Carboxyphenyl-i-alanine (fig. 87) seems to be rather widely distributed. Crucif. Lunaria Resed. Reseda Cucurbit. many (p. 1256) Irid. Iris tingitana 1-(+ )-Citrulline (a-Amino-S-carbamido-valeric acid; H2N . CO . NH(CH2)3. CH(NH2) . COOH) is discussed by Dunnill and Fowden (1965) who say that as an intermediate in the glutamic

372 CHEMOTAXONOMY OF FLOWERING PLANTS

acid ---> arginine pathway it is probably present in all plants but often in very small amount. The 3 acids arginine, citrulline, and ornithine have been called the ornithine family'. They seem to be interconvertible in the plant. I have records of citrulline from Jugland. Carya, Juglans, Pterocarya Betul. Alnus, Betula, Carpinus, Corylus, Ostrya Fag. Nothofagus Caryophyll. Agrostemma Annon. Annona Calycanth. Calycanthus Laur. Persea Crucåf. Brassica Vitac. Vitis (sap) Cucurbit. Citrullus lanatus (where it was first found), and many others, in relatively large amount (p. 1256) Eben. Diospyros Lili. Galtonia Irid. Freesia Cucurbitin (3-Amino-pyrrolidine-3-carboxylic acid; fig. 87) Cucurbit. Cucurbita moschata Cyclo-alliin (fig. 87) contains sulfur. Lili. A11åum spp. Cystathionine is known in combination as selenocystathionine. Does it occur free in higher plants ? Cysteine (HS. CH2 . CH(NH2) . COOH) is a `protein' amino-acid, but may be lacking in protein-hydrolysates, presumably because it is easily oxidized to cystine. 04.5-Dehydro-pipecolic acid (Baikiain; fig. 87) Legum. Acacia spp., Baikiaea plurijuga (wd) Palmae. Phoenix dactylzfera (frt) Deamino-canavanine may be secondary. Legum. Canavalia ensiformis a,y-Diamino-butyric acid Legum. Lathyrus spp. (sds) Lili. Polygonatum multiflorum (rhiz.) a,ß-Diamino-propionic acid (H2N . CH2 . CH(NH2) . COOH) Legum. Mimosoideae Dihydro-alliin (H3C. CH2 . CH2 . SO. CH2 . CH(NH2). COOH) Lili. Allium spp. 2,4-Dihydroxy-6-methyl-phenylalanine Caryophyll. Agrostemma githago (sd) l-3,4-Dihydroxy-phenylalanine (DOPA) is probably formed by oxidation of phenylalanine and/or tyrosine. See also melanins.

AMINO-ACIDS

373

Legum. Cytisus; Mucuna capitata, pruriens; Stizolobium (Mucuna) deeringianum (sd); Vicia faba (sd, sdlg) Euphorbi. Euphorbia lathyris (Liss, 1961), but not in 19 other spp. (Montant, 1957) Djenkolic acid (fig. 87) Legum. Albizia lophantha; Pithecolobium bigeminum, dulce, lobatum (`Jengkol'), multiflorum. See discussion under Leguminosae. 1-Glutamic acid (a-Amino-glutaric acid; HOOC .CH2 . CH2 . CH(NH2) . COOH) is a `protein' amino-acid and therefore universally distributed. It may also be free and occur as one of the main nitrogen-storage acids in several families. Several derivatives also occur. I have the following records: Myric.; Salic. (Salix, Populus); Betul. (Alnus, Betula, Carpinus, Corylus); Fag. (Castanea, Fagus, Quercus); Ulm. (Ulmus, much); Cact. (in all tested: one of main N-storage materials); Ranuncul. (several); Berberid. (Mahonia); Nymphae. (Nuphar, Nymphaea); Calycanth.; Papaver. (Papaveroideae, several); Saxifrag. (Philadelphus, Ribes); Ros. (Many); Legum. (Faboideae, several); Euphorbi. (Ricinus); Rut. (Phellodendron); Simaroub. (Ailanthus); Anacardi. (Rhus); Hippocastan. (Aesculus); Rhamn. (Rhamnus); Corn. (Cornus); Primul. (Cyclamen); Ole. (Forsythia, Fraxinus, Syringa); Gentian. (Gentiåna); Solan. (Solanum); Bignom. (Catalpa); Gesneri. (Achimenes); Caprifoli. (Symphoricarpos, Viburnum); Valerian. (Valeriana); Lili. (one of the main N-storage materials); Amaryllid. (Bravoa, Narcissus); Dioscore. (Dioscorea); Irid. (Tigridia); Bromeli. (in all tested: one of the main N-storage materials); Arac. (in all storage organs?); Zingiber. (Alpinia); Marant. (Maranta) l-Glutamine (H2N. CO . CH2 . CH2 . CH(NH2) . COOH) is the amide of glutamic acid (above). It is a `protein' amino-acid, but also occurs free: Cact. in all examined ? Ranuncul. several Arac. in several, as a N-storage material Glycine (a-Amino-acetic acid; H2N. CH2 . COON) is the simplest of the `protein' amino-acids, and one of the first to be discovered. It seems not to occur in quantity in the free state. l-Histidine (ß-Imidazole-a-amino-propionic acid; fig. 87) is a `protein' amino-acid. I have only a few records of it in the free state: Legum. Lupinus albus, luteus Comp. Helianthus annuus, Scorzonera hispanica Lili. not found by Fowden and Steward (1957) Gram. Secale cornutum

374

CHEMOTAXONOMY OF FLOWERING PLANTS

l-Homoarginine (a-Amino-e-guanidino-caproic acid) is obviously closely related to y-hydroxy-homoarginine and lathyrine. Legum. Lathyrus (sds of at least 36 spp., Bell, 1962) l-Homoserine (y-Hydroxy-x-amino-butyric acid) is, says Fowden (1962), an obligatory intermediate for the production of methionine and threonine from aspartic acid. See also azetidine-z-carboxylic acid. Legum. Pirum sativum (sdlg) y-Hydroxy-arginine occurs in marine animals and in Legum. Vicia (in all (17) examined; Bell and Tirimanna, 1963) l-ß-Hydroxy-glutamic acid (HOOC . CH2 . CH(OH) . CH(NH2) . COOH) Legum. Stizolobium niveum (in a globulin) Cucurbit. Cucurbita pepo (sd) y-Hydroxy-glutamic acid (HOOC . CH(OH) .CH2. CH(NH2) . COOH) Polemoni. Phlox decussata (free and in protein ?} Scrophulari. Linaria vulgaris (free) Lili. in at least z genera y-Hydroxy-homoarginine: a link between 1-homoarginine and lathyrine? Legum. Lathyrus (4 spp. of Bell's `group 3') 4-Hydroxy-hygric acid (4-Hydroxy-N-methyl-pyrrolidine-2-carboxylic acid) is related to betonicine and turicine. Euphorbi. Croton gubouga (bk) S-Hydroxy-lysine (H2N . CH2 . CH(OH) . CH2 . CH2 . CH(NH2) . COOH) does not occur in higher plants ? y-Hydroxy-y-methyl-glutamic acid occurs in large amount in a fern and, say Fowden and Steward (1957), in Lili. Calochortus sp. (sd, trace); Erythronium sp. (lvs, trace); Lilium longiflorum (IN's, trace); Littonia modesta (sd, trace); Puschkinia sp. (lvs, trace); Tulipa acuminata (lvs, trace), biflora (lvs, trace), clusiana (lvs, trace), fosteriana (lvs, trace), gesneriana (lvs, trace), linifolia (lvs, trace), praestans (lvs, trace), stellata (lvs, trace), sylvestris (lvs, trace), tarda (lvs, trace) 4-Hydroxy-pipecolic acid (4-Hydroxy-piperidine-z-carboxylic acid) Legum. Acacia, Albizia, Baikiaea Mus. Strelitzia reginae 5-Hydroxy-pipecolic acid has been found in ferns and in Legum. Acacia, Baikiaea, Saraca? Palmae. Phoenix, Rhapis l-Hydroxy-proline occurs in 2 forms (free, or combined ?). Salic. Populus (I form, pollen) Betul. Betula, Corylus (I form, pollen?) Santal. Santalum album (lvs, 2 forms) Gerani. Erodium Agay. Dracaena (free)

AMINO-ACIDS

375

Hypoglycin-A (ß-(Methylenecyclopropyl) alanine; fig. 87) Sapind. Blighia sapida (unripe aril, sd) Hypoglycin-B is a glutamyl-peptide of hypoglycin-A. Sapind. Blighia sapida Isoleucine (ß-Methyl-a-amino-valeric acid; H3C . CH2. CH(CH3) . CH(NH2) . COOH) is a ` protein' amino-acid which also occurs free in Fag. Fagus sylvatica (trace in bleeding sap) Legum. Glycine, Lupinus, Vicia Hippocastan. Aesculus hippocastanum (a little in bleeding sap) Lathyrine (ß-(2-Aminopyrimidin-4-yl) alanine; ?Tingitanine; fig. 87) is nearly related to 1-homoarginine. Legum. Lathyrus (at least 12 spp.) Irid. Iris tingitanus? l-Leucine (?Chenopodin; ß-Isopropyl-a-amino-propionic acid; (H3C)2CH . CH2 . CH(NH2) . COOH) was one of the first ` protein' amino-acids to be isolated. It is one of the more abundant acids of plant proteins. It, and isoleucine may be important in the production of hemiterpenes. Chenopodi. Chenopodium album (sap, `chenopodin') Legum. Lupinus, Pisum (etiolated sdlg), Vicia Hippocastan. Aesculus hippocastanum (trace in sap) Solan. Solanum tuberosum (tuber) Lili. present in all of the many species examined (Fowden and Steward, 1 957) 1-Lysine (a-e-Diamino-caproic acid) is a `protein' amino-acid, occurring to the extent of 1-6% in plant proteins. Vogel (1959) says that 2 biosynthetic pathways of lysine formation are known—via a-aminoadipic acid and via a-e-diamino pimelic acid. All of the few higher plants that he studied used the latter path. Legum. Lupinus, Pisum, Robinia, Vicia Lili. in some, at least exo(cis)--3, 4 Methanoproline Hippocastan. Aesculus parviflora (sd) l-Methionine (H3C . S . CH2 . CH(NH2) . COOH) is a constituent of most proteins and enzymes. Karrer (1958) says that it seldom occurs in the free state. It may arise from aspartic acid via homoserine. It is important in methylation. Lili. not found by Fowden and Steward (1957) Gram. `Phyllostachys edulis' (whatever that is, shoots) and in some other grasses (sds) a-Methylene-cyclopropyl-glycine (fig. 87) is a most unusual amino-

376 CHEMOTAXONOMY OF FLOWERING PLANTS

acid. The next higher member of the series, hypoglycin-A, also occurs in the Sapindaceae. See discussion under that family. Sapind. Litchi chinensis (sd) y-Methylene-glutamic acid (fig. 87) Legum. Arachis hypogaea (sdlg) Lill. Calochortus sp. (sd); Erythronium sp. (lvs, sd); Fritillaria meleagris (lys, much); Haworthia coarctata (lvs); Lilium longiforum (lvs, much); Notholirion (Lilium) thomsonianum (lvs); Tulipa acuminata (lvs), biflora (lvs), clusiana (lys), fosteriana (lvs), gesneriana (lvs, sd), greigii (lys), kaufmanniana (lvs), linifolia (lvs), montana (lvs), praestans (lvs), pulchella (lvs), stellata (lvs, much), sylvestris (lvs), tarda (lvs) y-Methylene-glutamine Legum. Arachis hypogaea (sdlg and plt—over 95% of total N in exuding sap is in this amide, says Fowden, 1962), Saraca indica (sd) Lili. Erythronium sp. (lvs, much; sd); Tulipa acuminata (lvs, much), biflora (lvs), clusiana (lvs), fosteriana (lvs, much; sd), gesneriana (lvs, much), greigii (lvs, much), kaufmanniana (lvs, much), linifolia (lvs), montana (lvs), praestans (lvs, much), pulchella (lvs, much), stellata (lvs), sylvestris (lvs), tarda (Ivs, much) y-Methyl-glutamic acid Legum. Glycine?; Lathyrus aphaca, maritimus Polygal. Polygala vulgaris Lili. Calochortus sp. (sd, much); Erythronium sp. (sd); Lilium longiflorum (lvs, much); Notholirion macrophyllum (lvs), thomsonianum (lvs) ; Puschkinia sp. (lvs) ; Tulipa biflora (lvs), clusiana (lvs), fosteriana (lvs), gesneriana (lvs), greigii (lvs), kaufmanniana (lvs), linifolia (lvs), montana (lvs), praestans (lvs), pulchella (lvs), stellata (lys), sylvestris (lvs) 5-Methyl-pipecolic acid Solan. Lycopersicum pimpinellifolium. Prelog and Jeger (196o) say: `The occurrence of 5-methyl pipecolic acid in the leaves of the tomatine-containing primitive Lycopersicum pimpinellifolium Mill. is of unusual interest in that it embraces in its structure that of ring F of the Solanum alkaloids.' Mimosine is treated as a pyridine alkaloid. N-Acetyl-l-djenkolic acid Legum. Mimosoideae (sds) N4-Ethyl-asparagine (HN(C2H5) . CO . CH2 . CH(NH2) . CO OH) Cucurbit. Ecballium elaterium and others. Fowden (1962) says it is not known from other families and that it may be regarded as an alternative to asparagine as a form of N-storage.

AMINO-ACIDS

377

N4-Hydroxyethyl-asparagine Cucurbit. Bryonia dioica N4-Methyl-asparagine Cucurbit. Corallocarpus epigaeus (Fowden and Dunnill, 1965) l-N-Methyl-tyrosine (Andirine; Geoffroyin; Ratanhin; Surinamin; fig. 87) Legum. Andira inermis, Ferreirea (Andira) spectabilis, Geoffraea surinamensis Krameri. Krameria triandra l-Norleucine (a-Amino-caproic acid) Euphorbi. Ricinus communis (a doubtful record) O-Acetyl-homoserine Legum. Pisum sativum Orcyl-alanine Caryophyll. Agrostemma githago (sd). It appears to be used in germination. It is formed from acetate and serine, through orsellinic acid (Hadwiger et al. 1965) a-Oxalylamino-y-amino-butyric acid occurs in equilibrium with aamino-y-oxalylamino-butyric acid (Bell and O'Donovan, 1966) in Legum. Lathyrus spp. a-Oxalylamino-ß-amino-propionic acid occurs in equilibrium with a-amino-ß-oxalylamino propionic acid (Bell and O'Donovan, 1966) in Legum. Lathyrus spp. l-Ornithine (a,8-Diamino-valeric acid; H2N . CH2 . CH2. CH2 . CH(NH2) . COOH) has been reported to occur in red algae, ferns, and a few higher plants. Betul. Alnus glutinosa (rt) Celastr. Catha edulis (lvs) l-Phenyl-alanine (ß-Phenyl-a-amino-propionic acid) is a `protein' amino-acid, amounting to from 3 to 5% or more in plant proteins. Its metabolism has been much studied. It has been reported to occur free in Legum. Lupinus, Phaseolus, Vicia Lili. less general than some other amino-acids (Fowden and Steward, 1957) l-Pipecolic acid (Pipecolinic acid; Piperidine-z-carboxylic acid) seems to be rather common in the free state. Fowden (1962) says: `The legumes Baikiaea plurijuga ... and several species of Acacia, contain mixtures of pipecolic acid, 5-hydroxy- and 4-hydroxy-pipecolic acids, and baikiain (04.5-dehydro-pipecolic acid). Interconversion of these amino acids may depend on...enzymes.' Legum. Acacia spp., Baikiaea plurijuga, Phaseolus vulgaris (from lysine), Saraca indica (sd), Trifolium repens (lvs)

378 CHEMOTAXONOMY OF FLOWERING PLANTS

Solan. Lycopersicum esculentum (in pits deficient in Fe and Mn; Possingham, 1956) Lill. Chionodoxa luciliae (lvs), Convallaria majalis (sd), Fritillaria imperialis (sd), Haworthia coarctata (lvs), Hosta lancifolia (lvs), Hyacinthus orientalis (lvs), Maianthemum canadense (Ns), Muscari armeniacum (lvs), Smilacina racemosa (lvs) l-Proline (Pyrrolidine-a-carboxylic acid; fig. 87) is a `protein' aminoacid. In plant proteins it amounts to from 3 to 5, or more rarely to 9%. Davies et al. (1964) say that tracer experiments support the view that it may arise from an a-amino-acid such as glutamic acid. It seems to be widely spread also in the free state. Betul. Betula (pollen), Corylus (pollen) Legum. it may be the chief soluble nitrogenous substance in members of the Faboideae. Rut. Citrus spp. (lvs, much) Gram. Phyllostachys (shoot), Zea (pollen) Lill. ` less general' than some other amino-acids Sarcosine (N-Methyl-glycine; H3C . NH . CH2 . COOH) Legum. Arachis hypogaea (in protein) Seleno-cystathionine: see also Selenium and Selenium compounds Legum. Astragalus pectinatus is said to have a compound of 2 x selenocystathionine and 1 x cystathionine Se-Methyl-selenocysteine Legum. Astragalus l-Serine (ß-Hydroxy-a-amino-propionic acid; CH2OH . CH(NH2) . COOH) is a `protein' amino-acid. It occurs in large amount in proteins of seaweeds, but in small amount in those of higher plants. It may arise from glycine and formate. It seems to occur free in many plants: Betul. Alnus, Carpinus, Corylus (little in all) Cad. Opuntia ficus-indica (little?) Simaroub. Ailanthus (little) Lili. general Irid. Gladiolus Bromeli. Ananas, Billbergia Arac. Zantedeschia aethiopica (rt, tuber) S-Methyl-l-cysteine Legum. Astragalus bisulcatus, Phaseolus vulgaris S-Methyl-cysteine-sulfoxide (H3C . SO . CH2. CH(NH2) . COOH) Crucif. Cabbage (lvs), turnip (lvs) Lili. Allium spp. + S-Methyl-methionine ((CH3)2S . CH2 . CH2 . CH(NH2). COOH) may, says Kjaer (1958), `be identical with the so-called vitamin U of cabbage

AMINO-ACIDS NH 2

COOH

~COOH 5 ( NH2 "-"LCOOH

\~1 r COOH

HOOC NH2

NH2

Y-Methylene-glutamic acid

Djenkolic acid

d-Methy lene-cyclopro pyl-glycine

COOH

COON

~V~ll

379

NI H2

Hypoglycin-A

2-Ami no-4- methyl hex- 5-ynoic acid

f`N ~COOH

COOH

~

NH2 f COON

N

H

H

I- Proline

Azetidine-2-

Cucurbitin

—carboxylic acid

COOH HO

\v

H2

HO

H Histidine

I-Tyrosine

N HO N

~COOH

0 NH2 J`

N-Methyl-tyrosine

H2Ny N

COON NH2

N

COON

m-Carboxyphenyl-

p-Uraci(-3-yl-alanine

Lathyrine

(Willardiine)

- I-alanine

O

COOH N

N' 'COON HH

NH2

H

5

N H

COON

2145 Dehydro-pipetoIic acid .(Baikiain)

I-Tryptophan

Fig. 87. Some amino-acids.

Cyclo-alliin

380 CHEMOTAXONOMY OF FLOWERING PLANTS

juice which appears to be of some promise in the treatment of peptic ulcers in human beings'. Crucif. Cabbage, turnip Umbell. Petroselinum crispum Comp. Lactuca sativa Lili. Asparagus S-Propyl-cystein-sulphoxide Lili. Allium l-Threonine (ß-Hydroxy-a-amino-butyric acid) is a `protein' aminoacid. It may arise from homoserine and perhaps from aspartic acid. Ulm. Ulmus? Crassul. Kalanchoe Legum. Lathyrus? Hippocastan. Aesculus Lili. it seems to be general. l-Tryptophan (ß-Indole-alanine; fig. 87) is a `protein' amino-acid. It seems not to be common in the free state. Legum. in seedlings of some species Celastr. Catha edulis Gram. in some members l-Tyrosine (p-Hydroxy-phenyl-alanine; fig. 87) is a `protein' aminoacid. It is said to constitute 1o% of the zein of maize. Fag. Fagus (trace) Ulm. Ulmus (trace) Hippocastan. Aesculus (tr.) Lili. `less general' than some other amino-acids Gram. Lolium, Secale, Zea (in zein) ß-Uracil-3-yl-alanine (Willardiine; fig. 87) Legum. Mimosoideae l-Valine (a-Amino-isovaleric acid; (CH3)2CH . CH(NH2) . COOH) is a `protein' amino-acid. It occurs free in Legum. Lupinus spp. (sdlgs), Vicia Hippocastan. Aesculus hippocastanum (sap, little)

II PEPTIDES GENERAL We know relatively little about the peptides of plants. Alston and Turner (1963), while discussing amino-acids, say: `Although most work has been devoted to single amino acids it is now evident that a variety of

PEPTIDES 381

peptides may exist, and these may prove, eventually, of considerable taxonomic importance.' The peptides consist of amino-acids, linked by so-called peptide linkages (—CO . NH—). The simplest of them, of which many are known, have but two amino-acids linked together. In these dipeptides the same acid may be repeated, as in glycyl-glycine, or two different ones may be involved, as in y-z glutamyl-ß-alanine. Compare these with the disaccharides. Somewhat more complicated are the tripeptides such as glutathione and the fungal tetrapeptide—malformin—of Aspergillus niger. I do not know of tetra- and pentapeptides from higher plants, but they are said to occur in marine algae. Some peptides are antibiotic, an example being gramicidin-S which is a cyclic decapeptide: Val Orn -* Leu D-Phe -* Pro y T Pro E- D-Phe 4- Leu 3% Zn in ash) Saxifrag. Philadelphus (indicator)

ELEMENTS

493

Rut. indicators? Aquifoli. Ilexglabra (up to 61.5 ppm dry wt) Viol. Viola tricolor var. calaminare (accumulator), other species may have up to 2% Zn in ash. Clethr. Clethra alnifolia (to 127.5 ppm dry wt) Plumbagin. Armeria elongata (o-42% Zn in ash), maritima var. helleri (4-5% Zn in ash) Comp. indicators? Zirconium (Zr). I have no records of zirconium in land plants, but freshwater plants are said to absorb it (concentration-factor 623o).

FATS AND FATTY-ACIDS GENERAL

Fats and fatty-oils (which are fats liquid at 'room temperature') are esters of fatty-acids with the trihydric alcohol glycerol. Theoretically fatty-acids can form esters with monohydric alcohols—and they do, to form waxes; with dihydric alcohols such as ethylene glycol—and they seem not to do this;' with trihydric alcohols such as glycerol—and we have seen that they do, to form fats; and with alcohols which have more than three -OH groups—but I have no knowledge of any such compounds. It seems strange that Nature is so selective! The fats are legion. They seem to occur in all living things, and in them in all living cells. We must distinguish between the universal 'body-fats', as they are called, and the more specialized 'depot-fats' which are stored (in plants) in some fruit-coats, in many seeds, and occasionally in other organs. Body-fats The ' body-fats' seem to vary rather little in composition. We have some information for leaf-lipids (Shorland, in Swain, 1963) which may be summarized here. The total leaf-lipids amount to about 7% of the dry matter. Much of this consists of galactolipids, only a little of true fat. Shorland says that linolenic acid is a major or chief fatty-acid component. He also says: 'The information on the fatty acid composition of leaf lipids is not sufficiently detailed or extensive to have any great taxonomic value.' There is some indication that although the leaf-lipids vary relatively But Varanasi and Malins (1969) have found what seem to be ethers of diols (like H37C18-O-CH2CH2CH2CH2CH2-O-C18H87 ?) in lipids of porpoise jaw oils.

494

CHEMOTAXONOMY OF FLOWERING PLANTS

little as compared with seed-fats, they may in some cases reflect any unusual composition of the latter. Thus, quoting Shorland again: The evidence suggests that the compositions of leaf and seed lipids are generally quite unrelated. Instances may be found, however, where the occurrence of an unusual acid in the seed fat is reflected in the lipids of other parts of the plant. Thus the cyclopropene acids, malvalic and sterculic ... , are found in both seed and leaf lipids of some species of Malvaceae and Sterculiaceae. Ximenynic acids, present in seed fats of certain members of the Olacaceae and Santalaceae, also occur as such, or in a related form, in other parts of the plant ...the occurrence of an unusual acid both in the lipids of the seeds as well as in other parts of the plants, appears to have special taxonomic significance. Fruit-coat fats These were also discussed briefly by Shorland (loc. cit.). Some information was available to him from sixteen families: Anacardi.,

Burser., Caprifoli., Capparid., Caryocar., Celastr., Cucurbit., Elaeagn., Euphorbi., Laur., Meli., Myric., Ole., Palmae, Sterculi. and Valerian. Most fruit-coat fats have palmitic, oleic and linoleic acids. Shorland says: `As with leaf lipids, fruit coat fats bear, as a rule, little resemblance to the seed fats from the same species.' We may illustrate this from the families Lauraceae and Palmae. Most of the Lauraceae have seed-fats with much lauric acid and little oleic acid. Laurus nobilis seed-fat, for example, has about 42% lauric acid and about 36% oleic acid (unusually high for the family), while its fruit-pulp has o to 3% lauric acid, 20-24% palmitic acid, 56-63% oleic acid, and 14-22% linoleic acid. The fruit-coat of the avocado (Persea gratissima) has 17% palmitic acid, 68% oleic acid and 8% linoleic acid: no lauric acid was recorded. In the Palmae most (all ?) members have seed-fats very rich in lauric acid (35-5o%) with lesser amounts of higher and lower members of the saturated series. In Elaeis guineensis fat is stored both in the seed (palm-kernel oil) and in the fruit-coat (palm oil). The former is typical of the seed-fats of palms, with 3-7% capric acid, 50-52% lauric acid, and 14-15% myristic acid. The latter has a quite different composition, with 32-47% palmitic acid and 40-52% oleic acid. Seed-fats These are of tremendous interest and importance. Much more work has been done upon them than upon body-fats and fruit-coat fats, few

FATS AND FATTY-ACIDS

495

of which are of direct economic value. (Palm-oil, mentioned above, and olive-oil are exceptions. I have no very recent figures for either but over 200,000 tons of palm-oil and something like I,000,000 tons of olive-oil are produced each year.) The seed-plants are the dominant plants of the world and their seeds with few exceptions (such as those of orchids) contain massive food reserves for the use of the embryo when germination occurs. The food may be stored in the nucellus (perisperm), in the endosperm, and/or in the embryo. It may be largely as carbohydrate (cereals), as protein in part (legumes) and/or as fats and fatty-oils. Where the storage material is fat or oil it is usually, but by no means always, in the endosperm. Man makes use of fat-storing seeds on a hugh scale. Wolff (1966) says that more than 20,000,000 tons of vegetable fats and fatty-oils are produced annually, mostly from seeds. A few examples of annual production will suffice here (not all the figures are recent) : Linseed oil (Linum usitatissimum)-6,000,000 acres in Argentina; 40,000,000 bushels from U.S.A. Cottonseed oil (Gossypium spp.)—about 500,00o tons of oil. Sesame oil (Sesamum indicum)—more than 3,000,000 acres. Corn oil (Zea mays)—at least Ioo,000 tons of oil. Olive-oil (Olea europaea)—about 1 ,000,000 tons. Coconut oil (Cocos nucifera)—at least 500,000 tons of nuts. Palm oil (Elaeis guineensis)—over 200,000 tons. Palm-kernel oil (Elaeis guineensis)—at least 500,00o tons of kernels. When fats are extracted for analysis from seeds we must remember that body-fats as well as depot-fats are included. In the case of seeds with much fat-storage the body-fats will be swamped and show up hardly at all in the analyses. In the case of seeds with quite low percentages of depot-fats the fatty-acids from the body-fats will loom large. One wonders how important this may be in interpreting the figures given for such seeds. Plants are curiously selective in the fatty-acids which they use in seed-fats. It is true that they produce a very large number of fatty-acids —I have included nearly 150 in the lists which follow, and I have certainly omitted many—but a large proportion of these are rare or occur in small amount. The ones used commonly are surprisingly few in number. Hilditch (1956) has this to say: Oleic and linoleic acids together probably account for about 8o per cent. or more of the total production of fatty acids in vegetable seed fats, whilst palmitic acid probably amounts to less than 1 per cent. of the total fatty acids produced in the world's seed fats. All other

496 CHEMOTAXONOMY OF FLOWERING PLANTS

component fatty acids found in seed fats, unsaturated or saturated, together make up, therefore, a little more than to per cent. of the whole of the seed fats produced annually in the world... Any complete theory of plant fat synthesis must account for the invariable appearance and overall predominance of oleic and linoleic acids, the invariable presence of palmitic acid, and for the occasional development in specific families or species of other acids, saturated or unsaturated, and also for the frequent constitutive resemblances between the rarer unsaturated acids and oleic acid. Why, we might emphasize, are the commonest fatty-acids in most cases the C18 acids ? The following list shows this to be so (the numbers are those of my sections): I. Stearic acid: in at least 8o families, though rarely in large amount. II. Oleic acid (see above) III. Linoleic acid (see above) IV. Linolenic acid is one of the commonest of the fatty-acids with 3 double bonds. V. Three out of four of the acids listed are C18. VI. None in plants ? VII. Almost all of the acetylenic acids listed are C18. VIII. The two fatty-acids here are C18. IX. C18 acids seem to be the commonest. X. All (?) C18 acids. XI. Several C18 acids are prominent. XII. Chaulmoogric acid (the C18 member of the series) is the most widely spread. XIII. A methyl-C18 acid occurs. Why, we might also ask, are virtually all fatty-acids of fats unbranched and with even numbers of C-atoms ? That there are exceptions shows that at least some plants can synthesize these oddities. Why, too, do some members of families behave uncharacteristically ? Hilditch (1956) recognizes that this is the case: It is curious to find, in a number of otherwise well-behaved botanical families, how here and there a quite extraordinary departure from the conventional seed fatty acids appears in isolated instances. Thus the monotony of the otherwise simple linoleic-rich' seed fats of the Compositae ... is relieved by the appearance in the seeds of Vernonia anthelmintica of vernolic' (12,13-epoxy-octadec-9-enoic) acid... ; Sterculia foetida, a member of a family which normally produces seed fats ...rich in stearic as well as palmitic acid, and with little

FATS AND FATTY-ACIDS

497

unsaturated acids other than oleic, yields a seed the fat in which contains a most unusual unsaturated acid of the structure CHS[CH,],. C=C . [CH2], . COOH. CH, Quite probably, of course, other similar phenomena will continue to come to light as time goes on. We shall see that the `most unusual' structure shown above turns up in at least four families of the Malvales (section ix and p. 1458). A paragraph or two on the composition of the triglycerides (fats) would seem to be in order here. We might expect that—given a number of molecules of different fatty-acids, and a number of glycerol molecules to form fats—the unions would be statistically random ones, the fat molecules having the different fatty-acids in the proportions expected. This is not the case: some plants, at least, seem preferentially to synthesize certain combinations. Thus Laurus nobilis seed-fat is said to have a higher percentage of trilaurin than would be expected from the fattyacid mixture resulting from hydrolysis of the fat. The seed-fat of Cuphea lanceolata contains more tridecanoin than would be expected (Litchfield, Miller, Harlow and Resier, 1967). Wolff (1966) says that the vernolic acid of Vernonia anthelmintica is present almost entirely as trivernolin; while in Euphorbia lagascae, the seed-oil of which has 57% vernolic acid, there is only 18.5% trivernolin. An interesting triglyceride is said to occur in Sapium sebiferum. It seems to have a tetra-ester constitution (see 8-hydroxy-n-octa-5-6-dienoic acid). How well do we know the fats of plants ? Scharapow (1958) says that one-third of all (higher ?) plants store oil or fat. The first edition of Hilditch's Chemical Constitution of Natural Fats (1940) listed about 400 plant fats, the second (1947) about 450, the third (1956) about 600, and the fourth (by Hilditch and Williams, 1964) about goo. The number examined by this time will be much above this—Wolff (1966) says less than I000—and there are obviously an enormous number that remain to be studied, the more so as a high proportion of the earlier analyses are suspect. We must remember how difficult it was, in the `good old days' of plant biochemistry, to analyse fat, and how easy it was to overlook odd fatty-acids occurring in small amounts. Today the task is vastly easier and the numbers of papers appearing are so large that I, for one, have been quite unable to keep up with the literature. We may still find much of chemotaxonomic interest in the lists that follow and may say with Shorland (in Swain, 1963): In conclusion, although the data on the types and distribution of fatty acids do not provide an unequivocal guide to the classification

498 CHEMOTAXONOMY OF FLOWERING PLANTS

of plants, many correlations of taxonomic significance have become apparent in spite of the small number of species examined up to now. It is believed that the results so far obtained justify more extensive investigations in this field and that the study of fats has a role in the chemical taxonomy of plants. Classification of fatty-acids As in so many of our chapters there is no completely satisfactory classification. Where does an acid with one -OH group and two double bonds belong, or an acetylenic acid with a cyclopropenyl group ? When we know more of the biosynthetic pathways we may know the answers to such problems of classification. In the meantime the classification followed here is: I. Saturated fatty-acids: 15 listed II. Fatty-acids with one double bond i. Oleic acid series A and B: 14 listed 2. Not in the oleic acid series: ig listed III. Fatty-acids with two double bonds i. Linoleic acid series A and B: 3 listed 2. Not in the linoleic acid series: 8 listed IV. Fatty-acids with three double bonds i. Linolenic acid series A and B: 2 listed 2. Not in the linolenic acid series: 8 listed V. Fatty-acids with four double bonds I. With bond arranged -(CH=CH)4-: I only 2. With bonds arranged -(CH=CH.CH2)4-: 2 listed 3. With bonds arranged otherwise: I only VI. Fatty-acids with five double bonds: none known from plants ? VII. Fatty-acids with acetylenic linkages I. With one acetylenic linkage: io listed 2. With two acetylenic linkages: 3 listed 3. With three acetylenic linkages: 4 listed VIII. Fatty-acids with a keto group: 4 listed IX. Fatty-acids with a cyclopropenyl group: 4 listed X. Fatty-acids with an epoxy group: 4 listed XI. Fatty-acids with one or more -OH groups I. Saturated fatty-acids with an w-OH group: Io listed a. Saturated fatty-acids with an -OH group in the a- (or 2) position: 2 listed 3. Saturated fatty-acids with an -OH group in other than the wor a- positions: 3 listed

FATS AND FATTY-ACIDS

499

4. Saturated fatty-acids with 2, 3, or 4 -OH groups: 6 listed 5. Unsaturated fatty-acids with i or more -OH groups: 9 listed XII. Fatty-acids with a terminal cyclopent-2-enyl group (the chaulmoogric series) : 9 listed XI I I. Branched-chain fatty-acids: 4 listed Biosynthesis Hendrickson (1965) says that the biosynthesis of fatty-acids is now well understood. They arise from acetate by carbon—carbon bond formation via an aldol-type condensation. This by repetition gives long chains with the characteristic even number of C-atoms. For details the reader is referred to chart 4 in Hendrickson's little book. We add a few further notes. Wolff (1966) says that fatty-acids with cyclopropenyl and epoxy groups coexist with acetylenic acids `in amounts and positions such as to suggest strongly that these various groups are related biosynthetically '. Odd C-number fatty-acids are very rare in plants. The occurrence of large quantities of C-17 acetylenic acids in Acanthosyris is therefore of great interest. They coexist with C-18 acids and Wolff suggests that a-oxidation leads to loss of one C-atom. In the case of sterculic acid (oddnumbered) Wolff argues that it is `undoubtedly formed by addition of 1 carbon to an even-numbered precursor' and that it gives rise to malvalic acid by a-oxidation. Wolff's paper is full of intriguing suggestions, some supported by evidence, others biosynthetically plausible. There is no doubt that we shall know within a few years a great deal about the origins and interrelationships of the fatty-acids. This will add enormously to the chemotaxonomic usefulness of these substances. Literature The literature on fats and fatty-acids is so immense that we can afford to cite only a minute fraction of it. Many more particular references are scattered through my lists, or are cited when discussing the plants involved. We shall refer here only to a few general sources which we have used extensively. A group of workers have been conducting a survey for new industrial fats and oils (Earle, Melvin, Mason, van Etten, Wolff and Jones, 1959 Earle et al. 196o; Earle, Wolff and Jones, 196o; Mikolajczak et al. 1961; Mikolajczak et al. 1962). Books on fats and oils include: Eckey (1954), Vegetable Fats and Oils; Gunstone (1958), An Introduction to the Chemistry of Fats and Fatty Adds; Hilditch (1940, 1947, 1956), The

500 CHEMOTAXONOMY OF FLOWERING PLANTS

Chemical Constitution of Natural Fats, editions 1, 2, and 3 and Hilditch and Williams (1964), edition 4; Jamieson (1944.), Vegetable Fats and Oils, edition z. Interesting surveys are those of Shorland (in Swain, 1963), and Wolff (1966).

I SATURATED FATTY-ACIDS GENERAL This series may be considered to begin with formic acid (H . COOH), and to proceed through acetic acid (CH3. COOH), and propionic acid (CH 3. CH2. COOH), to the higher members (CH3. (CH2).. COOH). The lower members occur as esters with monohydric alcohols; some higher members occur as esters of long-chain alcohols as waxes; members with even C-numbers from C4 to C28 or higher occur as esters of the trihydric alcohol glycerol as the fats and fatty-oils of living creatures. List and Occurrence n-Tetranoic acid (Butyric acid; CH3. (CH2)2. COOH) occurs in animal milk-fats. In plants it is found as esters in essential oils. I have no certain record of its occurrence in seed-fats. Does it occur (free ?) in: Sapind. Sapindus Myrt. Eucalyptus Umbell. occurrence ? n-Hexanoic acid (Caproic acid; CH3. (CH2)4. COOH) occurs in many fats but in small amount. We may note: Palmae. Cocos nucifera (endosperm, i%), pulposa (2%) n-Octanoic acid (Caprylio acid; CH3. (CH2)6 . COOH) rarely occurs in large amount in seed-fats. Ulm. Ulmus (several spp.), Zelkova (at least 1) have appreciable amounts; but absent (?) from Celtis (2), Chaetacme, and Trema. Lythr. Cuphea hookeriana (sd, 71%), painteri (sd, 78%) Palmae. probably in seed-fats of all. The records I have range from 1o% (Cocos pulposa) to 1% (Astrocaryum spp.) or possibly o% (Roystonia). n-Decanoic acid (Capric acid; CH3. (CH2)8. COOH) is a common constituent of seed-fats, but only in relatively few cases is it in large amount. Ulm. Early analyses seemed to support the split—Uemoideae with and Celtoideae without large amounts of capric acid—but later

FATS AND FATTY-ACIDS 50I

figures cut across this. See Ulmaceae for discussion. We may note: Ulmus spp. (sds, to 72%), Zelkova serrata (73%). Laur. Litsea zeylanica (sd, 4%), Neolitsea involucrata (sd, 37%), Sassafras albidum (sd + endocarp, 59%) Lythr. Cuphea hookeriana (sd, 24%), llavea var. miniata (sd, to 83%!), painteri (sd, 20%) n-Dodecanoic acid (Lauric acid; CH3. (CH2)10 • COOH) was first isolated from Laurus, and has subsequently been found to be characteristic of the seed-fats of Lauraceae and Palmae. It occurs in many other plant families but rarely in large amount. Myristic. members may average about 54% in seed-fats. Laur. Actinodaphne (sds, 90-96%), Cinnamomum (87-95%), Laurus nobilis (35-43%), Litsea (53-95%), Neolitsea (86%), Umbellularia californica (62%) Simaroub. Irvingia spp. (19-59%). Other genera have little? Vochysi. Erisma calcaratum? (one analysis reports 24%, another o%!) Salvador. Salvadora oleoides (sd, 2I-47%), persica (20%) Palmae. probably high in seed-fats of all Acrocomia (45%), Areca (r7?-54%), Astrocaryum (42-49%), Attalea (44-46%), Cocos nucifera (4-51%), Elaeis guineensis (50-52%), Hyphaene thebaica (32%), Manicaria saccifera (47%) n-Tetradecanoic acid (Myristic acid; CH3. (CH2)12. COON) seems to have been `chosen' for the seed-fats of the Myristicaceae. Most fruitcoat fats, too, seem to have some myristic acid. Myric. the so-called `wax' on fruits of Myrica is said to be a fat with large amounts of myristic acid. M. cerifera (33%), cordifolia (47-50%), mexicana (61%). Myristic. Myristica fragrans (sd, 6o-77%), irya (67%), malabarica (39%); Pycnanthus kombo (57-62%); Virola atopa (73%), bicuhyba (6773%), surinamensis (73%), venezuelensis (` much') Simaroub. Irvingia spp. (33-7o%). Other genera much less ? Vochysi. Erisma calcaratum (28-53%) Salvador. Salvadora oleoides (53%), persica (54%) Palmae. all or almost all seed-fats have from 9 to possibly 55% of myristic acid n-Hexadecanoic acid (Palmitic acid; CH3. (CH2)14. COON). Hilditch (1952), writing of oleic, linoleic, and palmitic acids, says that all three occur, sometimes in small proportion, in all seed fats. Fruit-coat fats may be very rich in palmitic acid. Caryocar. Caryocar villosum (sd-fat, 48%; frt-coat-fat, 45%) Rut. sd-fats average about 22% Except Rhopalostylis? (p. 1875)

502 CHEMOTAXONOMY OF FLOWERING PLANTS

Bombac. sd-fats average about 25% Combret. sd-fats average about 27% Sapot. Madhuca (sd-fat to 57%); other genera much less n-Octadecanoic acid (Stearic acid; CH3. (CH2)16. COOH) has been found in seed-fats of 8o families, says Karrer (1958). It is only rather seldom in large amount. Menisperm. Stephania (21%) Dipterocarp. Shorea robusta (44%), stenoptera (39-43%); Vateria indica (39-43%) Guttif. many, up to 6z% Capparid. Courbonia (to 39%) Burser. Dacryodes rostrata (31-40%); Canarium spp. (much less) Meli. several genera to 24% Anacardi. Mangifera (to 42%); other genera much less Sapind. Nephelium (to 31%); other genera less Sterculi. Theobroma to 35% Sapot. many to 6o% Convolvul. Cuscuta (3o%) In many of the genera with much stearic acid there is also oleic acid, and in the following genera the fatty-acids are almost entirely stearic + oleic : Shorea, Vateria, Allanblackia, Pentadesma, Palaquium, Mimusops, Madhuca, Butyrospermum, Dumoria, Payena. Families with very little stearic acid in their seed-fats include: Jugland., Betul., The., Crucif., Ros., Celastr., Bombac., Umbell., Solan., Lab., Palmae, and Gram. n-Eicosanoic acid (Arachidic acid; CH3. (CH2)18 . COOH) is widely distributed, but rarely in large amount in seed-fats. Legum. Abrus (5%), Acacia (to 2%), Albizia (to 11%), Arachis (hence the name, to z%), Butea (6%), Erythrina (3%), Pentaclethra (to 5%), Phaseolus (to 3%), Pongamia (to 5%), Tamarindus (4%), Trigonella (to 2%), Vicia (I %) Sapind. many have much more than have the legumes. Cardiospermum halicacabum (io%); Dodonaea viscosa (6%); Nephelium lappaceum (35%), mutabile (22%); Sapindus trifoliatus (ca. 22%); Schleichera trijuga (oleosa) (20-31%) n-Docosanoic acid (Behenic acid; CH3. (CH2)20. COOH) was found in oil of ben (or behen) (Moringa). It is rare and usually present only in small amount in seed-fats. Ochn. Lophira alata (to 34% ? Easily the largest percentage recorded), procera (2i%) Moring. Moringa pterygosperma (oleifera) (1-7%) Legum. general (?), but never in very large amount. Parkia

FATS AND FATTY-ACIDS 503

biglandulosa (8%, wrongly given as 39.4% in Karrer, 1958); Pentaclethra eetveldeana (iq.%), macrophylla (6%); Xylia xylocarpa (dolabriformis) (17%) Umbell. Ammi visnaga (some) n-Tetracosanoic acid (Lignoceric acid; CH3. (CH2)22. COOH) Aristolochi. Aristochia indica (root-oil has some) Legum. general (?) in small amount. Hegnauer (1956) says: Für die Leguminosen scheint nur das Trio Arachinsaure (C20), Behensaure (C22) and Lignocerinsaure (C24) charakteristisch zu sein. Die Summe der drei genannten gesattigten Fettsauren schwankt in den meisten diesbezuglich untersuchten Leguminosen-olen zwischen 1 and 25% des Totals der Fettsauren.' A few examples (arach.: behen.: lignocer. ; total) will illustrate Hegnauer's remarks. Abrus precatorius (5:5:3; 13 %) ; Adenanthera pavonina (lignoceric 25%); Butea frondosa (6:6:4; i6%); Cassia alata (lignoceric 15%); Dipteryx odorata (total 13-15%); Lupinus termis (total 6%); Pentaclethra eetveldeana (5:14:3; 22%), macrophylla (4:6:11; 2I%) Plantagin. Plantago ovata (1%) Other Karrer (1958) gives a list of fats from which lignoceric acid (presumably in small amounts) has been isolated. n-Hexacosanoic acid (Cerotic acid; CH3. (CH2)24. COOH) is known only from a few seed-fats. It seems likely that traces of it are present in those plants which produce arachidic, behenic, and lignoceric acids, since they obviously `specialize' in long-chain saturated acids. The waxes of palms and other plants are said to have much cerotic acid, but Hilditch (1956) says: `As already mentioned, "cerotic acid" of waxes is now recognized to be a mixture of several n-aliphatic acids of the even-numbered series, and is not solely n-hexacosanoic acid.' Olac. Ximenia americana (sd-fat, 2-15%) n-Octacosanoic acid (Montanic acid; CH3. (CH2)20. COOH) does not occur in seed-fats? It is present (I %) in leaf fat of buckwheat ? It occurs in the wax of Copernicia (Palmae). n-Tricontanoic acid (Melissic acid; CH3.(CH2)22.COOH) is not in seed fats ? It occurs in waxes, leaf-fats, etc., and has been reported from the fruit-coats of Illicium (Illici.) and Oenocarpus (Palmae). n-Dotriacontanoic acid (Lacceric acid; CH3. (CH2)30. COOH) has been reported to occur in carnauba wax.

504 CHEMOTAXONOMY OF FLOWERING PLANTS

II FATTY-ACIDS WITH ONE DOUBLE BOND List and Occurrence i. Oleic acid series may be divided into series A (cis-9-enoic acids) and series B (cis-3-enoic, cis-5-enoic, cis-7-enoic acids, etc.) SERIES A n-Dec-9-enoic acid (Caproleic acid; CH2=CH . (CH2)7 . COOH) occurs in milk-fat, but not in higher plants ? n-Dodec-9-enoic acid (CH3. CH2. CH=CH . (CH2)7 . COOH) occurs in butter-fat, but not in higher plants ? n-Tetradec-9-enoic acid (Myristoleic acid; CH3. (CH2)3 . CH=CH . (CH2)7 . COOH) occurs in many animal fats. In seed fats it has been recorded from Myristic. Pycnanthus kombo (24%); but not in other genera? Ochn. Lophira alata (< r%) Legum. Acacia cyclops (9%) Maly. Gossypium spp. ? Cucurbit. Citrullus colocynthis (< r%) n-Hexadec-9-enoic acid (Palmitoleic acid; CH3. (CH2) 5 . CH=CH . (CH2)7 . COOH) is probably as widely spread as oleic acid, says Hilditch (1952), but usually in small amounts. He says it may be present in larger amounts in aquatics, but my records seem all to stem from land-plants! Prote. Embothrium coccineum (23%), Lomatia hirsuta (23%), Macadamia ternifolia (20%); but Guevina avellana has hexadecI I-enoic add! Guttif. Platonia insignis (3%) Papaver. Argemone mexicana (1-6% ?); but absent from poppyseed oil ? Crucif. in small amount in many ? Legum. Acacia cyclops (9% ?), giraffae (8%) Maly. Gossypium herbaceum (eh?) Cucurbit. Hodgsonia capniocarpa (r%) AscØiad. Asclepias syriaca (10%) Bignoni. Doxantha unguis-cati (64%!) Comp. Cynara cardunculus (to 4%); other genera may have less Gram. wheat-germ (z%) Palmae. Areca catechu (8% ?), Cocos nucifera (1%?), Elaeis guineensis (04?) ?)

FATS AND FATTY-ACIDS 505

n-Octadec-9-enoic acid (Oleic acid; CH3. (CH2)7 . CH= CH . (CH2)7 . COOH) seems to be present in all natural fats and phosphatides. Many fatty-acids—linolenic; elaeostearic; parinaric; myristoleic; palmitoleic; n-eicos-ii-enoic; erucic; docos-13,16-dienoic; ximenic; lumequic—have one `half' or the other of oleic acid. This must surely be of some significance. The amount of oleic acid in seed fats of angiosperms varies enormously: Jugland. Carya cordiformis (72-88%), illinoensis (79%); other genera much less ? Betul. Corylus avellana (56-91%) Olac. Coula edulis (95%!). Variable amounts in other members. Ros. Crataegus oxyacantha (81%); Prunus amygdalus (to 77%), armeniaca (to 79%), laurocerasus (73%) (table 68). Caric. Carica papaya (8o-81%) At the other end of the scale are families with very low percentages of oleic acid: Salvador.: Salvadora oleoides (5-12%), persica (5%); Flacourti.: Caloncoba echinata (z%), welwitschii (< OA). Some fruit-coat fats are rich in oleic acid: Myristic. Myristica fragrans (ca. 8o%) Ole. Olea europaea (70-85%) Palmae Oenocarpus bataua (79-81%) n-Eicos-9-enoic acid (Gadoleic acid; CH3. (CH2)s . CH=CH . (CH2)7 . COOH) occurs in the liver of the cod (Gadus). It may occur in small amounts in some seed-fats, but I have no records of it. SERIES B n-Hexadec-7-enoic acid (CH3. (CH2)7 . CH=CH . (CH2)5. COON) has not been found in any plant fat ? n-Octadec-9-enoic acid (Oleic acid): above in Series A. n-Eicos-I 1-enoic acid (CH3.(CH2)7 . CH=CH. (CH2) 9. COOH) appears to be widely spread in dicotyledons. In seed fats we may note: Ranuncul. Delphinium hybridum (18%; Chisholm and Hopkins, 1 956) Ochn. Lophira (to 2% ?) Crucif. general? Hilditch (1956) says: `Eicos-11-enoic acid... has not so far been observed to exceed about 13 per cent. of the total acids in a Cruciferous seed fat. In the rape and mustard oils it rarely exceeds 5 or 6 per cent., but in some instances (Charlock and Camelina) in which it occurs in larger proportions it may actually exceed the amount of erucic acid which is also present.'

506 CHEMOTAXONOMY OF FLOWERING PLANTS

Legum. Acacia (to 2% ?), Erythrina crista-galli (9% ?) Tropaeol. Tropaeolum majus (zo%; Hopkins and Chisholm, 1953) Sapind. Cardiospermum halicacabum (42%, ' unique among the true natural fats' say Chisholm and Hopkins, 1958). Other genera that probably have this acid are Dodonaea (4%?), Nephelium (to 4% ?), Sapindus (to 22% ?) The liquid seed-wax of Simmondsia is said to have much eicos-t 1enoic acid. n-Docos-13-enoic acid (Erucic acid; CH3. (CH2)7 . CH=CH . (CH2)11. COOH) is the cis-form, and until recently it was thought that the trans-form (brassidic acid) did not occur. It has now been reported, with erucic acid (!), in the perianth of Fritillaria camschatcensis by Shibata and Takakuwa (1959)• Crucif. general? Ranging from 55% (Brassica campestris) to 3% (Camelina sativa) or even o% ? (Hesperis matronalis: has this been re-examined by modern methods ?) Limnanth. Limnanthes douglasii (13%) and other spp.; Floerkea (see discussion under family). Tropaeol. Tropaeolum majus (69%), minus? (82%) n-Tetracos-l5-enoic acid (Selacholeic acid; CH3. (CH2)7 . CH=CH . (CH2)13 . COOH) seems, says Hilditch (1956), to be 'a characteristic component of the fats of many Elasmobranch fish ...'. It is rare in seed fats. Olac. Ximenia spp. (in small amounts) Crucif. Lunaria biennis (21%, Wilson et al. 1962) n-Hexacos-17-enoic acid (Ximenic acid; CH3. (CH2)7 . CH=CH . (CH2)15 . COOH) is known only from seedfats of Olac. Ximenia americana (9 to z5%), caffra and var. (3 to 7%) n-Octacos-19-enoic acid (CH3. (CH2)7 . CH=CH . (CH2)17 . COOH) is, like ximenic (above) and lumequic acids (below), known only from seed fats of Olac. Ximenia americana and var. (to Iz%), caffra and var. (5 to Io%) n-Triacont-2i-enoic acid (Lumequic acid; CH3. (CH2)7 . CH=CH . (CH2)1 2 . COOH) Olac. Ximenia americana and var. (to 7%), caffra and var. (3 to 50/0) n-Dotriacont-z3-enoic acid (CH3. (CH2)7 . CH=CH . (CH2)21. COOH) Olac. Ximenia (in small amount ?)

FATS AND FATTY-ACIDS 507 2.

Not in the Oleic acid series

List and Occurrence The possibilities here are very numerous but less than a dozen of these acids seem to occur in higher plants. n-Dec-4-enoic acid (Obtusilic acid; CH3. (CH2)4 . CH=CH. (CH2)2. COOH) occurs, with the related linderic and tsuzuic acids (below) in seed fats of Laur. Lindera obtusiloba, umbellata (cis-, 4%); Litsea? n-Undec- 1 o-enoic acid (CH2=CH.(CH2)8.COOH) occurs in fungi and conifers, but not, I think, in angiosperms. n-Dodec-4-enoic acid (Linderic acid; CH3. (CH2)6 . CH=CH . (CH2)2 . COOH) occurs in seed fats of Laur. Lindera hypoglauca (much ?), obtusiloba, strychnifolia (little), umbellata (cis-, 47%I); Litsea glauca (much ?) n-Tetradec-2-enoic acid (?Macilenic acid; CH3. (CH2)10 . CH=CH . COOH) Myristic. Myristica fragrans (mace, in small amount ?) n-Tetradec-4-enoic acid (Tsuzuic acid; CH3. (CH2)8. CH=CH . (CH2)2 . COOH occurs in seed fats of Laur. Lindera hypoglauca (little ?), obtusiloba, umbellata (cis-, 5%); Litsea glauca, japonica n-Hexadec-3t-enoic acid (CH3. (CH2)11. CH=CH . CH2 . COOH) has been reported from Chenopodi. Spinacia (leaf-fat) Scrophulari. Antirrhinum (leaf fat) Comp. Helenium bigelowii (seed fat, io%; Hopkins and Chisholm, 1964); absent from H. hoopesii? It is said to occur in at least 29 composites. n-Hexadec-iic-enoic acid Prote. one member n-Hexadec-i2-enoic acid (Tanacetum-oil acid; CH3. (CH2)2 . CH=CH . (CH2)10. COOH) occurs in spores of Lycopodium and in Comp. Tanacetum vulgare (flower-fat) n-Octadec-3t-enoic acid Comp. at least 7 species n-Octadec-6c-enoic acid (Petroselinic acid; CH3. (CH2)10 • CH=CH . (CH2)4. COON) is one of several monounsaturated C18 acids occurring in Nature (see oleic, petroselidic, elaidic, iso-oleic, cis-n-octadec-ii-enoic) Euphorbi. Mallotus japonicus (seed-oil ?) Simaroub. Picrasma quassioides (seed-oil, in large amount)

508 CHEMOTAXONOMY OF FLOWERING PLANTS

Arali. Hedera helix (seed-oil, 62%). The occurrence here is quoted as supporting relationship to Umbelliferae. I have no records of petroselinic acid in other members of the Araliaceae, however. Umbell. seed-fats of many n-Octadec-6t-enoic acid (Petroselidic acid; Tarelaidic acid) is known only from Umbell. in small amounts with petroselinic add (above). n-Octadec-9t-enoic acid (Elaidic acid): note that the cis-form is oleic acid above. Elaidic add is said to occur in fungi and rather doubtfully in Ranuncul. Delphinium staphisagria (seed-oil) Zygophyll. Tribulus terrestris (fruit-oil) Solan. Physalis peruviana (seed-oil) n-Octadec-ro-enoic acid (Iso-oleic acid) occurs in seed fats and in fruit-coat-fats. It is recorded from Ranuncul. Delphinium staphisagria (seed-fat) Ros. Cydonia (seed-fat), Malus (seed-fat), Pyrus (seed-fat), Rosa (seed-fat) Ole. Olea europaea (fruit-coat-fat) Arac. Pinellia tuberifera (tuber) n-Octadec-rrc-enoic acid (Asclepic acid) has been found in horselipids, in fungi, and in Asclepiad. AscØias syriaca (seed-fat, 15%; Chisholm and Hopkins, r96o) Bignoni. one member n-Eicos-5c-enoic acid Ranuncul. in one member ? Limnanth. Limnanthes douglasii (seed-fat, 65%), and at least 6 other spp. (see family) n-Docos-5c-enoic acid Limnanth. Limnanthes douglasii (seed-fat, 7%), and at least 6 other spp. (see family)

III FATTY-ACIDS WITH TWO DOUBLE BONDS r. Linoleic acid series GENERAL This group of unsaturated acids, with -CH=CH . CH2. CH=CHgrouping, may be considered to belong to two series (A and B), corresponding to those noted above for the oleic acid series.

FATS AND FATTY-ACIDS 509

List and Occurrence SERIES A n-Hexadec-9c, i 2c-dienoic acid (CH3 . (CH2)2 . CH=CH . CH2. CH=CH . (CH2)7 . COOH) seems to be rare. Legum. Acacia giraffae (seed-fat, some; but is it cis-, cis-?) Asclepiad. Asclepias syriaca (seed-fat, z%; probably cis-, cis-) n-Octadec-9c,12c-dienoic acid (Linoleic acid; CH3. (CH2)4. CH=CH . CH2. CH=CH . (CH2)7 . COOH) has, says Hilditch (1956): `been observed, in small or (often) large proportions, in every vegetable fat so far examined; it is as ubiquitous as oleic acid or palmitic acid... '. Notably high amounts have been found in Jugland. .7:glans spp. (to 76%); less in other genera ? Ulm. Celtis mississippiensis (74%), occidentalis (77-78%); Chaetacme microcarpa (8z%) Urtic. Urtica dioica (79%) Cucurbit. usually in fairly large amount Solan. Atropa belladonna (67%), Hyoscyamus niger (56-82%) Comp. usually in fairly large amount Agay. at least 13 species (in 5 genera) have 52-89% SERIES B n-Octadec-9,12-dienoic acid is linoleic acid (above). n-Docos-13,16-dienoic acid Crucif. Brassica campestris (rape-seed-oil, in small amount) 2. Not in the Linoleic acid series n-Deca-2,4-dienoic acid Euphorbi. Sapium discolor ? (seed-fat), sebiferum (seed-fat, 4-5%) n-Dodeca-2,4-dienoic acid Euphorbi. Sebastiana ligustrina (seed-fat, 5% ?) n-Octadeca-5t,9c-dienoic acid Ranuncul. in one member n-Octadeca-9t,izt-dienoic acid Bignoni. Chilopsis linearis (seed-fat, 15%; Chisholm and Hopkins, 1963) n-Octadeca-lot,Izt-dienoic acid Bignoni. Chilopsis linearis (seed-fat, I z%)

510 CHEMOTAXONOMY OF FLOWERING PLANTS

(-)-n-Octadeca-5,6-dienoic acid (Laballenic acid) is an allenic acid. Lab. Leonotis nepetaefolia (seed-fat). Probably of general occurrence in the Stachyoideae. (It is in 53 spp. ?) Comp. (This acid ?) Dicoma zeyheri (with its methyl ester, up to z•8% of dry wt) n-Octadeca- ?, ?-dienoic acid: a dienoic acid, perhaps one of the three above, has been reported from Chrysobalan. Parinari n-Eicosa- ?, ?-dienoic acid Ranuncul. Delphinium (1%) n-Docosa-5c,13c-dienoic acid Limnanth. Limnanthes spp. (seed-fats)—see family.

IV FATTY-ACIDS WITH THREE DOUBLE BONDS 1. The linolenic acid series GENERAL As with the oleic acid and linoleic acid series, we may distinguish two series (A and B) having one `end' or the other of linolenic acid itself. They are all cis,cis,cis- ? List and Occurrence SERIES A n-Octadeca-9,12,15-trienoic acid (Linolenic acid) seems to be the only member of Series A to occur in higher plants. Leaf fats may be rich in linolenic acid, and Hilditch (1956) points out that horse depot-fats have a considerable amount. He says: `It may be concluded that (like the pig...) the horse is capable of directly assimilating the natural fats present in herbage or seeds which form major parts of its food: pasture grass fats are rich in linolenic acid...'. Jugland. Pterocarya (sd-fat, probably fairly high—see family) Ros. Rosa canina (sd-fat, 14-32%), rubiginosa (sd-fat, i6%); Filipendula ulmaria (Ulmaria palustris) (sd-fat, 47%) Lin. Linum usitatissimum (' linseed-oil', 3o-6o%). Surprisingly, I have no records from other members of the family. Euphorbi. Euphorbia calycina (sd-fat, 6o-66%), erythraeae (53%), marginata (45%; Mercurialis perennis (67%); Tetracarpidium conophorum (63-68%)

FATS AND FATTY-ACIDS 511

Lab. Hyptis spicigera (sd-fat, 60-66%); Lallemantia iberica (sdfat, 53%), but royleana (none!); Ocimum kilimandscharicum (sdfat, 61-65%); Perilla ocymoides (sd-fat, 63-7o%); Salvia hispanica (sd-fat, 47-69%)

SERIES B n-Hexadeca-7,10,13-trienoic acid Crucif. Brassica napus (leaf-lipids, but is it cis, cis, cis- ?) n-Octadeca-9,12,15-trienoic acid is linolenic acid (above). 2. Not in the linolenic acid series The acids known to occur are all C18 acids, i.e. they are isomers of linolenic acid. n-Octadeca-9c,I1t,13t-trienoic acid (a-Elaeostearic acid) occurs in large quantities in a few seed-fats. Ros. Prunus yedoensis (35%) Chrysobalan. Cyclandrophora laurina (3x34%), Licania spp. (to 17%), Parinari spp. (to 7o%) Euphorbi. Aleurites spp. (47-81%), Garcia nutans (93-95%!), Ricinodendron africanus (49-53%), but absent from, or in very small amount in, some other genera. Cucurbit. Momordica spp. (seed-kernel, to 65%), Telfairia occidentalis (x9%) Valerian. Centranthus macrosiphon (5o%), rube' (43%); Valeriana officinalis (45%) n-Octadeca-6,9,12-trienoic acid (y-Linolenic acid) occurs in fungi and in the seed-fats of Mor. Humulus lupulus Onagr. Oenothera biennis (8-i o%), lamarckiana (3-8%), rhombipetala (5%) Boragin. Onosmodium occidentale (8% ?) Lili. Astelia banksii (18%), neo-caledonica (22%), solandri (zz%), trinervia (25%); Collospermum hastatum (14%), microspermum (iz%) (Morice, 1967—see under Liliaceae). n-Octadeca-8c,1 ot,12c-trienoic acid Bignoni. Jacaranda ovalifolia (3o%) n-Octadeca-8t,iot,i2c-trienoic acid (Calendic acid) occurs in seed-fats of some composites: see Chisholm and Hopkins (196o, 1966). Comp. Calendula officinalis (47%), stellata (5o%), and all (?) other species; Osteospermum hyoseroides (36%).

512 CHEMOTAXONOMY OF FLOWERING PLANTS

n-Octadeca-9t, I it, 13 c-trienoic acid Bignoni. Catalpa ovata (seed-fat, 40%), speciosa (present); Chilopsis linearis (sd-fat, to 25%) n-Octadeca-9c,IIC,I3t-trienoic acid (Punicic acid; Trichosanic acid) occurs in seed-fats of Cucurbit. Cayaponia grandifolia (to 39%), Cucurbita, Momordica spp. (to 56%), Trichosanthes Punic. Punica n-Octadeca-3t,9c,12C-trienoic acid is said to occur in Comp. Calea (this acid ?) and at least 21 other species. n-Octadeca-5t,9c,i2c-trienoic acid Ranuncul. in at least it species.

V FATTY-ACIDS WITH FOUR DOUBLE BONDS List and Occurrence 1. With bonds arranged -(CH=CH)4n-Octadeca-9c,iic,i3c,i5c-tetraenoic acid (oc-Parinaric acid) Chrysobalan. Cyclandrophora (Parinari) laurina (sd-fat, to 56%) Balsamin. Impatiens balsamina (sd-fat, 29-42%), biflora (fulva) (sd-fat, 51%), holstii var. (sd-fat, 13%), noli-tangere (sd-fat, 32%), parviflora (sd-fat, 46%), roylei (glanduligera) (sd-fat, 40-50%), sultani (sd-fat, 27%) 2. With bonds arranged -(CH=CH . CH2)4n-Eicosa-5,8,11,14-tetraenoic acid (Arachidonic acid) : of doubtful occurrence ? Gram. Oryza sativa (embryo ?) Typh. Typha angustata (sd-fat ?) n-Octadeca-6c,9c, i 2c, i 5c-tetraenoic acid Boragin. Anchusa azurea (seed-fat, 3% ?), capensis (sd-fat, 4% ?); Lappula echinata (sd-fat, 19% ?) ; Myosotis arvensis (sd-fat, 7% ?); Onosmodium occidentale (sd-fat, 8%) (Craig and Bhatty, 1964) 3. With bonds arranged otherwise n-Octadeca-3t,9c,I2c,i5c-tetraenoic acid Bignoni. Tecoma Stans (sd-fat, 19%)

FATS AND FATTY-ACIDS 513

VI FATTY-ACIDS WITH FIVE DOUBLE BONDS GENERAL Acids with five double bonds arranged -(CH.----CH. CH2)5- have been found in brain phosphatides. It would not be surprising to have them `turn up' in plant lipids.

VII FATTY-ACIDS WITH ONE OR MORE ACETYLENIC (-C=C-) LINKAGES (see also IX) GENERAL The list of acetylenic compounds occurring in higher plants is formidable (p. 85). Much of our information stems from the work of Sörensen and his coworkers, and Bohlmann et al. We deal here only with the acetylenic fatty-acids occurring in seed-fats. The chemotaxonomy of these is discussed under Santalales. List and Occurrence i. Acids with one acetylenic linkage Docos-13-ynoic acid (Behenolic acid) Crucif. Brassica (rape oil) n-Heptadeca-iot,i6-dien-8-ynoic acid Santal. Acanthosyris spinescens (sd) n-Heptadec-rot-en-8-ynoic acid (Pyrulic acid) Santal. Acanthosyris?, Pyrularia pubera (sd-oil) 7-Hydroxy-n-heptadeca-Iot,l6-dien-8-ynoic acid Santal. Acanthosyris spinescens (sd) 7-Hydroxy-n-heptadec-rot-en-8-ynoic acid Santal. Acanthosyris spinescens (sd) 8-Hydroxy-n-octadeca-r It,17-dien-9-ynoic acid Santal. Acanthosyris spinescens (sd) 8-Hydroxy-n-octadec-x It-en-9-ynoic acid Olac. Ximenia caffra (sd-fat; 3-4%) Santal. one member 9-Hydroxy-n-octadec-Iot-en-I2-ynoic acid (Helenynolic acid) Comp. Helichrysum bracteatum (sd) n-Octadeca-9c,I4c-dien-I2-ynoic acid (14,15-Dehydro-crepenynic acid) occurs in fungi and Legum. Afzelia quanzensis (sd-oil) 17 cco

514 CHEMOTAXONOMY OF FLOWERING PLANTS

n-Octadeca-IIt,17-dien-9-ynoic acid Santal. Acanthosyris spinescens (sd) n-Octadec-9c-en-I2-ynoic acid (cis-Crepenynic acid) Legum. Afzelia quanzensis (sd-oil) Comp. Crepis foetida (seed-oil, 6o%). Wolff (1966) says that it may be in 22 species of the family. n-Octadec-IIt-en-9-ynoic acid (Santalbic acid; Ximenynic acid) Olac. Ximenia americana var. microphylla (sd-fat, 22%), caffra (sd-fat, 24%); but absent from other genera ? Santal. seems to be more or less general. See under Santalales. n-Octadec-17-en-9-ynoic acid Santal. Acanthosyris spinescens (sd) n-Octadec-6-ynoic acid (Tariric acid)—Hilditch (1956) says: Unsaturation commencing at the sixth atom of the C18 chain...is a well-marked characteristic of acids in the seed fats of a few botanical families. In the monoethenoid series it is confined to petroselinic acid, which, however, is a prominent component of all Umbelliferous seed fats and of one or two seed fats in other families (Araliaceae, Simarubaceae). The monoethynoid analogue tariric acid occurs in seed fats of some species of Picramnia (also a member of the Simarubaceae), whilst a third tri-ethenoid acid of analogous structure is (so far) uniquely represented in the seed fat of Oenothera.. . Simaroub. Picramnia camboita (sd-fat), carpenterae (sd-fat), lindeniana (sd-fat, 20%), pentandra (sd-fat, much), sow (sd-fat, 90%!), tariri (sd-fat) (Steger and van Loon, 1933) ; but absent from other members of the family ? n-Octadec-9-ynoic acid (Stearolic acid): this acetylenic analogue of the ubiquitous oleic acid' was found by Hopkins and Chisholm (1964) in Pyrularia. Santal. Exocarpus cupressiformis (sd-fat, 6%); Pyrularia pubera (sd-fat, 19%); Santalum acuminatum (sd-fat, 3%), album (sdfat, 3%) Sterculynic acid: see section Ix. 2.

Acids with two acetylenic linkages

8-Hydroxy-n-Octadec-17-en-9,11-diynoic acid (Bolekic acid; Isanolic acid) Olac. Ongokea klaineana (gore) (sd-fat, 15-5o% in different analyses) n-Octadec-13t-en-9,I x-diynoic acid (Exocarpic acid) Santal. Buckleya distichophylla (seed-oil, 29%; Hopkins and Chisholm, 1966), Exocarpus spp. (rts)

FATS AND FATTY-ACIDS 515

n-Octadec-17-en-9,Il-diynoic acid (Erythrogenic acid; Isanic acid; ?Ongokic acid) turns red in light or when heated, hence one of its trivial names. Olac. Ongokea klaineana (gore) (seed-fat, 15 to 40% in different analyses) 3. Acids with three acetylenic linkages n-Dec-zt-en-4,6,8-triynoic acid Comp. Tripleurospermum (as methyl ester ?) n-Dec-2c-en-4,6,8-triynoic acid Comp. Artemisia vulgaris

VIII FATTY-ACIDS WITH A KETO GROUP (see also XII) List and Occurrence Glyoxylic acid (H. CO . COOH) occurs free, says my former colleague G. H. N. Towers, in every plant. It occurs, too, as ureides in some plants. It is not a fatty-acid. Iso-licanic acid is like a-licanic acid, but is cis-, trans-, cis-. Chrysobalan. Licania rigida (seed-fat) a-Keto-ß-hydroxy-butyric acid (CH3. CH(OH). CO. COOH) Eric. Vaccinium vitis-idaea (frt) a-Keto-y-hydroxy-butyric acid (CH2(OH) . CH2. CO . COOH) Eric. Oxycoccus quadripetalis (frt), Vaccinium vitis-idaea (frt) 4-Keto-n-octadeca- ?9c, 1 1 t, I 3t-trienoic acid (4-Keto-oc-elaeo-stearic acid; a-Licanic acid) Chrysobalan. Licania arborea (sd-fat, 73-74%), crassifolia (sd-fat, 65% or more), rigida (sd-fat, 55-82%, different analyses), venosa (sd-fat, 50%); Parinari annamense (sd-fat, 22%), corymbosum?, laurina?, sherbroense (sd-fat, 35-48%) Pyruvic acid (CH3. CO. COOH) is not really a fatty-acid. It is said to occur (free ?) in Crassul. Kalanchoe (lys) Legum. Arachis (sdlg), Pisum, Trifolium Euphorbi. Ricinus communis (sdlg) Umbell. Daucus carota Lab. Mentha piperita Solan. Solanum tuberosum Lili. Allium, Tulipa gesneriana (bulb) I 7-2

516 CHEMOTAXONOMY OF FLOWERING PLANTS

IX FATTY-ACIDS WITH A CYCLOPROPENYL GROUP GENERAL A few fatty-acids with a cyclopropenyl (—C=C—) group are known to CHa

occur in seed-fats of higher plants. They seem to be restricted to the Malvales (Table Ø), providing a very good example of the use of fattyacids in taxonomy.

List and Occurrence `Bombacic acid': a C18 acid with a cyclopropenyl group ? It may be identical with malvalic acid (below). Bombac. Ceiba pentandra z-Hydroxy-sterculic acid (2-Hydroxy-8(z-octyl-x-cyclopropenyl)-octanoic acid; fig. 107) Bombac. Bombacopsis glabra, Pachira insignis Malvalic acid (fig. 107) seems to cause the pinkish `whites' of eggs from hens eating malvaceous plants. It occurs in leaves and seeds ? Tili. Tilia sp. (sd-oil) Maly. Althaea rosea (sd-oil, 4%), Hibiscus syriacus (sd-oil, 14-16%), Lavatera trimestris (sd-oil, 6-8%), Gossypium sp. (` cottonseed', 1 %). Some other members give the `halphen test' and may have malvalic acid. Bombac. Bombacopsis glabra (sd-oil, 3%), Bombax (oleagineum?) (sd-oil, 5%) Sterculi. Pterospermum acerifolium (sd-oil, 16%), Sterculia foetida (sd-oil, trace to io%) Sterculic acid (fig. 107) Tili. Tilia sp. (sd-oil, < 1%) Maly. Althaea rosea (sd-oil, 1%), Hibiscus syriacus (sd-oil, 2-3%), Lavatera trimestris (sd-oil, < i%), Gossypium hirsutum (cottonseed, < 1 %) Bombac. Bombax (oleagineum ?) (sd-oil, zz%), Pachira aquatica (sd-oil, some) Sterculi. Brachychiton?, Firmiana?, Pterospermum acerifolium (sdoil, some), Sterculia foetida (sd-oil, 70%), parviflora (sd-oil, much) Sterculynic acid (8,9-Methylene-octadec-8-en-17-ynoic acid; fig. 107) has been found by Jevans and Hopkins (1968) in Sterculi. Sterculia alata (sd-fat, 8%)

FATS AND FATTY-ACIDS 5r7

CH3.CH2.CH — CH.(CH2.CH=CH)2. (CH 2)7 •COOH \0 Epoxylinoleic acid

CH3.(CH

2)7 • C = C.(CH2 )6.COOH CH2 Malvalic acid

CH3.(CH2)7.0=C .(CH2)7.COOH

CH2 Sterculic acid CH3.(C H2 )7.0=C .(CH2 )6 .0 H.COOH 1/ CH2 OH 2-Hydroxy-sterculic acid CH=C.(CH2)7.0 = C.(CH2)6.000H CH2 Sterculynic acid

Fig. 107. Some epoxy- and cyclopropenyl- fatty-acids.

X FATTY-ACIDS WITH AN EPDXY GROUP GENERAL As recently as 1956 Hilditch wrote of vernolic acid (in Vernonia) : ` ...so far this is the only known occurrence in nature of a higher fatty acid containing an epoxy group.' We know today that several of these acids occur, and there is little doubt that others will be found. List and Occurrence trans-9,Io-n-Epoxy-octadecanoic acid (Epoxy-stearic acid) Ole. Olea europaea (fruit-coat oil) Comp. one sp. ?

518 CHEMOTAXONOMY OF FLOWERING PLANTS

cis-15,16-n-Epoxy-octadeca-9c,1 zc-dienoic acid (Epoxylinoleic acid; fig. 107) Crucif. Camelina sativa (sd-fat) cis-9, i o-n-Epoxy-octadec-1 zc-enoic acid (Coronaric acid) Comp. Chrysanthemum coronarium (sd-fat), and 2 other members of the family. cis-12,13-n-Epoxy-octadec-9-enoic acid (?Epoxyoleic acid; Vernolic acid) Euphorbi. Cephalocroton cordofanus (seed-fat, 7o% according to one report, none to another!), Euphorbia lagascae (sd-oil, 57%), and one other member of the family. Maly. Abutilon ( CH3. (CH2)n . CH3 (where n is odd). It is clear that we know far too little about these substances to get much of chemotaxonomic interest out of them. We may note a few suggestive facts, however. (a) If we plot the numbers of families in which each of the saturated normal hydrocarbons occur against the C-numbers (fig. 134), it is clear, even from my very incomplete records, that the commonly occurring members are C23—C35. The occurrence in a plant of any of these hydrocarbons would be of limited interest. The less commonly occurring members (below C23 and above C35) might well be of great interest. (b) In the Tubiflorae a few analyses are available from 6 of the 26 families. All the hydrocarbons recorded lie between C24 and C35, i.e. none is unusual. (c) In the Scrophulariaceae (Tubiflorae) a few records of leaf-waxes from Bacopa, Digitalis and Hebe are interesting. Eglinton, Hamilton and

HYDROCARBONS 649

20 19 n- even

18

odd "x---x~

17 16

branched even

15

1

odd

14

13 12

/ / xX t ! / 1

4)10 E9 m L.` 8 7 6 5 4

3

/ x

x

2

! X 1 x /

/

1 11 yxx--. x 10---Q % fi tt 1 /

1

/

t 1 4 1

1

, d .

/ i /

1 b.

t

\ R

44 1

I

7 9 11

13 15 17 19 21 23 25 27 29 31 33 35 37

39

C-Atoms

Fig. 134 Frequency of occurrence of n- and branched alkanes.

Martin-Smith (1962) found that normal hydrocarbons with odd-Cnumbers predominated in Hebe but: `within the genus Hebe the major constituent is C29 in H. odora, C31 in H. parviflora and H. diosmifolia, and C33 in H. stricta, thus giving an immediate chemotaxonomic distinction'. The analysis of Bacopa monnieri is very similar to that for Hebe parvifiora (fig. 13S). At least one species of Digitalis has the C30 hydrocarbon, which is in Bacopa and in Hebe (4 spp.) in small amount. (d) In Solanum (Mecklenburg, 1966) all the zo species examined had both normal (C25 to C31) and branched (C23 to C32) alkanes in their inflorescence waxes. Mecklenburg concluded that: `In general, the results of this work tend to confirm relationships between species thought to exist on the basis of morphological, cytogenetic, and interfertility data.' 22

GCO

650 CHEMOTAXONOMY OF FLOWERING PLANTS

Hebe odora

H.parviflora v.arborea

H diosmifolia

H stritta //

Bacopa monnieri

24 25 26 27 28 29 30 31 32 33 34 35 C-Atoms Fig. 135 n-Alkanes of the leaf-waxes of the Scrophulariaceae (Eglinton et al. for Hebe)

(e) The Crassulaceae have been relatively fully investigated by Eglinton et al. (1962) and Herbin and Robins (1968). The members have normal and branched hydrocarbons from C25 to Cab, with C29, C31 and C33 in largest amounts. See fig. 135 for Kalanchoe. (f) More than 6o species of the genus Aloe of the Liliaceae have been studied by Herbin and Robins (1968). They found leaf-cuticular waxes (entered in my list) to show species specificity in composition. The perianth-wax alkanes proved even better chemotaxonomically. Branched alkanes were found in one leaf-wax. Alkenes were found in two perianth waxes and in all style and filament waxes. (g) If we plot the alkanes of Eucalyptus (19 spp.), Agave (19 spp.),

HYDROCARBONS 651

80 Eucalyptus 70

i•

ri

o---o-

Agave

I

i

i

Kalanchoe 60

(Herbin and Robins,1968)

50

O 40

x~I

30

20

10

s

o-

21

213

25

r

27

~

29 C-Atoms

I

31

I

33

37

35

Fig. 136 n-Alkanes of some plants.

and Kalanchoe (5 spp.) we see that the patterns are quite distinct (fig. 136). The unsaturated hydrocarbons, alkenes, seem to be few in number and of little taxonomic value. Olea (Oleaceae) seems to have several, but its product olive-oil has been much investigated. List and Occurrence 1. Normal Alkanes The first few members of the series are gases, the next liquids, and only with the C16 member do we come to a solid. I have no record of any of these alkanes below C,. 22-2

652 CHEMOTAXONOMY OF FLOWERING PLANTS

n-Heptane (C7H16) occurs in large quantity in the turpentine of Pinus jeffreyi. In angiosperms it is recorded from Pittospor. Pittosporum resiniferum (frt) n-Octane (C8H18): I have no records. n-Nonane (C9H20) is recorded from conifers and from Guttif. Hypericum sarothra Pittospor. Pittosporum eugenioides (If-oil, 6o-70%), pentandrum (frt ?) n-Decane (C10H221: I have no records. n-Undecane (n-Hendecane; C11H24) is recorded from conifers. n-Dodecane (C12H26): I have no records. n-Tridecane (C13H26) is probably secondary ? Sterculi. Theobroma cacao (` cocoa' ?) Palmae. Cocos nucifera (coconut-oil ?) n-Tetradecane (C14H30): I have no records. n-Pentadecane (C16H32) Zingiber. Hedychium spicatum (rhiz.-oil), Kaempferia galanga (rt -oil) n-Hexadecane (Cetane; Dioctyl; C16H34) Ros. Rosa sp. (petals: some doubt of this ?) n-Heptadecane (C17H36) Ros. Rosa sp. (`wax') n-Octadecane (C18H38): I have no records. n-Nonadecane (C10H40) Ros. Rosa sp. n-Eicosane (Didecyl; C20H42) Crucif. Brassica (`Brussels sprouts') Ros. Rosa sp. ? Legum. Acacia farnesiana (fl.) Comp. Artemisia sp. Lili. Aloe (lys of t, t%) n-Heneicosane (C21H44) is said to occur in green algae and in Ros. Rosa sp. ? Myrt. Eucalyptus (lys of to, to t%) Lili. Aloe (lys of 26, to 4%) Agay. Agave (lys of 4, tr.) n-Docosane (C22H46) Ros. Rosa sp. ? Rhamn. Rhamnus sp. Myrt. Eucalyptus (lys of 15, to 2%) Lili. Aloe (lys of 33, to 7%) Agay. Agave (lys of 6, tr.)

HYDROCARBONS 653

n-Tricosane (C23H48) Betul. Corylus avellana (pollen) Crassul. Crassula (lys of i, tr.), Echeveria (lys of i, tr.), Kalanchoe (lys of i, tr.) Ros. Malus (apple, tr.), Rosa sp. ? Gerani. Geranium macrorrhizum (ess. oil) Myrt. Eucalyptus (lys of r7, to 8%) Arali. Nothopanax simplex (ess. oil) Scrophulari. Hebe (lvs) Lili. Aloe (lys of 54, to 8%) Agay. Agave (lys of 14, to 1%) n-Tetracosane (C24H 50) Crassul. Crassula (lys of 2, to 2%), Echeveria (lys of I, tr.), Kalanchoe (lys of r, tr.) Myrt. Eucalyptus (lys of 19, to 19%) Ole. Olea europaea (olive-oil) Scrophulari. Hebe odora (1f-wax, little) Comp. Chrysanthemum indicum (fl.) Lili. Aloe (lys of 57, to 7%) Agay. Agave (lvs of x5, to r%) Palmae. Attalea excelsa (wax) Gram. Avena n-Pentacosane (C25H52) Salic. Populus (2) Crassul. Aeonium (lys of 18, to 2%), Crassula (lys of 3, to 4%), Echeveria (lys of 2, tr.), Kalanchoe (lys of 4, to i%; petals of 2, tr.), Sedum (lys of x, tr.) Ros. Acaena anserinifolia (lvs and st.), Malus (apple, tr.), Rosa sp. Legum. Ferreirea Rut. Citrus (2) Thymelae. Pimelea prostrata (lys and st., 3%) Myrt. Eucalyptus (lys of 19, to 33%) Arali. Nothopanax simplex (ess. oil) Eric. Gaultheria (lys and st. of 2, to 4%) Solan. Mandragora, Nicotiana, Solanum spp. Scrophulari. Hebe (lys of 3) Lili. Aloe (lys of 62, to 25%) Agay. Agave (lys of 19, to 7%) Gram. Arundo conspicua (lys, 4%) Typh. Typha n-Hexacosane (C26H54) Crassul. Aeonium (lys of 19, to r%), Aichryson (lys of r, tr.), Crassula (lys of 3, to 4%), Echeveria (lys of 2, tr.), Greenovia

654 CHEMOTAXOMY OF FLOWERING PLANTS (lys of 3 or more, tr.), Kalanchoe (lys of 3, to i%), Monanthes (lys of 4, tr.), Sedum (Iys of 1, tr.) Ros. Acaena anserinifolia (lys and st., 1%), Rosa sp. ? Euphorbi. Euphorbia (5, to 2%) Myrt. Eucalyptus (lys of 19, to 15%) Ole. Olea europaea (olive-oil) Solan. Solanum spp. (infl.) Scrophulari. Hebe (lf-waxes of 3) Comp. Chrysanthemum indicum (fl.) Lili. Aloe (lys of 6z, to I3%), Phormium tenax (rhiz., 4%) Agay. Agave (lys of 19, to 7%), Cordyline australis (rhiz., z%), Dracaena draco (5%) Gram. Lolium multiflora (1 %) n-Heptacosane (C27H66) occurs in ferns and in Crassul. Aeonium (lys of 22, to 8%), Aichryson (lys of 1 or z, to r%), Crassula (lys of 4, to 3%), Echeveria (lys of 2, to I%), Greenovia (lys of z or more, to 1 %), Kalanchoe (lys of 5, to 1 %; petals of z, to 4%), Monanthes (lys of 7, to 1%), Sedum (lys of 3, to 1%) Ros. Malus (apple, i%) Euphorbi. Euphorbia (6, to 51%) Thymelae. Pimelea prostrata (lys and st., 2%) Myrt. Eucalyptus (lys of 19, to 56%) Arali. Nothopanax simplex (ess. oil) ? Eric. Gaultheria (lys and st. of z, to 3%) Ole. Olea europaea (olive-oil) Solon. Solanum spp. (infl.) Scrophulari. Bacopa monnieri; Hebe (If-waxes of 4) Lili. Aloe (lys of 62, to 50%) Agay. Dracaena draco (12%) Palmae. Copernicia (wax) Gram. Lolium multiflora (7%) n-Octacosane (C28H58) Crassul. Aeonium (lys of 19, to 2%), Aichryson (lys of 1, tr.), Crassula (lys of 4, to 4%), Echeveria (lys of z, to 2%), Greenovia (lys of 1 or more, tr.), Kalanchoe (lys of 5, to OA; petals of z, tr.), Monanthes (lys of 4, tr.), Sedum (lys of 2, to I%) Ros. Acaena anserinifolia (lys and st., 2%), Rosa sp. Euphorbi. Euphorbia (6, to 3%) Tili. Tilia europea (fl.) Maly. Malva rotundifolia Thymelae. Pimelea prostrata (lys and st., 3%) Myrt. Eucalyptus (lys of 19, to 8%)

HYDROCARBONS 655

Eric. Gaultheria (lys and st. of 2, to 3%) Solan. Solanum spp. (infl.) Scrophulari. Bacopa monnieri, Hebe (If-waxes of 4) Comp. Antennaria dioica (fl.) Lili. Aloe (lys of 63, to i8%), Phormium tenax (rhiz., 3%) Agay. Agave (lis of 19, to 11%), Cordyline australis (rhiz., 3%), Dracaena draco (7%) Gram. Arundo conspicua (lys, 5%), Lolium multiflora (1%)

n-Nonacosane (C29H60) Salic. Populus Caryophyll. Cerastium Crucif. several, often in very large amount Crassul. Aeonium (lys of 25, to 12%), Aichryson (lvs of 2 or 3, to z%), Crassula (lys of 4, to 12%), Echeveria (lys of 3, to 9%), Greenovia (3 or more, to 2%), Kalanchoe (lvs of 5, to 1%; petals of z, to 12%), Monanthes (lys of 7, to OA), Sedum (lys of 3, to 9%) Ros. Acaena anserinifolia (lys and st., It %), Malus (apple-peel wax, in very large amount) Legum. `bean', Gleditsia, Spartium Euphorbi. Euphorbia (6, to 25%) Rut. Citrus Thymelae. Pimelea prostrata (lys and stem, 65%) Myrt. Eucalyptus (Iys of 19, to 70%) Onagr. Chamaenerion, Epilobium Corn. Cornus Arali. Nothopanax simplex (ess. oil) Eric. Gaultheria (lys and st. of 2, to z6%) Asclepiad. Cryptostegia grandiflora Solan. Solanum spp. (infl.) Scrophulari. Bacopa monnieri, Hebe odora (chief hydrocarbon)

and 3 others Lili. Aloe (lys of 63, to 63%), Phormium tenax (rhiz., to 47%) Agay. Agave (lys of 19, to 35%), Cordyline australis (rhiz., 15%), Dracaena draco (22%) Gram. Lolium multiflora (40%), Zea

n-Triacontane (C30H62) Caryophyll. Cerastium Crassul. Aeonium (lys of zi, to z%), Aichryson (lys of 2 or 3, to 4%), Crassula (lys of 4, to 3%), Echeveria (lys of 3, to 1%), Greenovia (lys of i or more, tr.), Kalanchoe (lys of 5, to t%; petals of 2, to i%), Monanthes (lys of 2, to 3%), Sedum (lys of 3,

to 2%) Ros. Malus, Rosa

656 CHEMOTAXONOMY OF FLOWERING PLANTS

Gerani. Geranium macrorrhizum (ess. oil) Euphorbi. Cluytia, Euphorbia (5, to 3%) Hippocastan. Aesculus Thymelae. Pimelea prostrata (lys and st., 2%) Myrt. Eucalyptus (lys of 18, to 2%) Eric. Gaultheria (!vs and st. of 2, to 3%) Hydrophyll. Eriodictyon glutinosum (lys) Solan. Solanum spp. (infl.) Scrophulari. Bacopa monnieri (little), Digitalis, Hebe (lys of 4, in small amounts) Comp. Achillea, Anthemis, Arnica, Carpesium Lili. Aloe (lys of 62, to i4%), Phormium tenax (rhiz., to 3%) Agay. Agave (lys of 19, to Io%), Cordyline australis (rhiz., 3%), Dracaena draco (6%) Gram. Lolium multiflora (1%) n-Hentriacontane (C31HM) Crucif. ` mustard leaf-wax', more than 5o% Crassul. Aeonium (lys of 24, to 79%), Aichryson (lys of 2 or 3, to 17%), Crassula (lys of 4, to 77%), Echeveria (lys of 3, to 55%), Greenovia (lys of 3 or more, to 9%), Kalanchoe (lys of 5, to 3o%; petals of 2, to 32%), Monanthes (lys of 7, to 52%), Sedum (lys of 3, to 8o%) Ros. Acaena anserinifolia (lys and st., S9%), Malus (apple, tr.) Legum. `bean leaf-wax', 48% Euphorbi. Euphorbia (5, to 7o%), Pedilanthus pavonis (wax) Thymelae. Pimelea prostrata (lys and st., 13%) Myrt. Eucalyptus (lys of 19, to io%) Eric. Arbutus, Gaultheria (lys and st. of 2, to 56%) Apocyn. Ervatamia wallichiana (lys, bk) Solan. Solanum spp. (infl.) Scrophulari. Bacopa monnieri (chief hydrocarbon), Hebe (chief hydroc. of 2) and 2 others Lili. Aloe (lys of 62, to 96%), Phormium tenax (rhiz., to 8%) Agay. Agave (lys of 19, to 8o%), Cordyline australis (rhiz., io%), Dracaena draco (31%) Gram. Arundo conspicua (lys, 12%), Leptochloa digitata (chief hydroc. of stem-wax), Lolium multiflora (40%) n-Dotriacontane (Dicetyl; C32H86) Crassul. Aeonium (lys of 21, to 5%), Aichryson (lys of 2 or 3, to 4%), Crassula (lys of 4, to 7%), Echeveria (lys of 3, to 4%), Greenovia (lys of 3 or more, to 3%), Kalanchoe (lys of 5, to 5%; petals of 2, to 3%), Monanthes (lys of 7, to 2%), Sedum (lys of 3, to 5%)

HYDROCARBONS 657

Ros. Acaena anserinifolia (lys and st., 2%), Alchemilla vulgaris Euphorbi. Euphorbia? Eric. Gaultheria (lys and st. of 2, to 4%) Lab. Mentha Myopor. Myoporum laetum (this, or C34H70) Lili. Aloe (lys of 52, to 8%), Phormium tenax (rhiz., 2%) Agav. Agave (lys of 19, to 5%), Dracaena draco (1%) Gram. Arundo conspicua (lys, 2%) n-Tritriacontane (C33H68) Cact. Opuntia sp. Crassul. Aeonium (lys of 23, to 8o%), Aichryson (lys of 2 or 3, to 62%), Crassula (lys of 4, to 57%), Echeveria (lys of 3, to 46%), Greenovia (lys of 3 or more, to 82%), Kalanchoe (lys of 5, to 87%; petals of 2, to 51%), Monanthes (lys of 7, to 94%), Sedum (lvs of3,to47%) Ros. Acaena anserinifolia (lys and st., 19%), Malus (apple, tr.) Euphorbi. Euphorbia (4, to i8%), Pedilanthus pavonis (wax) Eric. Gaultheria (lys and st. of 2, to 7%) Asclepiad. Cryptostegia grandifiora (lys) Lili. Aloe (lys of 47, to 58%) Agav. Agave (lys of 19, to 67%), Dracaena draco (4%) Gram. Arundo conspicua (lys, 3%), Lolium multiflora (3%) n-Tetratriacontane (C34H70) Crassul. Aeonium (lys of 17, to 3%), Aichryson (lys of 2 or 3, to 2%), Crassula (lys of 3, to 3%), Echeveria (lys of 3, tr.), Greenovia (lys of 3 or more, to i2%), Kalanchoe (lys of 5, to OA; petals of i, tr.), Monanthes (lys of 5, to 0/0) Scrophulari. Hebe (lys and st. of 2, to 1%) Myopor. Myoporum laetum (this, or C32H66) n-Pentatriacontane (C35H,2) Cact. at least one Papaver. Fumaria officinalis Crassul. Aeonium (lys of 22, to 13%), Aichryson (lys of 2 or 3, to 6%), Crassula (lys of 3, to 3o%), Echeveria (lys of 3, to i %), Greenovia (lys of 3 or more, to 14%), Kalanchoe (lys of 5, to 5%; petals of i, 1%), Monanthes (lys of 6, to 4%), Sedum (lys of i, tr.) Pittospor. Pittosporum undulatum (frt) Maly. Gossypium sp. Asclepiad. Gymnema sylvestre Hydrophyll. Eriodictyon glutinosum (lys) Verben. Vitex lucens (lys)

658 CHEMOTAXONOMY OF FLOWERING PLANTS

Scrophulari. Hebe (lys and st. of 2, to 16%) n-Hexatriacontane (C86H74): I have no records. n-Heptatriacontane (C37H76) Cact. Opuntia sp. n-Dohexatriacontane (C62H126) Gram. Leptochloa digitata (stem-wax, in small amount) 2.

Saturated Branched-chain Hydrocarbons

I have listed these as iso-, but some of the records may be of anteisoforms. Iso-pentacosane (C25H52) Crassul. Aeonium (lys of i, tr.) Solan. Solanum spp. (infl.) Lili. Phormium tenax (rhiz.) Iso-hexacosane (C28H54) Crassul. Aeonium (lys of 1, tr.) Solan. Solanum spp. (infl.) Lili. Phormium tenax (rhiz.) Iso-heptacosane (C27H56) Crassul. Aeonium (lys of 8, to 2%), Greenovia (lys of 3, tr.), Monanthes (lys of i, tr.) Euphorbi. Euphorbia (2, to I%) Solan. Solanum spp. (infl.) Scrophulari. Hebe (lys and st. of i) Lili. Phormium tenax (rhiz., 2%) Agav. Cordyline australis (rhiz., 1%) Iso-octacosane (C28H58) Crassul. Aeonium (lys of 6, to 2%) Ros. Alchemilla alpina Euphorbi. Euphorbia (i, tr.) Solan. Solanum spp. (infl.) Lili. Phormium tenax (rhiz.) Iso-nonacosane (C2oH60) Crassul. Aeonium (lys of 17, to 16%), Aichryson (lys of 2, to 2%), Greenovia (lys of i, 2%), Monanthes (lys of 5, to I %) Ros. Acaena anserinifolia (lys and st., I %) Euphorbi. Euphorbia (2, to 1%) Thymelae. Pimelea prostrata (lys and st.) Solan. Solanum sp. (infl.) Scrophulari. Hebe (lys and st. of 3) Lili. Phormium tenax (rhiz., to 4%) Agav. Cordyline australis (rhiz., 1%)

HYDROCARBONS 659

Iso-triacontane (C30H62) Crassul. Aeonium (lys of 8, to x%) Ros. Acaena anserinifolia (lys and st., i%) Euphorbi. Euphorbia (i, tr.) Solan. Solanum spp. (infl.) Lili. Phormium tenax (rhiz.) Iso-hentriacontane (C31H64) Crassul. Aeonium (lys of 24, to 3o%), Aichryson (lys of 3, to 7%), Greenovia (lys of 4, to z%), Monanthes (lys of 2, to 1%) Ros. Acaena anserinifolia (lys and st., x %) Euphorbi. Euphorbia (i, tr.) Thymelae. Pimelea prostrata (lys and st.) Solan. Solanum spp. (infl.) Scrophulari. Hebe (lys and st. of 3) Lili. Phormium tenax (rhiz., 3%) Agav. Cordyline australis (rhiz., x%) Iso-dotriacontane (C32H66) Crassul. Aeonium (lys of 14, to 3%), Aichryson (lys of 2, to 7%) Solan. Solanum spp. (infl.) Iso-tritriacontane (C33H68) Crassul. Aeonium (lys of 20, to 39%), Aichryson (lys of 3, to 14%), Greenovia (lys of 3 or more, to 3%), Monanthes (lys of 5, to 2%) Ros. Acaena anserinifolia (lys and st.) Scrophulari. Hebe (lys and st. of 2, to x%) Iso-tetratriacontane (C34H70) Crassul. Aeonium (lys of 5, to i%), Aichryson (lys of i, z%) Iso-pentatriacontane (C33H72) Crassul. Aeonium (lys of 16, to 6%), Aichryson (lys of 2 or 3, to 3%), Greenovia (Ws of 1, or 2, to 2%) Scrophulari. Hebe (lys and st. of i, 0/3)

3. Some Unsaturated Hydrocarbons This is a heterogeneous group of substances which I have arranged alphabetically. Arachidene (C13H38) Legum. Arachis hypogaea Butylene (CH2=CH .CH2 . CH3 or CH3. CH=CH. CH3 ; C4H8) Crucif. Diplotaxis tenuifolia (lys) Diallyl (CH2=CH. CH2. CH2. CH=CH2; C6H10) Comp. Ormenis multicaulis Ethylene (CH2=CH2; C2H4) is evolved by ripening fruits, etc. Fading flowers of Vanda (Orchid.) are said to produce > 340o ,ul per kg per hr.

66o

CHEMOTAXONOMY OF FLOWERING PLANTS

Gadusene (C18H32) Gram. wheat-germ Hexadecadiene (C19H30) Ole. Olea europaea Hypogene (C15H30) Legum. Arachis hypogaea z-Methyl-5,Iz-tetradecadiene (C16H22) Comp. Echinacea angustifolia (rt) z-Methyl-6,1z-tetradecadiene Comp. Echinacea angustifolia (rt) Nonadecadiene (C19H36) Ole. Olea europaea Nonylene (C9H18) Burser. Bursera delpechiana (oil) Octacosatetraene (C28H50) Ole. Olea europaea Octylene (CH3. (CH2)6 . CH=CH2 ; C2H16) Gutt Hypericum? Tricosatriene (C23H42) Ole. Olea europaea Tridecadiene (C13H21) Ole. Olea europaea

II ALICYCLIC HYDROCARBONS are dealt with 23 terpenes III AROMATIC HYDROCARBONS Styrene (Cinnamene; Cinnamol; Cinnamomin; Phenylethylene; Styrol; Styrolene; Vinyl-benzene) Hamamelid. Liquidambar orientalis (storax, styrax) Xanthorrhoe. Xanthorrhoea hastilis (resin)

KETONES GENERAL This is probably an unnatural group, biosynthetically speaking, even though we have excluded monoterpenoid ketones, acetylenic ketones, ketosugars, keto-fatty-acids, furan derivatives, chakones and other flavonoids, and the quinones (which may be called diketones).

KETONES 66i

We are left with: I. Aliphatic ketones II. Aromatic ketones i. Acetophenones 2. Benzophenones 3. Other aromatic ketones III. Other cyclic ketones

I ALIPHATIC KETONES GENERAL We have excluded from this section monoterpenoid ketones (see monoterpenoids), acetylenic ketones (see acetylenic compounds), and the ketosugars (see carbohydrates). (a) It is clear that the Rutaceae are rich in these ketones. (b) In the Magnoliales we have a few records from Annonaceae (i), Schisandraceae (z), Lauraceae (3 in z genera). We have no records from Ranunculales. (c) In the Tubiflorae the closely related Verbenaceae (r) and Labiatae (3 in 3 genera) have aliphatic ketones.

List and Occurrence Acetone (Dimethyl-ketone; Propanone) is, says Karrer (1958), often a secondary product formed during distillation of essential oils, etc. I have a few records for what they are worth.

Legum. Phaseolus Euphorbi. Hevea, Manihot Erythroxyl. Erythroxylum Umbell. Coriandrum Lab. Pogostemon Butan-2,3-dione (Diacetyl; CH3 . CO. CO. CH3) is often produced secondarily in the extraction of essential oils. It seems, however, to be responsible for the odours of some flowers. Annon. Polyalthia canangoides var. angustifolia (fl.)

Logani. Fagraea racemosa (fl.) But-2-o1-3-one (Acetoin; Acetyl-methyl-carbinol; CH3. CH(OH) . CO . CH3)

Ros. Fragaria?, Rubus? Legum. `bean leaves' Gram. Zea mays (lvs)

662

CHEMOTAXONOMY OF FLOWERING PLANTS

Decan-2-one (Methyl-octyl-ketone; CH3. CO . (CH2)7 . CH3) Rut. Ruta graveolens (oil), montana (oil) Hentriacontan-22-ol-I6-one (22-Hydroxy-palmitone) Santal. Santalum album (1f-wax) Hentriacontan-i6-one (Aethalone; Palmitone; CH3. (CH2)14 . CO . (CH2)14 . CH3) occurs in bacteria and in Santal. Santalum album (1f-wax) Comp. Tagetes grandiflora (fl., probably) Heptacos-I¢-one (Myristone; CH3 . (CH2)12 • CO. (CH2)12. CH3) Legum. Medicago sativa (not confirmed ?) Heptan-2-one (Methyl-n-amyl-ketone) Laur. Cinnamomum zeylanicum (oil) Rut. Ruta montana (oil, trace) Myrt. Eugenia caryophyllata (cloves) 2-Methyl-hept-z-en-6-one Urtic. Urtica dioica Gerani. Pelargonium Rut. Citrus? Sterculi. Theobroma cacao Lab. Ocimum canum Verben. Lippia citriodora Comp. Artemisia scoparia Gram. Andropogon citratus, nardus Zingiber. Zingiber officinale Nonacosan-15-one (Dimyristyl-ketone; Di-n-tetradecyl-ketone) Crucif. Brassica (1f-wax) Nonan-z-one (methyl-n-heptyl-ketone) Rut. Boronia ledifolia var., Phellodendron sp., Ruta chalepensis, and other spp. Myrt. Eugenia caryophyllata (cloves) Palmae. Cocos nucifera (oil) Octan-z-one (Methyl-n-hexyl-ketone; z-Octanone) Rut. Ruta montana (oil, trace) Octan-3-one (Ethyl-n-amyl-ketone; 3-Octanone) Lab. Lavandula vera (oil); Mentha Pentan-2-one (Methyl-n-propyl-ketone) Bromeli. Ananas sativus (frt, trace) Tridecan-2-one (Methyl-n-undecyl-ketone) Schisandr. Schisandra nigra (1f-oil, to i%) Undecan-z-one (Enodyl; Luparone; Methyl-n-nonyl-ketone) Mor. Humulus lupulus (` luparone') Schisandr. Schisandra nigra (ess. oil) Laur. Litsea odorifera (1f-oil)

KETONES 663

Saurur. Houttuynia cordata (oil) Legum. Glycine max (soy-bean oil) Rut. Boronia ledifolia (1f-oil); Citrus limetta (frt-peel-oil); Fagara xanthoxyloides (frt-peel); Phellodendron amurense (frt-oil); Ruta bracteosa (oil, much), chalepensis (oil, much), graveolens (` enodyl'), montana (much) Palmae. Cocus nucifera (oil), Elaeis guineensis (palm-kernel oil) Undec- i -en-io-one (CH2=CH . (CH2)7 . CO. CH3) Lour. Litsea odorifera

II AROMATIC KETONES. i Acetophenones List and Occurrence Acetophenone (Hypnone; Methyl-phenyl-ketone; fig. 137) seems to be widely distributed. Salic. Populus balsamifera (buds) Urtic. Urtica dioica Prote. Stirlingia latifolia The. Camellia (green tea, trace) Tili. Corchorus olitorius? Cist. Cistus creticus, ladaniferus Irid. Iris Acetovanillone (Apocynin; 3-Methoxy-4-hydroxy-acetophenone; fig. 137) seems to be very widely distributed. Cact. Echinocereus engelmannii, Mammillaria runyonii, Neolloydia texensis Apocyn. Apocynum androsaemifolium (rt), cannabinum (rt, apocynin) Amaryllid. Buphane disticha (bulb) Irid. Iris Acetovanillone-glucoside (Androsin; Gluco-acetovanillone) Cad. Neolloydia texensis (plt) Apocyn. Apocynum androsaemifolium (rt, androsin') Acetovanillone-4-ß-primveroside (?Neolloydosin) Cact. Neolloydia texensis (plt, neolloydosin') Acetoveratrone (3,4-Dimethoxy-acetophenone) Irid. Iris 3,4-Dihydroxy-acetophenone occurs in a conifer (Picea), but not (?) in angiosperms. a-Hydroxy-acetophenone (o-Hydroxy-acetophenone) Rubi. Chione glabra (wd, bk)

664 CHEMOTAXONOMY OF FLOWERING PLANTS

H3CO

2

6

3

5 4

Acetophenone

OH

OCH3 OCH3

OH

Acetovanillone

Phloracetophenone-4,6-dimethyl-ether.

Fig. 137 Some acetophenones.

4-Hydroxy-acetophenone (Ameliarol ; Piceol ; p-Hydroxy-acetophenone) is the aglycone of salinigrin. Salic. Populus trichocarpa (buds) 2-Hydroxy-5-methoxy-acetophenone Primul. Primula acaulis (rhiz.; as glycoside) 2-Hydroxy-6-methyl-acetophenone Elaeocarp. Elaeocarpus polydactylus (lvs) 6-Methoxy-paeonol Xanthorrhoe. Xanthorrhoea arborea, preissii, reflexa, tateana (these occurrences have been questioned by later workers) 4-Methyl-acetophenone (Oryzanone) is an attractant for the rice stem borer. Gram. Oryza sativa Paeonol (Peonol; 2-Hydroxy-4-methoxy-acetophenone) Paeoni. Paeonia moutan (rtbk) Primul. Primula auricula (rt-oil, as glucoside ?) Xanthorrhoe. Xanthorrhoea arborea (resin), reflexa (resin) Paeonol-glucoside (Gluco-paeonol) Paeoni. Paeonia arborea (rt) Phoracetophenone (z,4,6-Trihydroxy-acetophenone) Rut. Zanthoxylum alatum, aubertia Phloracetophenone-4,6-dimethyl ether (Brevifolin; Xanthoxylin; fig. 137) Euphorbi. Hippomane mancinella (lvs) Rut. Fagara arenaria (lvs, frt); Geijera parviflora, salicifolia; Zanthoxylum (Xanthoxylum) alatum (sd), aubertia (sd), rhetsa (frt) Myrt. Eucalyptus bakeri (lvs, oil) Comp. Artemisia brevifolia (plt, brevifolin'), Blumea balsamifera (ess. oil) Phloracetophenone-2,4,6-trimethyl ether Amaryllid. Lycoris radiata (bulb)

KETONES 665 HO HO OH

OCHS

4

Benzophenone

Cotoin

OH

OH

Maclurin

Scleroin

Fig. 138 Some benzophenones.

Salinigrin (Ameliaroside; Picein; Pungenin ?; Salicinereine; 4-Hydroxyacetophenone-ß-n-glucopyranoside) occurs in a conifer (Picea) and in Salle. Salix cinerea (bk), nigra; Populus? Ros. Amelanchier vulgaris (bk, ameliaroside') Verben. Clerodendron trichotomum (bk)

II.2 Benzophenones List and Occurrence Benzophenone (Diphenyl-ketone; fig. 138): does not occur as such? Cotoin (2,6-Dihydroxy-4-methoxy-benzophenone; fig. 138) occurs in ` coto-bark'. Is this from Nectandra coto (Laur.) or from Rudgea (Rubi.) ? Hydro-Cotoin (6-Hydroxy-2,4-dimethoxy-benzophenone) occurs in ` para-coto-bark' (Nectandra or Rudgea?). 4-Hydroxy-benzophenone (p-Hydroxy-benzophenone) Magnoli. Talauma mexicana (lys) Maclurin (Laguncurin; 2,4,6,3',4'-Pentahydroxy-benzophenone; fig. 138)

Mor. Chlorophora (Madura, Morus) tinctoria Legum. Acacia sp. Combret. Laguncularia racemosa (bk, laguncurin') Methyl-hydro-cotoin (2,4,6-Trimethoxy-benzophenone) occurs in ` para-coto-bark' (Nectandra or Rudgea?) and in Rhamn. Rhamnus purshiana (bk) Methyl-protocotoin (Oxyleucotin; 2,4,6-Trimethoxy-3',4'-methylenedioxy-benzophenone) occurs in `para-coto-bark' (Nectandra or Rudgea ?). Protocotoin (6-Hydroxy-2,4-dimethoxy-3',4'-methylenedioxybenzophenone) occurs in `para-coto-bark' (Nectandra or Rudgea ?).

666

CHEMOTAXONOMY OF FLOWERING PLANTS

Scleroin (2,5-Dihydroxy-3,4-dimethoxy-benzophenone; fig. 138) occurs with neoflavanoids, which it resembles, in Legum. Machaerium scleroxylon (htwd)

II.3 Other aromatic ketones GENERAL Again we have difficulties in classification. By no means all of the compounds listed here are biogenetically related. Some seem to be terpenoid, some are derivatives of phenolic adds. It is obvious that the large and much-investigated family Myrtaceae has many of these substances. An interesting group occurs in Humulus. Another group of related ketones occurs in the Zingiberaceae. List and Occurrence Adhumulone is an isomer of humulone. Mor. Humulus lupulus Angustione (fig. 139) was the first natural biketone (or triketone) to be described. Myrt. Backhousia angustifolia (lvs) Anise-ketone (Anise-acetone; Anisyl-ketone; p-Methoxy-phenyl-acetone) Illici. Illitium verum (frt-oil) Umbell. Foeniculum vulgare (oil), Pimpinella anisum (oil) Aristolone: may be a sesquiterpene? Aristolochi. Aristolochia debilis (rt) Aritasone: may be a diterpene? Chenopodi. Chenopodium ambrosioides (ess. oil) Baeckeol (fig. 139) Myrt. Baeckea crenulata (1f-oil ?), frutescens (ess. oil), gunneana var. latifolia (If-oil); Darwinia grandiflora Bis(p-hydroxycinnamoyl)-methane Zingiber. Curcuma longa Cohumulone—see humulone. Mor. Humulus lupulus Colupulone—see humulone. Mor. Humulus lupulus Conglomerone is very like baeckeol. Myrt. Eucalyptus conglomerata (1f-oil)

KETONES 667

Cryptone (fig. 139) occurs in Pinus and Rut. Zanthoxylum rhetsa (frt-oil, 1-) Myrt. Eucalyptus cneorifolia (oil, l-), dumosa (1-), hemiphloia (1-). micrantha (oil, l-), polybracteata (oil, l-), viridis (1-) Umbel?. Oenanthe phellandrium (oil, d-) Curcumin (Diferuloyl-methane; fig. 139) Zingiber. Curcuma aromatica (rt ?), longa (rhiz.), tinctoria, xanthorrhiza (rhiz.) Dehydro-angustione is said to be toxic in soil. Myrt. Backhousia angustifolia (lvs), Eucalyptus rarifiora Dihydro-ionone Comp. Saussurea lappa (rt-oil, cis-) Eugenone is very like baeckeol. Myrt. Eugenia caryophyllata (wild form) Flavesone (fig. 139) Myrt. Eucalyptus decorticans (ess. oil), Leptospermum flavescens (ess. oil) Humulone (fig. 139) is one of a group of related substances occurring in the much-investigated hops. Mor. Humulus lupulus (resin) p-Hydroxy-cinnamoyl-feruloyl-methane Zingiber. Curcuma longa p-Hydroxy-propiosyringone may be a `building brick' of lignin, particularly of angiosperms. p-Hydroxy-propiovanillone may be a `building brick' of lignin. d-a-Ionone (fig. 139) Rut. Boronia megastigma (ess. oil) Lythr. Lawsonia inermis (fl.-oil) Comp. Saussurea lappa (rt-oil) ß-Ionone (Boronione) Rut. Boronia megastigma (ess. oil) Lythr. Lawsonia inermis (fl.-oil) Comp. Saussurea lappa (rt-oil) a-Irone is closely related to the ionones. Trid. Iris florentina (rt), germanica, pallida (rt) ß-Irone Trid. Iris germanica y-Irone Trid. Iris spp. Leptospermone (Leptospermol; fig. 139): is this also a sesquiterpene ? Myrt. Eucalyptus?; Leptospermum flavescens (1f-oil), scoparium (ess. oil)

668 CHEMOTAXONOMY OF FLOWERING PLANTS

o, HO

OCH3 OCH3

H3CO

O

O

0

HO

OH

OCH3 Curcumin

Cryptone

Angustione Baeckeol

HO O,

yw..)ø

I.

OH# HO II

O

0 Humulone

Flavesone

d-.(- lonone

.O

oO

II

O

0

Leptospermone

Hedeomol 1,1,3 Trimethyl-

Zingerone

-cyclohexan-2-one

Fig. 139 Some aromatic ketones.

Lupulone--see humulone. Mor. Humulus lupulus d-I-Methyl-cyclohexan-3-one (Hedeomol; fig. 139) Lab. Hedeoma pulegioides (ess. oil), Mentha canadensis? (ess. oil) Gram. Andropogon nardus (oil) Methyl-gingerol Zingiber. Zingiber officinale (rhiz.) 1 -Phenyl-butan-3-one (Methyl-ß-phenyl-ethyl ether) Pandan. Pandanus odoratissimus (fl.-oil) Santenone (7T-Nor-camphor): should be placed among the monoterpenes? Santal. Santalum album Shogaol Zingiber. Zingiber officinale (rhiz.) Tasmanone Myrt. Eucalyptus risdoni

KETONES 669

1, i,3-Trimethyl-cyclohexan-2-one (fig. 139) Cist. Cistus creticus (oil), ladaniferus (oil) Zingerone (fig. 139) Zingiber. Zingiber officinale (rhiz.)

III OTHER CYCLIC KETONES GENERAL A few ketones have cyclopentane or cyclopentene rings, and these may be considered briefly here. Some of them, at least, are effective when used against insects. Is this of biological significance for the plants producing them ? List and Occurrence Calythrone (fig. 140) Myrt. Calythrix tetragona var. A (ess. oil), virgata (ess. oil) Cinerin-I (fig. 140) is an active principle of `pyrethrum'. Does it occur as such ? Cinerin-II is very like cinerin-I. It, too, is said to be an active principle of pyrethrum'. Does it occur as such ? Cinerolone is derived from pyrethrin-I. Does it occur as such ? Cyclopentan-x-one (fig. 140) has been found in wood-oil, but secondarily ? 3-Isopropyliden-x-acetyl-cyclopent-5-ene (fig. 140): should this be treated as a monoterpene? Myrt. Eucalyptus globulus (ess. oil) 3-Methyl-z-pentenyl-cyclopent-z-en-t-one (Jasmone) Rut. Citrus (fl. oil) Ole. Jasmimum grandiflorum (fl.-oil, cis-) Lab. Mentha piperita (oil) Pyrethrin-I (fig. 140) is a constituent of `pyrethrum'. Comp. Chrysanthemum cinerariaefolium (fl.) (and other spp. ?) Pyrethrin-II is a constituent of `pyrethrum'. Comp. Chrysanthemum cinerariaefolium (fl.) (and other spp. ?) Pyrethrolone is derived from `pyrethrum'. Does it occur as such ? `Pyrethrum' is, says Hill (1952), of at least 3 sources: Chrysanthemum cinerariaefolium (Dalmatian insect flowers), the most important; C. coccineum (Persian ditto); and C. marschallii (Caucasian ditto). `Pyrethrum' is one of the most effective of natural products for use

670 CHEMOTAXONOMY OF FLOWERING PLANTS

3

O Cyclopentan-1-one

24,4-Trimethyl-

3-Isopropyliden-

-cyclopentan-1-

-1-acetyl-cyclo-

Calythrone

pent- 5-ene

- one

'o Cinerin-I

Pyrethrin-1

Fig. 140 Some cyclic ketones.

against insects. It is not toxic to man. Some, at least, of its active ingredients have been listed above. 2,4,4-Trimethyl-cyclopentan- i -one Lab. Mentha pulegium (ess. oil)

LACTONES GENERAL As in so many other cases classification is difficult. We include here a number of lactones with five-membered heterocyclic rings. Many lactones with six-membered rings, however, are a-pyrones and we have treated them as such. A few are obviously derived from hydroxy-fatty adds. Some alkaloids, such as those of Stemona, are lactones. Many sesquiterpenes are mono- or di-lactones. At least one acetylenic lactone is known, and it is treated with its parent as an `acetylenic compound'. Many fungal products which are antibiotic are lactones, and a few of the lactones of higher plants are said to be antibiotic, too. Note the occurrence of ten or more phthalides in the Umbelliferae.

LACTONES 671

List and Occurrence Anemonin (fig. 141) is a dimer of protoanemonin. Ranuncul. Aconitum napellus ?; Anemone pulsatilla (and other spp.) ; Clematis (2); Ranunculus (several spp.) Biglandulinic acid Euphorbi. Euphorbia biglandulosa (as a calcium salt in latex) 3-n-Butyl-phthalide (fig. 141) Umbell. Apium graveolens (sd-oil), Levisticum officinale (rt-oil), Ligusticum acutilobum (rt-oil) Cnidilide Umbell. Cnidium officinale (rt) ` Cnidium-lactone': a mixture ? Umbell. Cnidium officinale (rt) Cuscutalin: what is this ? Convolvul. Cuscuta Eleutherol (fig. 141) is a naphthalide. Irid. Eleutherine bulbosa (bulb) Grantianic acid—the necic acid of grantianine—is a lactone. Hibiscic acid ( ?Hibiscus acid; (+)-Allo-oxycitronic acid-lactone) Maly. Hibiscus sabdariffa (Ivs, fl., fruiting-calyx) Holigarna-lactone is, says Karrer (1958), of uncertain structure. He has `hlygarna-lactone'. Anacardi. Holigarna arnottiana (sd) 3-Isobutylidene-3a,4-dihydro-phthalide Umbell. Apium graveolens (odorous constituent) 3-Isobutylidene-phthalide (fig. 141) Umbell. Apium graveolens (odorous constituent) 3-Isovalidene-3a,4-dihydro-phthalide Umbell. Apium graveolens (odorous constituent) 3-Isovalidene-phthalide Umbell. Apium graveolens (odorous constituent) Junceic acid—the necic acid of junceine—is a lactone. Leucodrin (Proteacin; Protexin; fig. 141): belongs here ? It occurs (always ?) as leucoglycodrin. Leucoglycodrin (p-Glucosyl-leucodrin) Prote. Leucadendron adscendens (lvs), concinnum (lvs), stokoei (lvs) Ligusticum-lactone (3-Butylidene-phthalide; fig. 141) Umbell. Levisticum officinale (rt-oil), Ligusticum acutilobum (frtoil) Ligustilide (fig. 141) Umbell. Cnidium officinale (rt), Ligusticum acutilobum (rt)

672 CHEMOTAXONOMY OF FLOWERING PLANTS

OCH3

°C-Methylene-

°C - Methoxy A '

butenolide

Proto-anemonin Anemonin

-butyrolactone

O

0 3-n-Butyl-phthalide

Ligusticum -lactone

Ligustili de

Meconine

HO

O

(tn .'

Qc—io HO HO On

u O

O'' O

CH2OH

HO OH

Eleutherol /3 -Soringeni n

3-Isobutylidene- phthalide

Fig.

141

Leucodrin

Some lactones.

Meconine (6,7-Dimethoxy-phthalide; Mekonin; Opianyl; fig. I4I) is the `bottom' of a phthalide-isoquinoline alkaloid. Ranuncul. Hydrastis canadensis (rt) Papaver. Papaver somniferum a-Methoxy-6.a' il-butenolide (fig. 141) Lili. Narthecium ossifragum (infl.) a-Methylene-butyrolactone (fig. 141) is said to be bacteriostatic. Lili. Erythronium americanum (chiefly as a glycoside ?) Monocrotalic acid, a necic acid, is a lactone (but not in the alkaloid monocrotaline ?). Neocnidilide Umbell. Apium graveolens (frt-oil), Cnidium officinale (rt) Peperic acid is said to be an autoxidation product of mentho foran, but it also occurs naturally in Lab. Bystropogon mollis (oil) Protoanemonin (fig. 141) is the aglycone of ranunculin. It is said to be antibiotic.

LACTONES 673

Ranuncul. Anemone pulsatilla, Caltha ?, Clematis (8), Ranunculus (several) Ranunculin is a glycoside of protoanemonin. Ranuncul. Ranunculus acris, arvensis, bulbosus, sceleratus Sceleranecic acid—a necic acid—is a dilactone? `Sedanolide' is a mixture of neocnidilide and n-butyl-phthalide. Umbell. Apium graveolens (sd-oil) Sedanonic acid anhydride Umbell. Apium graveolens (sd-oil) ?, Cnidium officinale (rt), Levisticum officinale (rt-oil) a-Sorigenin is a naphthalide. It is the aglycone of a-sorinin. ß-Sorigenin (fig. 141) is the aglycone of ß-sorinin. Rhamn. Rhamnus japonica (bk, free ?) a-Sorinin is a-sorigenin-5 primveroside. Rhamn. Rhamnus japonica (bk) ß-Sorinin is ß-sorigenin-5 primveroside. Rhamn. Rhamnus japonica (bk)

LIGNANS GENERAL Haworth (1937), writing of `natural resins', pointed out the importance of the union of two C6-C3 units in the formation of certain components of the resins. He proposed, because of their frequent occurrence in wood, the generic name lignane'. The name, but without the final `e', seems to have been adopted, and we now speak of lignans as a class. Some of the lignans are, at the same time, lactones. Erdtman (in Todd, 1956), has much to say of lignans in connection with conifer taxonomy. He says (p. 474): The lignans must be considered to be typical examples of secondary constituents. They form a rather large group of substances of varying structure in which, however, there are two easily recognizable C6-C3 units condensed together at the ß-carbon atom of the side chains. It seems out of the question that such compounds could be synthesized in Nature except from primary C6-C3 compounds. ..In the laboratory, one can in fact prepare compounds of lignan type by the dehydrogenation of, for example, isoeugenol (to an analogue of conidendrin), ferulic acid (to an analogue of pinoresinol), and coniferyl alcohol (to dl-pinoresinol).

674 CHEMOTAXONOMY OF FLOWERING PLANTS

Hearon and MacGregor, at about the same time (1955), say: In relationship to other non-carbohydrate plant constituents the lignans would represent a dimer stage intermediate between monomeric propyl-phenol [C6–C3] units and lignin[s]. Naturally occurring trimers and tetramers have not been reported. Some of the lignans found in wood may be due to pathogenic factors. Thus Erdtman (in Swain, 1963) says that Hasegawa and Shirato found large amounts of the lignan iso-olivil (which occurs `normally' in the resin of an olive, Olea cunninghamii) in the wood of a Prunus suffering from attack by a fungus. The lignan is said not to occur in the fungus or in the Prunus when alone. We may wonder about this, however. I believe some of the depsides produced by lichens—and which were said not to be formed by either of the lichen partners alone—are, in fact, formed by the fungal partners when grown under appropriate conditions in pure culture. Although lignans appear to be widely distributed in higher plants our records from angiosperms are still too few for many generalizations. We may note a few suggestive facts, however. (a) I have no records at all from monocotyledons. Are lignans indeed absent from that great group ? (b) A disproportionate number of records come from Magnoliales, Ranunculales, Piperales and Aristolochiales, orders which are considered to be closely related. Thus we have (numbers of lignans present in brackets): Magnoliales 1. Magnoli. Liriodendron tulipifera (i) 3. Himantandr. Galbulimima baccata (2), belgraveana (I) 7. Myristic. Myristica otoba (3), Virola (I) 14. Monimi. Piptocalyx moorei (1) 17. Laur. Eusideroxylon zwageri (1) ; Ocotea usambarensis 0), veraguensis (1) 18. Hernandi. Hernandia ovigera (4) Ranunculales 2. Berberid. Diphylleia grayi (I); Podophyllum emodi (6), peltatum (6), sikkimensis (I ) Piperales 2. Piper. Piper cubeba (1), lowong (I ), peepuloides (I) Aristolochiales 1. Aristolochi. Asarum blumei (I ), sieboldii (i)

LIGNANS 675

List and Occurrence Arctigenin (fig. 14z) is the aglycone of arctiin. Comp. Arctium lappa (frt) Arctiin was the first lignan-glucoside to be discovered. Comp. Arctium lappa (frt) Asarinin is a stereoisomer of sesamin. Aristolochi. Asarum blumei (l-) Rut. Acronychia muelleri (lvs, d-); Zanthoxylum carolinianum (bk, l-), clava-herculis (bk, 1-) Calopiptin Monimi. Piptocalyx moorei Cicutin is the Cs-epimer of deoxy-podophyllotoxin. Umbell. Cicuta maculata (rt) Collinusin Euphorbi. Cleistanthus collinus (lvs) Cubebin Piper. Piper cubeba (frt) Dehydro-podophyllotoxin Berberid. Podophyllum peltatum Demethylenedioxy-deoxy-podophyllotoxin Hernandi. Hernandia ovigera (sd-oil) 4'-Demethyl-podophyllotoxin (fig. 142) Berberid. Podophyllum emodi (resin), peltatum 4'-Demethyl-podophyllotoxin-glucoside (fig. 142) has glucose at x. Berberid. Podophyllum emodi (rhiz.) Deoxy-podophyllotoxin (Anthricin; Hernandion; Silicicolin) occurs in conifers and in Hernandi. Hernandia ovigera (sd-oil) Berberid. Podophyllum peltatum (resin), pleianthum Umbell. Anthriscus silvestris (rt) Diaeudesmin Piper. Piper peepuloides (frt) Diphyllin Berberid. Diphylleia grayi (rt) Euphorbi. Cleistanthus collinus (lvs) 1-Eudesmin (Pinoresinol dimethyl ether) Myrt. Eucalyptus hemiphloia (Kino) Convolvul. Humbertia madagascariensis (wd) Eusiderin Laur. Eusideroxylon zwageri (wd) d-Forsythigenol (d-Pinoresinol-methyl ether; Phillygenin; Phillygenol) is the aglycone of forsythin.

676 CHEMOTAXONOMY OF FLOWERING PLANTS

Forsythin (Phillyrin; Philyroside) is dimorphic. Ole. Forsythia (3), Olea?, Phillyrea (3) Galbacin Himantandr. Galbulimima baccata (bk) Galbulin (fig. 142) Himantandr. Galbulimima sp. (bk) Galcatin Himantandr. Galbulimima baccata (bk) Galgravin Himantandr. Galbulimima belgraveana (bk) Gmelinol Verben. Gmelina leichhardtii (wd) l-Guaiaretic acid (fig. 142) Zygophyll. Guaiacum officinale (resin) Hydroxy-otobain Myristic. Myristica otoba (frt-oil), Virola cuspidata (bk) d-Iso-olivil Ros. Prunus (diseased wd) Ole. Olea cunninghamii (resin) Iso-otobain Myristic. Myristica otoba (frt-oil) Justicidin-A (Diphyllin-methyl ether) (but the formula I have seems not to be that of diphyllin-methyl ether). Rut. Cneoridium dumosum (plt) Acanth. Justicia hayatai var. decumbens Justicidin-B Acanth. Justicia hayatai var. decumbens Liriodendrin is a diglucoside of lirioresinol. Magnoli. Liriodendron tulipifera (bk) Lirioresinol is a stereoisomer of syringaresinol. How does it differ from (— )-lirioresinol-C ? Saliv. Populus sp. (— )-Lirioresinol-C Apocyn. Aspidosperma marcgravianum (wd) Lyonia-xyloside ((+ )-Dimethoxy-isolariciresinol-xyloside; fig. 142) Betul. Alnus glutinosa Ros. Sorbus Eric. Lyonia sp. Nordihydro-guaiaretic acid Zygophyll. Larrea cuneifolia, divaricata (lvs), nitida Olivil Ole. Olea europaea (wd)

LIGNANS 677

OH X

01-1

OCHS

Arctigenin

4-Demethyl-podophyllotoxin

Galbulin

CH3 OH

Guaiaretic Acid

? Sesamin

Lyonia-xyloside

Otobain

Skeletons of lignans Fig. 142 Some lignans.

(+ )-O,O-Dimethyl-lirioresinol-B Apocyn. Aspidosperma marcgravianum (wd) Otobain (fig. 542) Myristic. Myristica otoba, Virola cuspidata oa-Peltatin Berberid. Podophyllum peltatum (rt) a-Peltatin-glucoside Berberid. Podophyllum peltatum ß-Peltatin Berberid. Podophyllum peltatum (rt) Picropodophyllin, Picropodophyllin-acetate, etc., are artefacts ?

678 CHEMOTAXONOMY OF FLOWERING PLANTS

Podophyllotoxin occurs in conifers and in Berberid. Diphylleiagrayi; Podophyllum emodi and var. hexandrum (resin), peltatum (rhiz.), pleianthum Podophyllotoxin acetate Hernandi. Hernandia ovigera Podophyllotoxin-glucoside Berberid. Podophyllum emodi Sesamin (Pseudo-cubebin; fig. 142) seems to be widely distributed. Laur. Ocotea usambarensis (bk, d-) Piper. Piper lowong. (frt, d-) Aristolochi. Asarum sieboldii var. seoulensis (1-) Rut. Fagara viridis (bk, d- and i-), xanthoxyloides (rtbk, d- and 1-); Flindersia? Pedali. Sesamum angolense (d-), indicum (d-) Sesamolin: the formula given in K. (1958) looks wrong! Pedali. Sesamum indicum Sesangolin Pedali. Sesamum angolense Sikkimotoxin: related to podophyllotoxin? Berberid. Podophyllum sikkimensis (rhiz., rt) Symplocosin is said to be a lignan-glucoside yielding symplocosigenol (an enantiomorph of forsythigenol) and glucose. Symploc. Symplocos lucida (japonica) (bk) Syringaresinol Salic. Populus sp. Veraguensin Laur. Ocotea veraguensis (wd)

LIGNINS GENERAL Botanists have recognized for a very long time that certain tissues of vascular plants—xylem, bast-fibres, sclereids of various kinds and distribution, pith (sometimes), and even (but rarely) stomata—may be `lignified'. Such tissues react differently from `unlignified' tissues to stains and some reagents, and the relative constancy of these differences has led botanists until comparatively recently to think of an entity, lignin, which conveys the character of `woodiness' to lignified tissues. Yet seventy years ago Mäule showed that in general the woods of gymnosperms and angiosperms differ in their colour reaction when chlorinated and then treated with ammonia (p. 75). This has suggested

LIGNINS 679

to some investigators the possibility that more than one kind of lignin exists, and that groups of plants may be characterized by their lignins. But lignins have proved refractive and we cannot, even today, use lignin chemistry to any great extent in chemotaxonomy. I have been involved a little in this problem. In the 194os Hibbert and others were subjecting woods to alkaline oxidation and were obtaining quite large yields of vanillin and syringaldehyde (fig. 143). When Hibbert told me that he got syringaldehyde from maple, but not from spruce wood, I suggested that Mäule's reaction (mentioned above) might be due to presence of the syringyl grouping in the one but not in the other. We were able to show (Creighton, Gibbs and Hibbert, 1944) that this was indeed the case. Creighton also found that some monocotyledons seemed to have a third grouping in their lignin, yielding p-hydroxy-benzaldehyde (fig. 143) in addition. Already it had been shown by others that at least one species of Podocarpus (a gymnosperm) is unusual in giving a positive Mäule reaction like an angiosperm. We were able to demonstrate that this (and some other) species of Podocarpus, Tetraclinis articulata (of the gymnospermous Cupressaceae), members of the gymnospermous (?) Gnetales, and perhaps all cycads, give positive Mäule reactions and that their lignins yield syringaldehyde. An important observation was that the ratio syringaldehyde: vanillin is about 3 :I for most angiosperms. Some `primitive' angiosperms seemed to have lower ratios, and this is correlated with a weaker Mäule reaction (Towers and Gibbs, 1953). We also amassed evidence suggesting the separation of Negundo from Acer. There is some reason, then, to believe that there is not one lignin, but several; or that lignin varies in its exact structure from species to species, or even during the development of a single plant. Alston and Turner (1963) see some hope for further use of lignin(s) in chemotaxonomy: Lignin is a plant product which potentially is of great systematic value, especially if technical advances occur which provide a method of analysing the sequential linkages of the building units and their cross linkages.' There is abundant evidence that C6—C3 units such as coniferyl alcohol (fig. 143) are the building blocks of lignin(s). It has been shown, for example, that C14 coniferyn (the glucoside of coniferyl alcohol) is very efficiently incorporated into spruce lignin. Freudenberg and others have postulated a polymeric structure for lignin(s), and some dimers such as the lignans (see our preceding section) are known, and have even been synthesized enzymatically. The relationship of the C6—C3 units involved in lignin(s) to the flavonoids is clear. Bate-Smith (1963) even goes so far as to say that

68o

CHEMOTAXONOMY OF FLOWERING PLANTS

CHO

CHO

OH

OH

CHO

OCH3H3CO

p-Hydroxy-benzaldehyde

GH2OH

Vanillin

H3CO

CH HO

CH

OCHS OH

Syringaldehyde

COOH CH.NH2

COON

CH2

CH CH

+ NH3

OCH3 OH

Coniferyl alcohol

Pinores nol (a lignan)

Phenyl--- Cinnamic+Ammonia -alanine acid

Fig. 143 Substances believed to be involved in lignin(s).

lignins may `be regarded as flavonoids in the wider sense', and that: `the presence of leucoanthocyanins, flavonols and hydroxy acids in the leaves is associated with the uninhibited deposition of lignin [hence woodiness] whereas the presence of flavones and methoxy acids in leaves is associated with a tendency for suppression of lignification'. Harborne (1966) enlarges on this and says: `The relative wealth of flavone production in some herbaceous plants, e.g. members of the Compositae, may represent a means of avoiding a build-up of lignin precursors.' Some, at least, of the 'lignin-precursors' are said to arise from one of the `protein' amino-acids, phenyl-alanine (fig. 143).

CHEMOTAXONOMY OF

FLOWERING PLANTS R. DARNLEY GIBBS Emeritus Professor of Botany, McGill University, Montreal, Canada

VOLUME II FAMILIES

McGILL-QUEEN'S UNIVERSITY PRESS MONTREAL AND LONDON '974

© McGill—Qreen's University Press 1974 ISBN o 7735 0098 7 Library of Congress Catalog Card No. 73-79096 Legal Deposit 2nd Quarter 1974 Printed in Great Britain at the University Printing House, Cambridge, England (Brooke Crutchley, University Printer)

MELANINS GENERAL The name `melanin' has been variously used. It has been employed for any dark-brown or black substance (or mixture) occurring in plant or animal. Because there is abundant evidence that a group of substances so named would be chemically and biosynthetically unnatural, attempts have been made to use the term melanins only for those dark-coloured polymeric indole derivatives that involve tyrosine, dihydroxy phenylalanine (DOPA), and dopamine, and tyrosinase and oxygen. We may cite first of all the brief review by Thomas (1955), who points out that the `melanins' of higher plants may include indole derivatives— though no such melanin had at that time been isolated and analysed— and other non-nitrogenous `melanins' such as the phytomelanes of the Compositae, Japanese lac, and many oxidation products of phenols. The true N-containing melanins, he says, may be variable. Some may contain sulfur, and some (all ?) may exist as melanoproteins. The animal (true) melanins are insoluble in hot strong acids, but more or less soluble in alkalis. He gives, as a possible unit of such melanins, the dimer of fig. 144. In 1958 Thomas has a further article on melanin (he uses the singular form). He says that the first real clue as to the nature of melanin came from the work of Bertrand and Bourquelot (1894-6) who noted that in Rhus spp., the sources of lac, there seems to exist the system: (laccase) laccol

> lac

while in other plants one may have: (tyrosinase) Tyrosine

> black pigment

Thomson (1965) says that true melanins are probably produced by the legumes Vicia faba, Cytisus nigricans and Sarothamnus scoparius, and the banana. He gives a melanin unit (fig. 144) that differs slightly from that of Thomas. Andrews and Pridham (1967) investigated the `melanins' of some higher plants which have DOPA (ß-(3,4-dihydroxy phenyl)-L-alanine) or dopamine (ß-(3,4-dihydroxy phenyl) ethylamine), and compared them with enzyme-synthesized `melanins'. They got the following results for nitrogen content, etc. Astragalus cicer (pod), N 1•z% Baptisia australis (pod), N 1.6% [68x ]

68z

CHEMOTAXONOMY OF FLOWERING PLANTS

/, . 0 0

Thomas (1955)

Thomson (1965)

Fig. 144. Possible melanin units. Lupinus polyphyllus (pod), N 1.3%; alkali fusion gave catechol, protocatechuic acid and 5,6-dihydroxy-indole. Vicia angustifolia (pod), N i-4%; alkali fusion as above V. faba (fl.), N 2•I%; alkali fusion as above V. faba (pod), N P3% Musa sp. (epicarp), N 1.5% Tyrosine-melanin (synthesized with phenolase), N 7.1% Dopamine-melanin (synthesized with phenolase), N 6.8% They concluded: `The melanins from plants which contain DOPA and related compounds have been examined and shown to be largely composed of the catechol-type pigment. Some indole units also appear to be present, however.' The book Melanins by Nicolaus (1968) contains little more about the melanins of higher plants. The co-called phytomelanes of the Compositae, which blacken fruitwalls, and sometimes other parts of many species, seem not to contain nitrogen, or to have very little of it, and are not true melanins. Hegnauer (1964) lists work, largely by Hanausek, on the distribution of these substances in the tribes of the Compositae: Vernonieae absent (5 genera) Eupatorieae present in fruits of many (19 ?) genera. Astereae absent (z6 genera) Inuleae rare; but present in Caesulia axillaris (frt), Sphaeranthus sp., Ammobium sp., Inula helenium (rhiz., rt). Heliantheae present in spp. of 56 genera Helenieae present in Jaumeinae, Heleniinae and Tagetinae; but absent from Riddelliinae. Anthemideae absent from spp. of 10 genera. Senecioneae rare; absent from spp. of zo genera; but present in Arnica.

MELANINS 683

Calenduleae absent from spp. of 3 genera. Arctoteae absent from spp. of 8 genera. Cardueae (Cynareae) rare; absent from Brotera, Carlina, Centaurea, Cirsium, Cynara, Galactites, Onopordon, Serratula, Silybum (but see below), and Xeranthemum; but present in Echinops, Carthamus, and Silybum marianum (fruits of some). Mutisieae rare; present in Perezia (rhiz., rt); but not in fruits of spp. of Dicoma, Gerbera, Leuceria, and Moscharia. Cichorieae absent from spp. of 24 genera. Much information on blackening of plants or their extracts is scattered through this book under cigarette and hot-water tests, the aucubin-type glycosides, irritant plants (urushiol, etc.).

NAPHTHALENE AND SOME OF ITS DERIVATIVES GENERAL Again we have a dilemma. Naphthalene itself (fig. 145) is a hydrocarbon and might be discussed with other members of that `group'. Its derivatives include aldehydes, alcohols, lactones and quinones. We have sections for naphthaquinones (p. 699) and for lactones (p. 670) elsewhere. Some derivatives, such as those of Ulmus, are really sesquiterpenes, and are considered with them (p. 796). It seems desirable to deal with naphthalene itself and yet other of its derivatives here. According to Ruwet (1966) the cotyledons of Impatiens balsamina have a naphtholglycosidase which hydrolyses 1,z,4-trihydroxy-naphthalene-4 glucoside (fig. 145). The free I,2,4-trihydroxy-naphthalene is then auto-oxidized to z-hydroxy-1,4-naphthaquinone (lawsone; fig. 145). Ruvet says that the same or a similar enzyme from leaves of Juglans regia may be responsible for the formation of juglone.

List and Occurrence 4,5-Dihydroxy-2-methyl-naphthalene (fig. 145): see also diospyrol. Eben. Diospyros mollis (frt) 4.,5-Dimethoxy-6-hydroxy-z-methyl-naphthalene (Macassar-II ; fig.145) Eben. Diospyros celebica (htwd—`macassar ebony') 4,5-Dimethoxy-6-hydroxy-2-naphthaldehyde Eben. Diospyros ebenum (htwd) Diospyrol (fig. 145) is a dimer of 4,5-dihydroxy-z-methyl-naphthalene. Eben. Diospyros mollis (frt)

684 CHEMOTAXONOMY OF FLOWERING PLANTS

7

2

6

3 HO OH

Naphthalene

4,5-Dihydroxy-2- methyl- naphthalene

OGLUC. 4,5 -Di methoxy-6 -

HO OH

Diospyrol

O

HO OH

1,2,4-Trihydroxy- Lawsone

-hydroxy-2-methyl- -naphthalene-4-naphthalene

Musizin

-glucoside

Fig. 145. Naphthalene and some derivatives.

Musizin (3-Acetyl-4,5-dihydroxy-2-methyl-naphthalene; fig. 145) Rhamn. Maesopsis eminii (htwd—' musizi') Lili. Dianella laevis Naphthalene (fig. 145) is said to occur in a lichen and in Myrt. Eugenia caryophyllata (cloves) Comp. Saussurea lappa (rt-oil) Irid. Iris germanica Gram. Oryza sativa (sdlg, with methyl- and p-dimethyl-naphthalene) I,z,4-Trihydroxy-naphthalene-4-glucoside (fig. 145) may be the precursor of lawsone (fig. 145, and see above). Balsamin. Impatiens balsamina (cotyledons) I,4,5-Trihydroxy-naphthalene-4-glucoside may be the precursor of juglone (fig. 151 and p. 7o). 4,5,6-Trimethoxy-2-methyl-naphthalene (Macassar-III) Eben. Diospyros celebica (htwd) 4,5,6-Trimethoxy-2-naphthaldehyde Eben. Diospyros ebenum (htwd) PYRONES GENERAL We may distinguish agyrones, of which cc-pyrone (coumalin) itself (fig. 146) may be considered to be the `parent'; and y-pyrones, of which y pyrØ (fig. 147) may be considered to be the parent.

a-PYRONES 685

I a-PYRONES GENERAL Only a few simple agyrones are known. These include the kawapyrones of Piper. They are lactones and some of them are named as such. The benzo-agyrones include the coumarins, isocoumarins, furocoumarins, etc. They are dealt with in a separate section (p. 44o). Some a-gyrones are phthalides and some are derivatives of naphthalene. List and Occurrence Aparajitine (fig. 146) is the 6-lattone of 2-methyl-4-hydroxy pentacosanoic acid. Legum. Clitoria maritima, ternata Demethoxy-yangonin Piper. Piper methysticum Dihydro-kawain (Marindinin) Piper. Piper methysticum (st., rt) Dihydro-methysticin (Pseudo-methysticin) Piper. Piper methysticum (rt) Gentiopicroside (Erytaurine; Gentiamarin; Gentiopicrin; Sabbatin; Swertiamarin; fig. 146) has, says Paris (1963), the formula shown. It yields mesogentiogenin and glucose. Gentian. Chlora (1), Cicendia (1), Erythraea (1), Gentiana (2o), Pleurogyna (i), Sabbatia (at least 1), Swertia (3). Hyptolide is like massoilactone. Lab. Hyptis pectinata Kawain (fig. 146) Piper. Piper methysticum (rt) Massoilactone (fig. 146) Laur. Cryptocarya (Massoia) aromatica (bk-oil) 4-Methoxy-paracotoin Laur. Aniba fragrans Methysticin (fig. 146) Piper. Piper methysticum (rt) Mevalolactone (fig. 146) may be placed here. The biologically active form is R-(— )-mevalolactone. Opuntiol (fig. 146) Cact. Opuntia elatior Paracotoin (fig. 146) is said to occur in Bolivian ' coto-bark' and `Paracoto-bark'.

686

CHEMOTAXONOMY OF FLOWERING PLANTS

H3CO

0'0

H OH20~ 0 ~0

.(- Pyrone

(Coumal in)

Opu nt iol

Massoilactone

Aparajitine

OH

0 —. 0 ~0 ~

Mevalo lactone

6-PhenyI-coumalin

Paracotoin

O.GLUC.

Kawain

Methysticin

Gentiopicroside

Fig. 146. Some a-pyrones.

Parasorbic acid Ros. Sorbus aucuparia (unripe frt) 6-Phenyl-coumalin (fig. 146) is said to occur in `true' coto-bark. Yangonin Piper. Piper methysticum (rt)

II y-PYRONES

GENERAL We may recognize three groups of y-pyrones: 1. Simple y-Pyrones. 2. Chromones, derivatives of benzo-y-pyrone (fig. 148). See also flavonoids. 3. Xanthones, derivatives of dibenzo-y-pyrone (xanthone; fig. 149).

y- PYRONES 687 1

2

S ~ 0uj 4

u O

O Y- Pyrone

01-1

u O

O

Pyromeconic

Comanic

Matto!

Acid

Acid

(Laricinic Acid)

No OH COOH HOOC , , O , ,CODH HOOC . I 1 COOH

HOOC

or

O

O

I OH

Nö I

OH

OH O 0

Chelidonic Acid

Meconic Acid

2,3-Dihydro-3-methyl- 6-phenyl - Y -pyrone

Fig. 147. Simple y-pyrones.

II.I Simple y-Pyrones GENERAL Only a few simple y-pyrones seem to have been recorded from higher plants. One of them—chelidonic acid—is, however, very widely distributed. List and Occurrence Chelidonic acid (fig. 147) was found in more than half of the more than Imo species examined by Ramstad (1953). Kwasniewsky (1953) also lists many plants as containing the acid. We list only a few examples to show how widely spread it is. Papaver. Chelidonium majus, Stylophorum diphyllum (it, bound to an alkaloid) Berberid. Berberis vulgaris Campanul. Lobelia inflata and other spp. Rubi. Uragoga (Cephaelis) Lili. Asparagus (plt, fit), Colchicum, Convallaria (lvs), Gloriosa (lvs), Polygonatum (2), Schoenocaulon (sd), Veratrum (2) Comanic acid (fig. 147) Occurrence ?

688

CHEMOTAXONOMY OF FLOWERING PLANTS

2,3-Dihydro-3-methyl-6-phenyl-y-pyrone (fig. 147) Myrt. Myrtus bullata (ess. oil) Maltol (Laricinic acid; fig. 147) occurs in Larix and in Papaver. Corydalis ochotensis Meconic acid (fig. 147) : belongs here ? I find two formulae for it. Papaver. Papaver dubium, rhoeas, somniferum Pyromeconic acid (fig. 147) Comp. Erigeron annuus (lvs, fl.)

II.2 Benzo-y-pyrones (chromones)

GENERAL Many of the benzo-y-pyrones have other rings too. Thus some furochromones are known. Other substances which might be included here, such as deguelin, elliptone, and rotenone, are essentially isoflavanone derivatives and are treated with them (p. 609). Some of the other groups of flavonoids are also chromone or near-chromone derivatives. The occurrence of a unique group of benzo-y-pyrones in Ptaeroxylon and Cedrelopsis is of interest. These genera are removed from the Meliaceae by some taxonomists and placed in a little family Ptaeroxylaceae (q.v.). I know of no benzo-y pyrone in other members of the Meliaceae.

List and Occurrence Ammiol (2-Oxymethyl-5,8-dimethoxy-furo-4',5',6,7-chromone) Umbell. Ammi visnaga (sd) Angustifolionol (fig. 148) Myrt. Backhousia angustifolia (ess. oil) Chellol (fig. 148) is the aglycone of khellinin (chellol-2 glucoside). Does it occur free ? Eugenin (fig. 148) Myrt. Eugenia aromatica, caryophyllata (` cloves') Eugenitin (6-Methyl-eugenin) Myrt. Eugenia caryophyllata Heteropeucenin (fig. 148) Meli. Ptaeroxylon obliquum (htwd) Heteropeucenin-dimethyl ether Meli. Ptaeroxylum obliquum Heteropeucenin-7-methyl ether Meli. Ptaeroxylon obliquum

BENZO-y-PYRONES

7 6 HO 0

0 Benzo-Y-Pyrone (Chromone)

Angustifolionol

OH O

H3CO

HO

O

HO O

Eugenin

Peucenin

Chellol

CH0

HO 0

Visamminol

HO 0 . HO 0

Heteropeucenin

Ptaeroxylin

Fig. 148. Some benzo-y-pyrones (chromones). Isoeugenitin Myrt. Eugenia caryophyllata Isoeugenitol Myrt. Eugenia caryophyllata Karenin Meli. Ptaeroxylon obliquum (htwd) Khellin (Kellin; Visammin) Umbell. Ammi vinnaga (sd) Khellinin (Chellol-z-glucoside) Umbell. Ammi visnaga (sd) Khellinol (5-Norkhellin) Umbell. Ammi visnaga (sd) Peucenin (fig. 148) Meli. Ptaeroxylon obliquum (htwd) Umbell. Peucedanum ostruthium (rhiz.) Ptaerochromenol Meli. Ptaeroxylon obliquum (htwd) Ptaerocyclin Meli. Ptaeroxylon obliquum (htwd)

689

690 CHEMOTAXONOMY OF FLOWERING PLANTS

Ptaeroglycol Meli. Ptaeroxylon obliquum (htwd) Ptaeroxylin (Deoxy-karenin; fig. 148) Meli. Cedrelopsis grevei, Ptaeroxylon obliquum (htwd) Ptaeroxylinol Meli. Ptaeroxylon obliquum (htwd) Ptaeroxylone Meli. Ptaeroxylon obliquum Sorbifolin Rut. Spathelia sorbifolia (rt)

II.3 Dibenzo -y-Pyrones (Xanthones) GENERAL These plant constituents are derivatives of dibenzo-y-pyrone (xanthone; fig. 149). Karrer (1958) says that only a few xanthones have been found in plants but I have records of about 70, many of them from a paper by Gottlieb (1968). A useful review is that by Roberts (1961). Mostly they are free, but some at least occur also as glycosides. They are found in fungi, in lichens, and in at least one fern. In the higher plants they may occur in all parts. All are yellow to red-yellow in colour. Xanthone itself may not occur in plants, at least I have no record of it. The naturally occurring xanthones are hydroxy-, methoxy-, and other derivatives of xanthone. We have records of them from the following dicotyledonous families: Anacardiaceae (a few), Flacourtiaceae, Gentianaceae (several), Guttiferae (many: see discussion under that family), Hippocrateaceae, Leguminosae, Moraceae, Polygalaceae and Sapotaceae. From the monocotyledons we have: Liliaceae and Iridaceae. List and Occurrence Alvaxanthone Mor. Madura pomifera Bellidifolin (i,5,8-Trihydroxy-3-methoxy-xanthone; fig. 149) Gentian. Gentiana bellidifolia Celebixanthone (3,4,8-Trihydroxy-z-methoxy-I-(3-methyl-2-butenyl)xanthone) Gutt. Cratoxylon celebicum Corymbiferin (4,5-Di-O-methyl-corymbin) Gentian. Gentiana bellidifolia (it), corymbifera (as glycoside)

DIBENZO-y-PYRONES 691

Decussatin (8-Hydroxy-1,3,7-timethoxy-xanthone) Gentian. Swertia decussata Dehydrocyclo-guanandin Gutt. Calophyllum brasiliense 6-Dehydroxy-jacareubin Gutt. Calophyllum brasiliense, scriblitifolium (htwd); Kielmeyera ferruginea (bk), speciosa Demethyl-bellidifolin (Demethyl-swertianol) Gentian. Gentiana bellidifolia, Swertia tosaensis 6-Deoxy-jacarubin Gutt. Calophyllum inophyllum (htwd), scriblitifolium (htwd); Kielmeyera speciosa Deoxy-morellin Gutt. Garcinia morella Dihydro-isomorellin Gutt. Garcinia morella I, 3 -Dihydroxy-5-methoxy-xanthone Gutt. Calophyllum brasiliense I,7-Dihydroxy-8-methoxy-xanthone Gutt. Kielmeyera excelsa, ferruginea (bk), petiolaris 5,6-D i hydroxy-7-methoxy-xanthone Gutt. Kielmeyera corymbosa 6,7-Dihydroxy-8-methoxy-xanthone Gutt. Kielmeyera speciosa I,5-Dihydroxy-xanthone (fig. 149) Gutt. Mammea americana, Mesua ferrea 4,5-Dimethoxy-bellidin (4,7-Di-O-methyl-bellidin) Gentian. Gentiana bellidifolia (it) 4,7-Dimethoxy-bellidin Gentian. Gentiana bellidifolia (rt) 2-(3, 3 -Dimethylallyl)- I , 3, 5, 6-tetrahydroxy-xanthone Gutt. Calophyllum inophyllum (htwd) 2-(3, 3-Dimethylallyl)-r, 3, 5-trihydroxy-xanthone Gutt. Calophyllum scriblitifolium (htwd) 2-(3,3-Dimethylallyl)-I,3,7-trihydroxy-xanthone Gutt. Calophyllum scriblitifolium (htwd) Euxanthone (Purrenone; I,7-Dihydroxy-xanthone) seems to be more widely spread than most xanthones. Anacardi. Mangifera indica Gutt. Calophyllum sclerophyllum, Kielmeyera excelsa, Mammea americana, Mesua ferrea, Platonia insignis, Symphonia globulifera Gambogic acid Gutt. Garcinia hanburyi, morella

692 CHEMOTAXONOMY OF FLOWERING PLANTS

Gentioside (Gentiin; Isogentisin-3-primeveroside ?) Gentian. Gentiana lutea Gentisin (Gentianin (i); I,7-Dihydroxy-3-methoxy-xanthone; fig. 149) Gutt. Calophyllum brasiliense Gentian. Gentiana lutea, Swertia japonica Globuxanthone Gutt. Symphonia globulifera Guanandin Gutt. Calophyllum brasiliense I -Hydroxy-3,7-dimethoxy-xanthone Gutt. Calophyllum brasiliense I-Hydroxy-7,8-dimethoxy-xanthone Gutt. Kielmeyera petiolaris 5-Hydroxy-I,3-dimethoxy-xanthone Gutt. Kielmeyera coriacea, corymbosa, ferruginea (bk), speciosa 5-Hydroxy-6,7-dimethoxy-xanthone Gutt. Kielmeyera coriacea, corymbosa, ferruginea (bk), rupestris (wd), speciosa 6-Hydroxy-5,7-dimethoxy-xanthone Gutt. Kielmeyera speciosa 6-Hydroxy-7,8-dimethoxy-xanthone Gutt. Kielmeyera rupestris (wd), speciosa I-Hydroxy-7-methoxy-xanthone Gutt. Kielmeyera corymbosa, excelsa; Mesua ferrea 7-Hydroxy-8-methoxy-xanthone Gutt. Kielmeyera excelsa, speciosa 5-Hydroxy-6,7-methylenedioxy-xanthone Gutt. Kielmeyera corymbosa, speciosa 3-Hydroxy-I, 5,6-timethoxy-xanthone Gutt. Kielmeyera rupestris 5-Hydroxy-xanthone (fig. 149) Gutt. Calophyllum brasiliense, Mammea americana 7-Hydroxy-xanthone Gutt. Kielmeyera excelsa, speciosa; Mammea americana Isobellidifolin (I,3,8-Trihydroxy-5-methoxy-xanthone) Gentian. Gentiana bellidifolia Isogentisin (I,3-Dihydroxy-7-methoxy-xanthone) Gentian. Gentiana lutea Isoguanandin Gutt. Calophyllum brasiliense Isomorellic acid Gutt. Garcinia morella

DIBENZO-y-PYRONES 693

Jacareubin (fig. 149) Gutt. Calophyllum brasiliense, inophyllum (htwd), sclerophyllum and 3 other spp.; Kielmeyera ferruginea (bk) Maclura-xanthone (fig. 149) Mor. Maclura pomifera Mangiferin (Aphloiol; Hedysaride; z-C-ß-D-Gluco-pyranosyl-l,3,6,7tetrahydroxy-xanthone; fig. 149) seems to be the most widely spread xanthone. I have records of it from Anacardi. Mangifera indica Hippocrate. Salacia prinoides Flacourti. Aphloia madagascariensis, theaeformis Gutt. Hypericum humifusum (plt) Legumin. Hedysarum obscurum Sapot. Madhuca utilis (wd) Lili. Smilax glycyphylla Trid. Belamcanda chinensis; Crocus (2-3); Iris (all spp. of Pogoniris), dichotoma, pseudacorus Mangostin Gutt. Garcinia mangostana Mbarra-xanthone Gutt. Symphonia globulifera Mesuaxanthone-A (1,5-Dihydroxy-3-methoxy-xanthone) Gutt. Kielmeyera rupestris (wd), Mesua ferrea (htwd) 5-Methoxy-6,7-methylenedioxy-xanthone Gutt. Kielmeyera coriacea, corymbosa, rupestris (wd) 7-Methoxy-xanthone Gutt. Kielmeyera coriacea, corymbosa; Mammea americana Morellic acid Gutt. Garcinia morella Morellin Gutt. Garcinia morella Norathyriol (1,3,6,7-Tetrahydroxy-xanthone) has been found in a fern (Athyrium) and in Mor. Maclura pomifera Gutt. Symphonia globulifera Osaja-xanthone Mor. Maclura pomifera Gutt. Calophyllum scriblitifolium; Kielmeyera corymbosa, ferruginea (bk) Polygala-xanthone-A (fig. 149) Polygal. Polygala paenea (what is this ?) Polygala-xanthone-B Polygal. Polygala paenea

694 CHEMOTAXONOMY OF FLOWERING PLANTS

HO 6

3

7

2

OCH3

Dibenzo-Y-pyrone

Bellidifolin

1,5- Di hydroxy-

(Xant hone)

- xanthone

HO

HO

OCH3 HO 0 OH Gentisin

5-Hydroxy- xanthone.

Jacareubin

rp

OCH3

0

HO

OH

Maclura-xanthone

Mangiferin

Polygala-xanthone-A

Fig. 749. Some xanthones.

Scriblitifolic acid Gutt. Calophyllum scriblitifolium (htwd) Swerchirin (I,8-Dihydroxy-3,5-dimethoxy-xanthone) Gentian. Gentiana corymbifera, Swertia chirata Swertianol (I,3,5-Trihydroxy-8-methoxy-xanthone) is the aglycone of swertianolin. Gentian. Swertia japonica, tosaensis Swertianolin (Swertianol-i-glucoside) Gentian. Swertia japonica Swertinin (7,8-Dihydroxy-I,3-dimethoxy-xanthone) Gentian. Swertia decussata

DIBENZO-y-PYRONES 695

Symphoxanthone Gutt. Symphonia globulifera 1, 3 , 5, 6-Tetrahydroxy-xanthone Mor. Chlorophora tinctoria Gutt. Calophyllum sclerophyllum, Symphonia globulifera i,3,6,7-Tetrahydroxy-xanthone Mor. Chlorophora tinctoria 3 , 5 , 6-Trihydroxy-l-methoxy-xanthone Gutt. Calophyllum sclerophyllum i,5,6-Trihydroxy-xanthone (Mesuaxanthone-B) Gutt. Calophyllum inophyllum, Mesua ferrea (htwd), Symphonia globulifera Ugaxanthone Gutt. Symphonia globulifera (htwd) Xanthone (Dibenzo-y-pyrone; fig. 149): does not occur naturally?

QUINONES GENERAL We are indebted to Thomson (1957) for a general treatment of the naturally occurring quinones. He says: The Quinone pigments are the largest class of natural colouring matters but despite this they make relatively little contribution to natural colouring. About half the total number occur in higher plants distributed among some thirty families; they are found mainly in the bark or underground portions and if present elsewhere are usually masked by other pigments. Moreover quinones sometimes exist in the plant in a reduced form, having little or no colour... Over forty quinones have been isolated from micro-organisms, particularly from the lower fungi...A few quinones have been found also in lichens... derived from the fungal half of the symbiont. In the animal kingdom these colouring matters are confined to certain insects and marine animals, notably sea-urchins.... A more recent treatment of quinones, with much interesting material, is that of Mathis (in Swain, 1966). Another useful source of information is the book edited by Morton (1965). We may divide these substances for convenience of treatment into the following groups:

696 CHEMOTAXONOMY OF FLOWERING PLANTS

I. Benzoquinones: a. I,2-Benzoquinones, which seem not to occur in higher plants; b. i,4-Benzoquinones, of which almost 20 occur in higher plants. II. Naphthaquinones: a. I,2-Naphthaquinones, a small group; b. 1,4-Naphthaquinones, a larger group; c. 1,5-Naphthaquinones, if one can so describe cordeauxia-quinone. III. Anthraquinones, a large group. My list includes more than 70. IV. Dianthraquinones, which seem to be very rare. V. Phenanthraquinones and related substances. VI. Anthrones VII. Dianthrones VIII. Anthranols IX. Naphthacenequinones (2,3-Benzanthracene-quinones; Tetracenequinones), which seem not to occur in higher plants. A few plants seem able to produce an extraordinary number of these substances. Thus Tabebuia avellanedae (Bignoni.) has yielded from its heartwood at least 7 naphthaquinones (mostly 1,4.-, but one, at least, 1,2-) and 9 anthraquinones! The latter are thought to arise from the former by cyclization.

I BENZOQUINONES GENERAL Our knowledge of these compounds has been extended by a recent paper by Ogawa and Natori (1968). We distinguish here (a) 1,2-benzoquinones and (b) 1,4-benzoquinones. It is obvious that the Myrsinaceae are rich in these compounds. I have no record of benzoquinones from the families associated with the Myrsinaceae (Theophrastaceae, Primulaceae).

I.a 1,2-Benzoquinones List and Occurrence r,2-Benzoquinone (Ortho-benzoquinone; fig. 15o) does not occur in plants. Thomson (1957) goes so far as to say that: `No o-benzoquinones have been isolated from natural sources...'

BENZOQUINONES 697

I .b I,4-Benzoquinones List and Occurrence Acetyl-maesaquinone Myrsin. Maesa japonica (frt), tenera (frt) Ardisia-quinone-A (fig. 15o) is a benzoquinone dimer. Myrsin. Ardisia sieboldii (rtbk) Ardisia-quinone-B is a dimer. Myrsin. Ardisia sieboldii (rtbk) Ardisia-quinone-C is a dimer. Myrsin. Ardisia sieboldii (rtbk) 1,4-Benzoquinone (Paraquinone; fig. 15o) has been found in a cockroach and in Streptothrix, but not, I think, in higher plants. 2,5-Dihydroxy-3-methyl-6-n.nonyl-benzoquinone (Bhogatin) Myrsin. Maesa macrophylla 2,5-Dimethoxy-benzoquinone: does this occur in Legum. Dalbergia melanoxylon? 2,6-Dimethoxy-benzoquinone—someone has said (I can't trace the source): 'Ce pigment semble titre un constituant caracteristique de 1'ecorce des Simarubacees et des Meliacees.' Ranuncul. Adonis vernalis (plt) Guttiferae. Kielmeyera rupestris Meli. Khaya senegalensis (bk) Simaroub. Ailanthus altissima (sd); Eurycoma longifolia (bk); Picrasma ailanthoides, crenata (wd); Quassia amara (bk, wd ?) Embelin (Embelic acid?; Embelia-quinone; fig. 15o) Myrsin. Ardisia crenata (rt), japonica (rhiz.), sieboldii (bk, rtbk); Embelia barbeyana (rt), kilimandscharica (frt), ribes (frt), robusta (frt); Myrsine africana (fit), capitellata (frt), semiserrata (fit), sequinii (bk, rtbk, fit), stolonifera (frt); Rapanea neurophylla (fit), pulchra (fit) z-Hydroxy-5-methoxy-3-pentadecenyl-benzoquinone Myrsin. Ardisia crenata (fit), japonica (rhiz., fit), montana (rhiz.), quinquegona (fit) z-Hydroxy-5-methoxy-3-tridecenyl-benzoquinone Myrsin. Ardisia crenata (fit), japonica (rhiz., fit), montana (rhiz.), quinquegona (frt) 2-Hydroxy-5-methoxy-3-tridecyl-benzoquinone Myrsin. Ardisia crenata (frt), japonica (rhiz., fit), montana (rhiz.), quinquegona (fit) Maesaquinone (fig. 15o) Myrsin. Maesa emirnensis (fit ?), japonica (frt), tenera (fit)

698 CHEMOTAXONOMY OF FLOWERING PLANTS

0

0

0

0 H3CO

~OCH3

OH (CH2)10CH3

O 1,4-Benzoquinone

1,2-Benzoquinone

O

0

2,6-Dimethoxy-1,4 -Benzoqu i none

O

O

u

'' OH

HO

C19H37

O

Embelin

H i CH2)7 -C-C-(CH2)7 OH

HO

O

O Ardisia-quinone-A

Rapanone

Maesaquinone

O

0

"

H CO " 3

CH3

XI(CH2.CH=C•C I.12)n-1

OCHS

CH3

H3CO ((CH2.CH=C.CH2)nH 0

'O

Plastaquinones O

Ubiquinones

O OH

HO H23C11 ö

ow-123

Ö

OÖ Vilangin

Fig. iso. Some benzoquinones.

Perezone is also a sesquiterpene and is listed with other sesquiterpenes. Plastoquinones (fig. 15o) have been discussed by Redfearn (in Morton, 1965). The first to be isolated was called Kofler's quinone. It was found in Medicago sativa (Legum.). Several are now known to occur in the chloroplasts of higher plants. Polygonaquinone has a long (-C21H43) side-chain. Lili. Polygonatum falcatum Rapanone (Oxaloxanthin; fig. 15o) Connar. Connarus monocarpus (rt) Oxalid. Oxalis purpurea var. jacquinii (bulb) Myrsin. Aegiceras corniculatum (bk); Ardisia crenata (rt), japonica (rhiz.), macrocarpa (bk, htwd), quinquegona (bk), sieboldii (bk, rtbk); Myrsine sequinii (rtbk, wd), stolonifera (frt); Rapanea maximowiczii (bk, wd), pulchra (rtbk, bk)

BENZOQUINONES 699

Thymoquinone is dealt with as a monoterpene. Ubiquinones (fig. i 50) have been discussed by Crane (in Morton, 1965). They occur in the mitochondria of higher plants. In most animals and in higher plants n = Io (Glover, in Morton, 1965). In yeasts, fungi and bacteria n = 6 to 9. Vilangin (fig. 15o) is a dimer. Myrsin. Embelia ribes (frt), robusta (frt)

II NAPHTHAQUINONES GENERAL As in the case of the benzoquinones (above) we may recognize (a) 1,2- (or ortho-) and (b) 1,4- (or para-)-naphthaquinones. Can one call cordeauxiaquinone a 1,5-naphthaquinone? Thomson (1957) has this to say: `The majority of the naphthalene derivatives found in Nature are quinones and most of these, including the two ß-naphthaquinones [1,2-naphthaquinones], dunnione and diosquinone, are plant products. A group of closely related polyhydroxy derivatives is found in certain species of sea urchin and a few others [such as javanicin, fusarubin] are elaborated by microorganisms.' One of the tests extensively used by me, and called here juglone test A (p. 69), is a colour-reaction for juglone and other naphthaquinones. It seems to be given also by some benzoquinones. The difficulties of classification are again evident here. The mansonones seem to be sesquiterpenes of cadinene type, but they are also 1,4naphthaquinones. Biflorin is similar but is really a diterpene! It seems likely that naphthaquinones arise secondarily from naphthalene glycosides.

II .a 1,z-Napthaquinones List and Occurrence Biflorin (fig. 1511 may also be treated as a diterpene. Scrophulari. Capraria biflora (rt) Celastrol (i) (Tripterine) is said to be a 3,4-substituted derivative of diosquinone. Celastr. Celastrus standens (rt), Tripterygium wilfordii (rt) Celastrol-methyl ether (Pristimerin) Celastr. Celastrus disperma (rt?); Denhamia pittosporoides (rt?); Pristimera grahami (rt), indica (rt)

700 CHEMOTAXONOMY OF FLOWERING PLANTS

Diosquinone (8-Hydroxy-z,2-naphthaquinone; fig. isi) Eben. Diospyros tricolor Dunnione (fig. 151) Gesneri. Streptocarpus dunnii (lvs., fl.) ß-Lapachone Bignoni. Tabebuia avellanedae (htwd) Mansonones are dealt with as sesquiterpenes of cadinene type. I,2-Naphthaquinone (ortho-Naphthaquinone; fig. 151): does not occur as such ?

II . b I,2-Naphthaquinones These are much more common than are the 1,z-naphthaquinones (above), but they are still comparatively rare. List and Occurrence

Acetyl-shikonin Euphorbi. Jatropha glandulifera (bk) Alkannan (fig. iv) Boragin. Alkanna tinctoria (rt) Alkannin (Anchusa acid; Anchusin; Alkanna red; fig. 151) may be esterified with angelica-acid. See Boraginaceae for further discussion. Boragin. many herbaceous members Biramentaceone is a dimer. Droser. Drosera ramentacea Blighinone is said to be a complex 1,4-naphthaquinone. Sapind. Blighia sapida (frt) Chimaphilin (z,7-Dimethyl-I,4-naphthaquinone) seems to be restricted to

Pyrol. Chimaphila (2), Moneses, Pyrola (2) 3-Chloroplumbagin Droser. Drosera anglica, intermedia Dehydro-a-lapachone Bignoni. Tabebuia avellanedae (htwd) Deoxy-lapachol Bignoni. Tabebuia avellanedae (htwd) Dianellinone Lili. Dianella 2,3-Dimethoxy-I,4-naphthaquinone Balsamin. Impatiens balsamina (fl.)

NAPHTHAQUINONES 70I

3,3-Dimethylacrylyl-shikonin

Euphorbi. Jatropha glandulifera (bk) Diomelquinone-A (z(or 3)-Methyl-5-methoxy-6-hydroxy-I,4naphthaquinone) Eben. Diospyros melanoxylon (htwd) Diospyrin (fig. 151) is a dimer of 5-hydroxy-7-methyl-I,4-naphthaquinone. Eben. Diospyros montana Droserone (3, 5-Dihydroxy-z-methyl- I,4-naphthaquinone ; fig. 151) Droser. Drosera peltata (rhiz., rt), whittakerii Eleutherin (fig. 15 I ) Irid. Eleutherine bulbosa (bulb, which also has eleutherinol, a benzopyrone or naphthapyrone; eleutherol, a naphthalide; and iso-eleutherin, below). a-Hydro juglone (I,4,5-Trihydroxy-naphthalene) occurs as the 4-ß-Dglucoside in plants that are usually said to contain juglone? 8-Hydroxy-droserone (3,5,8-Trihydroxy-z-methyl-I,4naphthaquinone)

Droser. Drosera whittakerii 5-Hydroxy-7-methyl-ß-hydro-I,4-naphthaquinone Eben. Diospyros ebenum (frt) Isodiospyrin is a dimer of 7-methyl-juglone (or is it the dimethyl ether of this ?). Eben. Diospyros chloroxylon (st.) Iso-eleutherin differs only spatially from eleutherin. Irid. Eleutherine bulbosa (bulb) Juglone (Nucin; Regianin; 5-Hydroxy-1,4-naphthaquinone; fig. 151) may actually occur as a-hydrojuglone-4-13-D glucoside.

Jugland. Carya, Juglans, Platycarya, Pterocarya Lapachol (Greenhartin; Lapachic acid; Taiguic acid; Tecomin; fig. 151) occurs as a yellowish powder in the woods of some members of the

Bignoniaceae. Legum. Adenanthera?, Andira?, Intsia? (occurrence not confirmed ?)

Sapot. Bassia? (Illipe?) (occurrence not confirmed ?) Verben. Avicennia officinalis (wd), Tectona grandis (Thomson, personal communication, 1964)

Bignoni. Bignonia leucoxylon (wd); Paratecoma peroba (wd); Tabebuia avellanedae (htwd); Tecoma araliacea (wd), obtusata (wd) Lapachol-methyl ether

Bignoni. Tabebuia avellanedae (htwd) a-Lapachone

Bignoni. Tabebuia avellanedae (htwd)

702 CHEMOTAXONOMY OF FLOWERING PLANTS

Lawsone (Henna; Isojuglone; Naphthalenic acid; z-Hydroxy-1,4naphthaquinone ; fig. i51) Balsam. Impatiens balsamina (fl.), and perhaps other species Lythr. Lawsonia inermis (lvs, `henna') Lomatiol (w-Hydroxy-lapachol) Prote. Lomatia spp. (see discussion under family) Menaquinone-I is z-(3,3-dimethyl-allyl)-3-methyl-1,4-naphthaquinone Bignoni. Tabebuia avellanedae (htwd) Mansonones are treated as sesquiterpenes. z-Methoxy-1,4-naphthaquinone (Lawsone-methyl ether) Balsam. Impatiens balsamina, and perhaps other species 7-Methyl-juglone (Ramentaceone) is known both free and as a dimer (isodiospyrin). Droser. Drosera aliciae (lvs), burkeana (lvs), capensis (lvs), cistifolia (lvs), cuneifolia (lvs), hamiltoni (lvs), intermedia?, longifolia?, ramentacea, spathulata (lvs), tracyi (lvs), trinervia (lvs); but absent from Aldrovanda vesciculosa (lvs); Dionaea muscipula (lvs); Drosera auriculata (lvs), binata (lvs), dichotoma (lvs), indica (lvs), lunata (lvs); Drosophyllum lusitanicum (lvs) Eben. Diospyros ebenum (fit), melanoxylon (bk) 2-Methyl-naphthazarin Droser. Drosera anglica, intermedia 1,4-Naphthaquinone (para-Naphthaquinone; fig. 15i): does not occur free in plants ? Plumbagin (2-Methyl-5-hydroxy-1,4-naphthaquinone; 2-Methyl-juglone; Ophioxylin) seems to be rather widely spread. Droser. Aldrovanda vesiculosa (lvs); Dionaea muscipula (lvs); Drosera spp.; Drosophyllum lusitanwum (lvs) Plumbagin. in all (?) members of Plumbagineae (see discussion under family) Eben. Diospyros ebenum, maritima, mespiliformis, xanthochlamys Apocyn. Rauwolfia serpentina (rt., as `ophioxylin', occurrence not confirmed ?) Rubi. Rubia? Shikonin (d-Alkannin) is an optical isomer of alkannin. Boragin. Echium rubrum, Lithospermum erythrorhizon (rt, `shikone' in Japan, as a monoacetyl derivative, `Tokio-violet'), Macrotomia ugamensis, Onosma caucasicum Stypandrone (fig. 151) Lili. Stypandra grandis (rt) Vitamin-K1 (2-Methyl-3-phytyl-1,4-naphthaquinone; Phylloquinone) has been found in higher plants (Medicago, chloroplasts of spinach, etc.).

NAPHTHAQUINONES 703 HO 0

O

7

6 1,2-Naphthaquinone

Diosquinone

Dunnione

Biflorin

O OÖ OH HO Ö 1,4 -Naphthaquinone 0

Jug lone

u 0

HO 0

Lawsone (Iso-juglone)

Droserone

HO

Oil

O OH 0 Stypandrone H3CO 0

Eleutherin

HO

0

0

Alkannan HO 0

Cordeauxia-quinone

Alkannin

Lapachol

HO 0

HO 0

Diospyrin

Fig. i g i. Some naphthaquinones.

II .c I,5-Naphthaquinones? List and Occurrence Cordeauxia-quinone (fig. iv) was described as a i,¢-naphthaquinone, but the latest formula I have has the =0 groups in the 1,5 positions. Legum. Cordeauxia edulis (hairs!)

704 CHEMOTAXONOMY OF FLOWERING PLANTS

III ANTHRAQUINONES GENERAL The parent substance of this group maybe considered to be anthraquinone (fig. 153). Thomson (1957) says of them: `This group of natural quinones is by far the largest. About half the total number occur in higher plants, especially in the Rubiaceae...and most of the remainder are fungal products ...'. Many anthraquinones occur also as glycosides, and these are dealt with here for convenience. List and Occurrence 2-Acetoxymethyl-anthraquinone Bignoni. Tabebuia avellanedae (htwd) Alizarin (1,2-Dihydroxy-anthraquinone; fig. 152) is the aglycone of ruberythric acid. Rubi. Hedyotis auricularia (st., rt), Morinda umbellata (st., rt), Oldenlandia umbellata (rt), Rubia tinctorum (it) Alizarin- -methyl ether (1-Methoxy-z-hydroxy-anthraquinone) Rubi. Morinda citrifolia (rt), longiflora (it), umbellata (st., rt); Oldenlandia umbellata (rtbk); Rubia tetragona Alizarin-2-methyl ether Rubi. Morinda umbellata (it) Aloe-emodin (I,8-Dihydroxy-3-hydroxymethyl-anthraquinone; Rottlerin; fig. 152) seems to be rather widely distributed. Polygon. Rheum? Legum. Cassia (as glycoside ?) Rhamn. Rhamnus purshiana (bk) Lili. Aloe ferox, perryi, vera Anthragallol (i,2,3-Trihydroxy-anthraquinone) Rubi. Coprosma lucida (bk) Anthragallol-I,2-dimethyl ether Rubi. Coprosma (3, sometimes as glycoside), Oldenlandia umbellata Anthragallol-1,2-dimethyl ether-glycoside Rubi. Coprosma Anthragallol-I,3-dimethyl ether Rubi. Oldenlandia umbellata Anthragallol-z-methyl ether Rubi. Coprosma acerosa (bk, free and as glycoside), lucida (free ?)

ANTHRAQUINONES 705

Anthragallol-z-methyl ether-glycoside Rubi. Coprosma Anthraquinone (fig. 15z) is not listed by Karrer (1958) as occurring free in plants. I have records of it, but without authorities, in Legum. Acacia Anacardi. Quebrachia lorentzii (htwd) Anthraquinone-2-aldehyde Bignoni. Tabebuia avellanedae (htwd) Anthraquinone-z-carboxylic acid Bignoni. Tabebuia avellanedae (htwd) Aurantio-obtusin Legum. Cassia Chrysarone (3,5,6-Trihydroxy-z-methyl-anthraquinone ?) Polygon. Rheum rhaponticum (rt) ? Chryso-obtusin Legum. Cassia Chrysophanein is a ß-D-glucoside of chrysophanic acid. It is said to occur in lichens and in Polygon. Rheum rhaponticum (rt) ?, Rumex alpinus Legum. Cassia marilandica? Rhamn. Rhamnus spp. Chrysophanic acid (1,8-Dihydroxy-3-methyl-anthraquinone; Archinin; Chrysophanol; Rumicin; fig. 152) is the aglycone of chrysophanein. It is said to be very widely distributed. Polygon. Polygonum (z), Rheum (5), Rumex (about a dozen spp.) Saxifrag. Saxifraga delavayi Legum. Cassia (4 or more spp.) Euphorbi. Cluytia similis Rhamn. Rhamnus (4) ? Sonnerati. Sonneratia acida (caseolaris) Eric. Arbutus unedo (lvs, st.) Lili. Aloe vera (lvs) Coelulatin Rubi. Coelospermum Copareolatin (Areolatin; 1,5,6,7-Tetrahydroxy-z-methylanthraquinone; fig. 552) Rubi. Coprosma areolata Copareolatin-1 (or 5),6-dimethyl ether Rubi. Coprosma australis (bk) Damnacanthal Rubi. Damnacanthus indicus var. microphyllus (rt), major (rt); Morinda umbellata (rtbk) 2

GCO II

706 CHEMOTAXONOMY OF FLOWERING PLANTS

Damnacanthol (Lucidin-i-methyl ether) Rubi. Damnacanthus major (rt) Digitoluteine (I-Methoxy-z-hydroxy-3-methyl-anthraquinone) Scrophulari. Digitalis lutea (lys), purpurea (lys) Emodin (Archin; Frangula-emodin; Rheum-emodin; Senna-emodin?; fig. 152) is the aglycone of barbaloin, frangulin, gluco frangulin, jesterin, polygonin and rhamnocathartin. It seems to be widely distributed. Polygon. Rheum (3), Rumex Legum. Cassia (3, or more) Rhamn. Rhamnus (6, or more) Sonnerati. Sonneratia acida (caseolaris) Lili. Ala?, Simethis bicolor Frangulin (Cascarin; Franguloside; Rhamnoxanthin) is an artefact arising from gluco-frangulin (Thomson, 1957). Galiosin (Galicide; Pseudopurpurin-l-ß-primveroside; fig. 152) has been found by Hill and Richter (1937) in many members of the Galieae (Stellateae). Rubi. Asperula, Crucianella, Galium (many), Relbunium, Rubia Glucochrysarone is a glucoside of chrysarone. Polygon. Rheum rhaponticum Gluco-frangulin (Rhamnocathartin?; Emodin-7-rhamnoglucoside) Rhamn. Rhamnus cathartica ?, frangula (bk, rt, sd, frt) I-Hydroxy-anthraquinone Bignoni. Tabebuia avellanedae (htwd) z-Hydroxy-anthraquinone Rubi. Morinda umbellata (st., rt), Oldenlandia umbellata (rt) z-Hydroxymethyl-anthraquinone Bignoni. Tabebuia avellanedae (htwd) 1-Hydroxy-2-methyl-anthraquinone Rubi. Morinda umbellata (st., rt) z-Hydroxy-3-methyl-anthraquinone Rubi. Coprosma (2?) Bignom. Tabebuia avellanedae (htwd) Hystazarin-methyl ether (2-Hydroxy-3-methoxy-anthraquinone) Occurrence ? Iso-emodin (Rhabarberone; 3,5,8-Trihydroxy-2-methyl-anthraquinone) is said to occur both free and as glycoside. Polygon. Rheum officinale?, palmatum? Rhamn. Rhamnus (as glycoside) Jesterin: belongs here ? See Shesterin (an anthranol ?). Rhamn. Rhamnus Juzunal is probably 5-hydroxy-damnacanthal. Rubi. Damnacanthus indicus (rt), major (rt)

ANTHRAQUINONES 707

Lucidin (i,3-Dihydroxy-z-hydroxymethyl-anthraquinone) Rubi. Coprosma lucida (and others ?), Morinda umbellata (rt) Methoxy-alizarin Rubi. Relbunium (Galium?) atherodes (rt) 1-Methoxy-anth ra qu inone Bignoni. Tabebuia avellanedae (htwd) 2-Methoxy-anthraquinone Rubi. Morinda umbellata (st., rt) i -Methoxy-z-methyl-anthraquinone Rubi. Morinda umbellata (st., rt) 3-Methoxy-xanthopurpurine Rubi. Relbunium (Galium?) atherodes (rt), hypocarpium 6-Methyl-xanthopurpurin Rubi. Morinda umbellata (rtbk) Morindin is not, says Thomson (1957), a single glycoside. Morindone (1,5,6-Trihydroxy-z-methyl-anthraquinone) Rubi. Coprosma australis (bk); Morinda citrifolia (rt), persicaefolia (rt), tinctoria (it), umbellata? Munjistin (Xanthopurpurin-z-carboxylic acid; fig. 152) Rubi. Morinda umbellata (it); Rubia munjista (cordifolia) (rt), and z other species Munjistin-glycoside Rubi. Rubia (3) Nataloin: belongs here ? Lili. Aloe candelabrum Nor-damnacanthal Rubi. Damnacanthus, Morinda Obtusifolin Legum. Cassia Obtusin Legum. Cassia Oxymethyl-anthraquinone: what is this ? Legum. Cassia obovata (lys, pods), occidentalis (rt, lys, pods) Physcion (Emodin-methyl ether; Rheochrysidin; 3-Methyl-6-methoxyi,8-dihydroxy-anthraquinone) occurs in lichens, fungi, and Polygon. Polygonum, Rheum, Rumex Legum. Cassia marilandica (lys, also as glucoside), occidentalis (sd) Rhamn. Ventilago maderaspatana (rt, bk) Polygonin (Cuspidatin ?): a glycoside of emodin ? Polygon. Polygonum cuspidatum Pseudo-purpurin (Purpurin-3-carboxylic acid) is the aglycone of galiosin. Rubi. Galium (only as glycoside ?), Relbunium (free in 2 spp. ?), Rubia (only as glycoside) 2-2

708 CHEMOTAXONOMY OF FLOWERING PLANTS

9 7

1(a)

6

2(ß) 3(0 )

CH2OH

4(å)

O

O

Aloe-emodin

Alizarin

Anthraquinone

0 OH

HO O OH

HO 0 OH

HO 01110

HO

O

01110

HO

HO 0

Chrysophanic acid

Emodin

Copareotatin (Areolatin )

O

O.GLUC. XYL.

OH COOH n O OH

R HO 0

OH

(R=H or OH)

Gal lost n

Munjistin

Isorhodomycinones

Fig. i5z. Some anthraquinones.

Purpurin (Verantin; i,z,4-Trihydroxy-anthraquinone): occurs chiefly as glycoside ? Rubi. Relbunium (3), Rubia (3) Purpurin-glucoside: what is this?

Rubi. Rubia Rhein (Cassic acid; x,8-Dihydroxy-anthraquinone-3-carboxylic acid): occurs also as a glycoside ?

Polygon. Rheum (a), Rumex Legum. Cassia (several spp., free and as glycoside) Lili. Polygonatum multijlorum (rhiz., rt) Rheochrysin is a glucoside of physcion. Polygon. Rheum?, Rumex Ruberythric acid (Alizarin-z-ß-primveroside)

Polygon. Rheum? Rubi. Asperula, Crucianella, Galium, Oldenlandia, Rubia Rubiadin (i,3-Dihydroxy-z-methyl-anthraquinone) occurs also as glycosides. Rubi. Coprosma (3), Morinda umbellata (st., rt), Prismatomeris

malayana (rt), Rubia?

ANTHRAQUINONES 709

Rubiadin-3-ß-n-glucoside Rubi. Rubia tinctorum ? Rubiadin-l-methyl ether Rubi. Coprosma (4); Morinda longiflora (rt, lys), umbellata (st., rt, also as glycosides); Prismatomeris malayana (rt) Rubiadin-3-primveroside Rubi. Galium (2) Soranjidiol (i,6-Dihydroxy-2-methyl-anthraquinone) Rubi. Coprosma acerosa (bk), lucida (bk ?) ; Morinda citrifolia (rtbk `suranji') Tabebuin Bignoni. Tabebuia avellanedae (htwd) Tectoleafquinone Verben. Tectona grandis (lvs) Tectoquinone (2-Methyl-anthraquinone) Rubi. Morinda umbellata (st., rt) Verben. Tectona grandis (wd) Bignoni. Tabebuia avellanedae (htwd) I,2,6,8-Tetrahydroxy-3-methyl-anthraquinone (Alaternin) Rhamn. Rhamnus (probably as a glycoside) Xanthopurpurin (Purpuroxanthin; I,3-Dihydroxy-anthraquinone) Rubi. Morinda umbellata (st., rt), Rubia (3) Xanthopurpurin-l-methyl ether Rubi. Rubia (3) Xanthopurpurin-3-methyl ether Rubi. Rubia (3)

IV DIANTHRAQUINONES GENERAL Very few of these substances are known. Mathis (in Swain, 1966) lists only three, all in Cassia, of the Leguminosae. No doubt others will be found. List and Occurrence Cassiamin (fig. 153) Legum. Cassia Cassianin (fig. 153) Legum. Cassia Siameanin (fig. 1 53) Legum. Cassia

710 CHEMOTAXONOMY OF FLOWERING PLANTS

HO 0 OH

O

HO

0 OH Cassiamin

Hn 0

OH

Cassianin

H SO O 0

01010 it

HO 0 OH Siameanin

Fig. 153. Dianthraquinones.

V PHENANTHRAQUINONES AND RELATED SUBSTANCES GENERAL These are few in number. At least one (thelephoric acid) occurs in fungi. From higher plants I have records of but four. Doubtless others will be found. Phenanthraquinone itself (fig. 154) does not occur naturally ? List and Occurrence Cryptotanshinone (fig. 154) Lab. Salvia miltiorhiza (rt) Denticulatol (fig. 1 54) Polygon. Rumex chinensis (maritima) (rt) Tanshinone-I (fig. 154) Lab. Salvia miltiorhiza (rt) Tanshinone-II Lab. Salvia miltiorhiza (rt)

ANTHRONES 7II O

OH

OH Phenanthrene Phenanthraquinone Denticulatol

or

O Cryptotanshinone ?

O Tanshinone- I

Fig. 154. Phenanthrene, phenanthraquinone, and some related substances.

VI ANTHRONES GENERAL The anthrones are ketones obviously related to the anthraquinones and included with them by Karrer (1958). Few of them are known from higher plants, but those that have been found come largely from the same plants that yield anthraquinones. Anthrone itself (fig. 155) does not occur free ? List and Occurrence Aloe-emodin-9-anthrone (fig. 155) is the aglycone of barbaloin and isobarbaloin. Rhamn. Rhamnus (free ?) Barbaloin (fig. 155) is, says Karrer (1958), a C-glucosyl derivative of aloe-emodin-9-anthrone. Lili. Aloe (3) Chrysarobin (I,8-Dihydroxy-3-methyl-9-anthrone ?) is the 9-anthrone of chrysophanic acid? It occurs in fungi and Polygon. Rumex crispus (rt)

712 CHEMOTAXONOMY OF FLOWERING PLANTS HO O OH

CH2OH

CH2OH 6 H1105

Ant hror.e

Aloe-emodin-9-anthrone

Barbaloin

HO D ARAB .

Emodin-anthrone Homonataloin? Fig. 155. Some anthrones.

Legum. Andira araroba (bk), Cassia siamea (wd) ?, Ferreirea (Andira) spectabilis (htwd) Rhamn. Rhamnus crenata (bk), dahurica (frt), purshiana (bk) ? Lili. Polygonatum multiflorum (rhiz., rt) Emodin-anthrone (Frangula-emodin-anthrone; Protophyscihydron); (fig. 155) Rhamn. Rhamnus crenata (bk), dahurica (fit), frangula (bk) Frangularoside, says Thomson (1957), may be an anthrone or anthranolglycoside related to jesterin (which he equates with shesterin). Occurrence ? Homonataloin (fig. 155): a C-glycosyl compound with D-arabinose as the sugar ? Lili. Aloe candelabrum, distans (lvs) ?, macracantha (lvs) ? Iso-barbaloin: has the same structural formula as barbaloin? Lili. Aloe 1,6,8-Trihydroxy-3-methyl-Io-glucosido-oxyanthrone is perhaps the anthrone-glycoside of Rhamn. Rhamnus purshiana (bk) ?

VII DIANTHRONES GENERAL These complex substances may be regarded as derivatives of dianthrone (fig. 156), which does not, I think, occur naturally.

DIANTHRONES 713

HO 0 OH

H•

O

OH

HO 0

OH

HO HO

O

HO

OH

Dianthrone

(R1+ R2- C12 H3204 N2 Fagopyrin

HO 0 OH

HO 0

HO

OH

Hypericin ?

C6H12050 0 OH

HO HO

HO

HO 0 OH Hyperico-dehydro-dianthrone ?

COOH OOH

HO 0 OH C6H1205.O 0 OH Proto-hypericin

Senn oside-A

Fig. 156. Dianthrone and some derivatives. The forms in which they are present is by no means clear. Thomson (1957) thinks that some of the anthraquinones which have been isolated were originally present in the plants as dianthrones. Some, at least, of the dianthrones are photosensitizers. List and Occurrence Fagopyrin (fig. 156) is a photosensitizer and the cause of `fagopyrism'. Polygon. Fagopyrum esculentum Hypericin (Hypericumrot; Mycoporphyrin; fig. 156) occurs in fungi (?) and in Guttif. Hypericum Hyperico-dehydro-dianthrone (fig. 156) is the supposed precursor of proto-hypericin. Guttif. Hypericum Proto-hypericin (fig. 156) has been described as intermediate between emodin-anthranol and hypericin. Guttif. Hypericum

714

CHEMOTAXONOMY OF FLOWERING PLANTS

Anthranol

Emodin-anthranol

Fig. 157. Anthranols.

Pseudo-hypericin Guttif. Hypericum Sennidines-A and -B are optical isomers. They are the aglycones of sennosides-A and -B. Do they occur free ? Sennoside-A (fig. 156) Legum. Cassia angustifolia (lys) Sennoside-B Legum. Cassia angustifolia (lys ?)

VIII ANTHRANOLS GENERAL The small group of substances listed here may be considered to be derivatives of anthranol (fig. 157), which does not, I think, occur free. They seem to occur only in the Guttiferae and Rhamnaceae. List and Occurrence Emodin-anthranol (Emodinol; Frangula-emodin-anthranol; fig. 157) Guttif. Hypericum perforatum Rhamn. Rhamnus cathartica (frt) Physcion-anthranol-A Rhamn. Ventilago maderaspatana (rtbk) Physcion-anthranol-B Rhamn. Ventilago maderaspatana (rtbk) Rhamnicogenol is a pentahydroxy-z-methyl-anthranol, and is the aglycone of rhamnicoside. Does it occur free ? Rhamnicoside is a primveroside of rhamnicogenol. Rhamn. Rhamnus (in 6 spp.; but absent from 6 other spp.) Shesterin is said by some to be an anthranol, but others equate it with jesterin (an anthraquinone). Rhamn. Rhamnus cathartica (frt)

NAPHTHACENE-QUINONES 715

IX NAPHTHACENE-QUINONES GENERAL These substances seem to be restricted to soil streptomycetes and `may be a taxonomically very important criterion for this group', says Mathis (in Swain, 1966). The isorhodomycinones (fig. 152), which belong here, are not really very far removed from some of the anthraquinones found in higher plants. It would not be surprising if naphthacene-quinones are found to occur in higher plants, too.

STEROIDS GENERAL Steroids have a tetracyclic ring structure (fig. 158) in which R1 and R2 are usually methyl groups. R3 may be absent or have from 2 to Io C atoms. In some cases R3 contains nitrogen and so-called azasteroids result. We have dealt with these as steroidal alkaloids. The 4,4,14etrimethyl-steroids (fig. 158) are triterpenoid. Shoppee (1964) has an excellent book on the chemistry of the steroids and we have followed him where possible. I. Sterols and related compoundsare `steroid alcohols containing an aliphatic side-chain...occurring both free and as esters of higher aliphatic acids...All possess i 5-unsaturation and are often referred to as stenols whilst their saturated derivatives are called stanols' (Shoppee, 1964). I have also used Stoll and Jucker (in Paech and Tracey, 1955) as a source in compiling my list. II. Sex hormones III. Cardiotonic glycosides and aglycones Toads, and many higher plants, produce substances with remarkable cardiotonic activity. The compounds produced by plants are steroid glycosides. Shoppee (1964) deals with these substances as (1) cardenolides, (z) digitenolides, and (3) scilladienolides (bufadienolides). IV. Steroidal saponins and sapogenins Steroidal saponins are physiologically of great interest. They lower surface tension greatly, are haemolytic, and form stable foams when shaken in aqueous solutions (Saponin Test A, p. 78).

716 CHEMOTAXONOMY OF FLOWERING PLANTS

4

Basic ring structure

4,4,14 —Trimethyl

Sterol skeleton

steroids (Triterpenoid )

Fig. 158. Structures found in steroids.

When hydrolysed, they give sugars and C27-sapogenins. The triterpenoid saponins and sapogenins are dealt with elsewhere (p. 822). V. Azasteroids: here belong the steroid alkaloids which we have dealt with elsewhere (p. 337). The sterol-mixtures of plants may be quite complex. Knights (1965), for example, has found that the grains of oats (Avena sativa, Gramineae) have as the chief sterols ß-sitosterol, 05.24(28) - and 07.24(28) stigmastadienols. No less than 5 minor sterols are also present: cholesterol, brassicasterol, campesterol, stigmasterol, and A7-stigmastenol. Pollen Sterols Standifer, Devys and Barbier (1968) say: `Although the results of previous studies... indicated that no taxonomic relationships existed between the sterols in the pollen and the plant families, the number of analyses was enlarged to confirm this conclusion.' We should say that the number of analyses made is still far too few for any such conclusion.

I STEROLS AND RELATED COMPOUNDS GENERAL Many of the `sterols' listed here have been recorded only from single genera and have been named accordingly. Some, at least, of them will be found to be identical with sterols already known. Until they are better known, however, it seems wise to list them as I have found them in the literature.

STEROLS AND RELATED COMPOUNDS 717

An interesting feature is the occurrence of 24-methylene-cholesterol as the chief sterol in many pollen-grains. It seems to have no chemotaxonomic significance, but there may be some groups that are characterized by other pollen-sterols. Djerassi et al. (1963) say that the biosynthetic sequence mevalonate --> farnesol -~ squalene --> lanosterol -> cholesterol is, in general, well documented. List and Occurrence Adlumia-sterol Papaver. Adlumia fungosa (lvs, rt) Aegelin Rut. Aegle marmelos Anthesterol Comp. Anthemis Arbusterol: see also unedosterol. Eric. Arbutus unedo Arnisterine Comp. Arnica Bassisterol Sapot. Bassia (Madhuca?) Brassicasterol (24ß-Methylcholesta-5,22-dien-3ß-ol) Caryophyll. Cerastium? Crucif. Brassica rapa (sd) Gram. Saccharum officinarum Bryonol Cucurbit. Bryonia dioica Butyrospermol (Basseol; fig. 159) Mor. Artocarpus Euphorbi. Hura Hippocastan. Aesculus Sapot. Butyrospermum parkii (sd) Caf( f )esterol Rubi. Coffea sp. (oil) Calosterol Asclepiad. Calotropis gigantea Campesterol Crucif. Brassica campestris, Sinapis arvensis (sd) Legum. Glycine max (oil) Rut. Phellodendron amurense Simaroub. Eurycoma longifolia (bk) Gram. Triticum sativum (sd)

718 CHEMOTAXONOMY OF FLOWERING PLANTS

Carpesterol Solan. Solanum xanthocarpum Celastrol (2) Celastr. Celastrus Cholest-5-ene Euphorbi. Euphorbia laterifiora (lys, st.) Cholesterol (Cholest-5-en-3ß-o]) is more common in animals than in plants, but it does occur in some higher plants, both dicotyledons and monocotyledons. Sallc. Populus fremontii (chief sterol of pollen) Solan. Solanum tuberosum Comp. Haplopappus, Hypochaeris radicata (pollen); but absent? from Xanthium Dioscore. Dioscorea, Tamus Palmae. Phoenix Chondrilla-sterol is the 24ß-epimer of a-spinasterol. Comp. Chondrilla Citrostadienol (4a-Methyl-5a-stigmasta-7,24(28)-dien-3ß-ol) Rut. Citrus paradisi (peel) Citrullol Berberid. Caulophyllum thalictroides Cucurbit. Citrullus colocynthis Cluytianol Comp. Taraxacum officinale Coronasterol Apocyn. Tabernaemontana coronaria Cucurbita-sterol Cucurbit. Cucurbita pepo Cucurbitol Cucurbit. Cucurbita citrullus (Citrullus vulgaris?) Cycloart-23-en-3ß,25-diol Euphorbi. Euphorbia cyparissias Cyclo-artenol (,i 9-Cyclolanost-24-en-3ß-ol ; fig. 1 59) Ulm. Ulmus glabra (wd) Mor. Artocarpus integrifolia Euphorbi. Euphorbia (8), Hura Logani. Strychnos nux-vomica (sd) Cycloartenone: belongs here ? Mor. Artocarpus integrifolia Cycloeucalenol (4ß-Demethyl-24-methylen-cyclo-artenol) Legum. Erythrophleum guineense Myrt. Eucalyptus microcorys

STEROLS AND RELATED COMPOUNDS 719

Cyclolaudenol Papaver. Papaver somniferum (opium) Elemadienolic acid Burser. Canarium commune (resin) Elemolic acid (fig. 159) Burser. Canarium commune (resin) Elemonic acid Burser. Canarium commune (resin) Ergostanol (2413-Methy1-5a-cholestan-313-ol) Caryophyll. Cerastium alpinum (plt, y-) Ergosterol (24.ß-Methylcholesta-5,7,z2-trien-3ß-ol) Euphorbi. Hevea brasiliensis Rut. Citrus (peel of Rangpur lime) Gram. Triticum sativum 24-Ethylidine-cholesterol (15-Avenasterol) Crucif. Brassica napus f. annua (pollen) Euphol (4,4, I4ß-Trimethyl-5 x, i 3a., I4ß-cholesta-8,24-dien-3ß-oll Euphorbi. Euphorbia (1 o) Euphorbia-sterol Euphorbi. Euphorbia lathyris Euphorbol Euphorbi. Euphorbia (4) Ficosterol Mor. Ficus bengalensis Gloriosol Lili. Gloriosa superba Gobosterol Comp. Arctium minus Grindelol: identical with anonol? Annon. Annona muricata (anonol) Comp. Grindelia camporum Helisterol Comp. Helianthus annuus Hemidesmol Asclepiad. Hemidesmus indicus Hemidosterol Asclepiad. Hemidesmus indicus Homo-taraxasterol Comp. Taraxacum z z-Hydroxy-cholesterol Lili. Narthecium ossifragum a-3-Hydroxy-masticadienoic acid Anacardi. Schinus

720 CHEMOTAXONOMY OF FLOWERING PLANTS

Hygrosterol Acanth. Hygrophila spinosa Ipurganol Convolvul. Ipomoea purga Isotrifolin Legum. Trifolium pratense Lanosterol Euphorbi. Euphorbia (7, latex) Lippianol Verben. Lippia scaberrima Lophenol (4a-Methyl-5-oc-cholest-7-en-3ß-ol; fig. 159) Cast. Lophocereus schottii Macdougallin (14a-Methyl-A8-cholestene-3ß,6a-diol) Cact. Peniocereus fosterianus (plt), macdougalli; but not in P. greggii Masticadienoic acid Anacardi. Schinus 24(28)-Methylene-cholesterol (fig. 159) `...is often but not always the principal sterol in pollens from some species of plants'. Saliv. Salix sp. (pollen, chief sterol) Cact. Carnegiea gigantea (pollen, chief sterol) Crucif. Brassica napus f. annua, nigra; Sisymbrium irio (pollen; chief sterol in all ?) Ros. Malus sylvestris (pollen, chief sterol) Legum. Trifolium pratense (pollen, chief sterol) Cist. Cistus ladanifera (pollen) Gram. Phleum pratense, Secale cereale, Zea mays var. saccharata (pollen, chief sterol in all) 24-Methylene-cycloartanol Euphorbi. Euphorbia (2), Hura Moretenol (2IaH-Hop-22,29-en-3ß-o1): belongs here ? Euphorbi. Euphorbia lateriflora (lvs, st.), Sapium sebiferum (bk) Moretenone (2IaH-hop-28,29-en-3-one) Euphorbi. Euphorbia lateriflora (lvs, st.), Sapium sebiferum (bk) 31-Norcyclo-artanol (24-Demethyl-cyclo-eucalanol) occurs in a fern and in Lili. Smilax aspera (rt) Oleasterol Ole. Olea europaea Papaveristerol Papaver. Papaver somniferum Parkeol (Lanosta-9(II),24-dien-3ß-ol) Sapot. Butyrospermum parkii (sd)

STEROLS AND RELATED COMPOUNDS 72I

Peniocerol (6,8-Cholestene-3ß,6a-diol) Cact. Peniocereus fosterianus, greggii (rt), macdougalli (plt) Pollinastanol Fag. Castanea vulgaris (pollen) Betul. Corylus avellana (pollen) Raphanisterol Crucif. Raphanus raphinastrum Satisterol Gram. Oryza sativa Serposterol Apocyn. Rauwo fia serpentina Sitosterols: `the five sitosterols (Gr. sito, grain) are the most widely distributed plant sterols' (Shoppee, 1964). They take the place in plants that cholesterol does in animals. a-Sitosterol: there are actually 3 a-sitosterols (ai-, a2-, and a3-). Caryophyll. Cerastium a-Sitosterol esters Gram. Zea ß-Sitosterol (Cinchol; 22,23-Dihydro-stigmasterol; 24a-Ethylcholest-5en-3ß-ol; fig. 159) is very widely distributed indeed. My own list, which is very far from complete, has no less than 28 families of dicotyledons. Is there any significance in the fact that only one family of monocotyledons (Araceae) is included ? I suspect not! ß-Sitosterol esters Ulm. Ulmus glabra (wd) Ros. Sorbus Gram. Zea ß-Sitosterol-ß-D-glucoside (Ipuranol ?) seems to be widely distributed, but is there more than one form ? Legum. Caesalpinia bonducella? Elaeocarp. Aristotelia Rut. Casimiroa edulis?, Citrus sinensis Umbell. Daucus carota? Sapot. Madhuca butyracea (bk, frt), Mimusops elengi (htwd, rt) Convolvul. Convolvulus scammonica, Ipomoea orizabensis (as ipuranol) Solan. Solanum torvum y-Sitosterol (Clionasterol; 24ß-Ethyl-cholest-5-en-3ß-0l) Ros. Potentilla Legum. Clitoria ternatea (sd), Glycine max (sd) Rut. Aegle Verben. Clerodendron serratum (rtbk)

722 CHEMOTAXONOMY OF FLOWERING PLANTS

y-Sitosterol esters Gram. Zea Spinasterols—Shoppee (1964) says: `Four isomeric spinasterols, C29H280, have been isolated from spinach or alfalfa... [ß-, y-, and 6spinasterols] ... are probably 07-compounds differing in the position of the side-chain double bond.' a-Spinasterol (Bessisterol ? ; fig. 159) seems to be widely distributed. Chenopodi. Spinacia oleracea Legum. Medicago sativa (sd) Balsamin. Impatiens Cucurbit. Citrullus colocynthus, Luffa cylindrica (sd), Momordica cochinchinensis (bessisterol) Hippocastan. Aesculus Umbell. Bupleurum falcatum Myrsin. Aegiceras Sapot. Madhuca butyracea (bk, frt), Mimusops elengi ß-Spinasterol Chenopodi. Spinacia oleracea Legum. Medicago sativa (sd) y-Spinasterol Chenopodi. Spinacia oleracea (as glycoside) 8-Spinasterol Legum. Medicago sativa (sd) Stigmastanol (24a-Ethyl-5a-cholestan-3ß-ol) Tili. Tilia vulgaris (wd) Stigmastanone Simaroub. Samadera Stigmasterol (24a-Ethyl-cholesta-5,22-dien-3ß-ol) is widely distributed. Legum. Gleditsia, Glycine, Phaseolus, Physostigma Euphorbi. Mallotus paniculatus (st.) Tili. Tilia vulgaris (wd) Simaroub. Samadera Alangi. Alangium Myrsin. Aegiceras Asclepiad. Calotropis, Gymnema Rubi. Lasianthus, Morinda, Mussaenda, Psychotria Solan. Lycopersicum Comp. Echinacea, Enhydra, Inula, Mikania, Xanthium Dioscore. Dioscorea, Tamus 6:7-Stigmasterol Gram. Secale cereale (rye-germ oil) a-Theosterol Sterculi. Theobroma cacao

STEROLS AND RELATED COMPOUNDS 723

HO

Butyrospermol

Cycloartenol

Elemotic acid

Lophenol

24(28)-Methylene-cholesterol

A -Sitosterol

HO

HO

oC-Spinasterol

Fig. 159. Some sterols and related compounds.

Tirucallol is the zocc-methyl epimer of euphol. Euphorbi. Euphorbia tirucalli (latex), and z other spp. Trifolianol Legum. Trifolium incarnatum, pratense Trifolin Legum. Trifolium pratense Trifolitin Legum. Trifolium pratense oc-Tritisterol Gram. Triticum sativum ß-Tritisterol Gram. Triticum sativum oc-Typhasterol: a sitosterol? Typh. Typha angustata

724 CHEMOTAXONOMY OF FLOWERING PLANTS OH

OH

HO

O OH

OH

HO

Androstane-3ß.16 a,17a-triol

HO

Estriol (Oestriol)

Estrone (Oestrone)

Fig. z6o. Sex hormones which are said to occur in plants.

Unedosterol Eric. Arbutus unedo Vincetoxin: belongs here ? Asclepiad. Vincetoxicum officinale?

II SEX HORMONES GENERAL The production of sex hormones is usually considered to be a prerogative of the animal kingdom. Three types are formed by animals—estrogens (oestrogens), gestogens, and androgens. Little seems to be known about the occurrence of these substances in plants. The authors of a recent paper, in fact, have even concluded that their presence is doubtful. It is therefore of interest that Heftman, Ko and Bennett (1966) have confirmed that estrone (oestrone) does occur in the date palm, and that the seeds of pomegranate are an even richer source. It is evident from the few records available that no chemotaxonomic pattern emerges. List and Occurrence 5a-Androstane-3ß,i 6a, i 7a-triol (fig. 16o) Comp. Haplopappus heterophyllus Estriol (Oestriol; fig. 16o) Salle. Salix (catkins) Estrone (Oestrone; fig. 16o) Ros. Malus silvestris (sd) Punic. Punica granatum var. nana (sd) Palmae Phoenix dactylifera (pollen, sd)

SEX HORMONES 725

zoß-Acetoxy-3-oxopregn-4-ene(zoß-Dihydro-progesterone-acetate): belongs here ? Meli. Khaya grandifoliola

III CARDIOTONIC GLYCOSIDES AND AGLYCONES III .i Cardenolides GENERAL The cardenolides are cardiotonic glycosides which occur in a dozen or so families of flowering plants: Apocynaceae and Asclepiadaceae—many, reflecting the closeness of relationship of these two large families; Celastraceae—in Euonymus only?; Cruciferae—in a few species; Euphorbiaceae—in Mallotus only ? ; Leguminosae—in but z genera ?; Moraceae—in several genera; Ranunculaceae—only in Adonis spp. ?; Scrophulariaceae—many, in Digitalis and Isoplexis; Tiliaceae and Sterculiaceae of the Malvales—in one genus of each ( ?), with a common genin; and in Liliaceae—in at least 3 genera. It seems certain, from this distribution, that cardenolides have arisen independently several times. A remarkable feature of the cardenolides is that many of the sugars involved are known only in them: they seem not to occur free or in combination with other aglycans. It is difficult to compile an accurate list; synonymy is complicated and information scattered. A recent review by Singh and Rastogi (197o) has reached me too late for detailed consideration here, but I have been able to include some information from it. List and Occurrence Abobioside yields abomonoside and a sugar. Apocyn. Adenium boehmianum (plt) Abogenin (Acetyl-digitoxigenin ?) is the aglycone of abobioside and abomonoside. Apocyn. Adenium boehmianum (plt)—free ? Abomonoside yields acetyl-digitoxigen in and D-cymarose. Apocyn. Adenium boehmianum (plt) Acetyl-diginatin yields acetyl-diginatigenin and 3 x D-digitoxose ? Scrophulari. Digitalis Acetyl-digitoxin-a yields acetic acid, digitoxigenin, and 3 x D-digitoxose. Scrophulari. Digitalis spp.

726 CHEMOTAXONOMY OF FLOWERING PLANTS

Acetyl-digitoxin-ß : from Digilanid-A ? Scrophulari. Digitalis spp. Acetyl-digoxin-oc (Digorid-B) Scrophulari. Digitalis spp. Acetyl-digoxin-ß (Digorid-A) Scrophulari. Digitalis spp. Acetyl-gitaloxin (16-Formyl-acetyl-gitoxin) Scrophulari. Digitalis spp. Acetyl-gitoxin-« yields acetic acid, gitoxigenin and 3 x D-digitoxose. Scrophulari. Digitalis Acetyl-gitoxin-ß Scrophulari. Digitalis Acetyl-odorogenin-B (Acetyl-uzarigenin) Asclepiad. Xysmalobium Acetyl-odorotrioside-G: a glycoside of digitoxigenin? Apocyn. Nerium odorum i i -Acetyl-sarmentogenin Apocyn. Strophanthus sarmentosus Acetyl-thevetin Apocyn. Thevetia gaumeri (sd) Acofrioside-L yields L-acofriose and i 3.5-dianhydro periplogenin ? Apocyn. Acokanthera friesiorum (sd) Acofrioside-M: belongs here? Apocyn. Acokanthera friesiorum (sd), schimperi (sd) Acolongifloroside-E is incompletely characterized, says Shoppee (1964). Apocyn. Acokanthera friesiorum (sd), longiflora (sd) Acolongifloroside-G is incompletely characterized (1964). Apocyn. Acokanthera friesiorum (sd), longiflora (sd), schimperi (sd) Acolongifloroside-H Apocyn. Acokanthera friesiorum (sd), longiflora (sd), schimperi (sd) Acolongifloroside-J is incompletely characterized (1964). Apocyn. Acokanthera friesiorum (sd) ?, longiflora (sd) ? Acolongifloroside-K yields ouabagenin and L-talomethylose. Apocyn. Acokanthera friesiorum (sd) ?, longiflora (sd) ? Acoschimperosides: several of these have been designated by the letters -K, -N, -P, -Q, -S, -T, -U, -V, -W, -Y2, and -Z. Apocyn. Acokanthera schimperi: see below Acoschimperoside-P (Oleandrigenin-L-acofrioside) Acotaloside Apocyn. Acokanthera venenata Acovenoside-A (Venenatin; Acovenosigenin-A-acovenoside) Apocyn. Acokanthera venenata (sd) and 3 others

CARDIOTONIC GLYCOSIDES AND AGLYCONES 727

Acovenoside-B is a glycoside of aco-venosigenin-A. Apocyn. Acokanthera venenata Acovenoside-C (Acovenosigenin-A-acovenoside-[glucoside]2) Apocyn. Acokanthera venenata (sd) Acovenosigenin-A (fig. I6i) is the aglycone of the acovenosides. Adigoside Apocyn. Nerium oleander Adonitoxigenin (19-0xo-gitoxigenin) is the aglycone of adonitoxin. Ranuncul. Adonis vernalis (as glycoside ?) Adonitoxin (Adonitoxigenin-rhamnoside) Ranuncul. Adonis vernalis Adonitoxol yields adonitoxologenin and L-rhamnose. Ranuncul. Adonis vernalis Adynerigenin (?8(I4)-Anhydro-gitoxigenin) is the aglycone of adynerin. Adynerin yields D-diginose and adynerigenin. Apocyn. Nerium odorum (lvs), oleander (lvs) Afroside-B is a derivative of za, I Iß- or 2«,6%-dihydroxy-uzarigenin. Asclepiad. Gomphocarpus (Asclepias) fruticosus Alleoside-A (Erysimin; Helveticoside) yields D-digitoxose and strophanthidin (erysimidin). It seems to be widely distributed. Crucif. Cheiranthus allionii; Erysimum helveticum and other spp. Mor. Castilla elastica Apocyn. Strophanthus kombe Allo-emicymarin is said to yield D-digitalose and allo-periplogenin. Apocyn. Strophanthus (z) Allo-glaucotoxigenin Legum. Coronilla glauca (chiefly as glycoside) Allo-periplocymarin yields D-cymarose and allo periplogenin. Apocyn. Strophanthus kombe Allo-periplogenin is the aglycone of allo-emicymarin and allo periplocymarin. Allyonin Crucif. Erysimum marschallianum (?Cheiranthus allionii) Amboside (Sarmutogenin-D-diginoside) Apocyn. Strophanthus amboensis Anhydro-calotropagenin Asclepiad. Calotropis procera (lvs, st., free ?) Anhydro-canariengenin-A is the aglycone of anhydro-canarien-glycosideA. Anhydro-canarien-glycoside-A Scrophulari. Isoplexis ( Digitalis) canariensis (lvs) 16-Anhydro-deacetyl-nerigoside Apocyn. Nerium oleander (sd)

728 CHEMOTAXONOMY OF FLOWERING PLANTS

i6-Anhydro-digitalinum-verum yields i6-anhydro gitoxigenin, D-digitalose, and glucose? Apocyn. Adenium honghel (sd., rt); Nerium odorum (bk) ? i6-Anhydro-strospeside (16-Anhydro-deglu co- digitalinum-verum) Apocyn. Adenium multiflorum (sd), Strophanthus (i) Antialloside Mor. Antiaris toxicaria (sd) Antiarigenin (fig. 161) is the genin of a- and f-antiarin. a-Antiarin (Antiarigenin-antiaroside) Mor. Antiaris toxicaria (latex), Antiaropsis, Ogcodeia ß-Antiarin (Antiarigenin-L-rhamnoside) Mor. Antiaris toxicaria (latex, sd), Ogcodeia y-Antiarin Mor. Antiaris toxicaria (latex) Antiarojavoside Mor. Antiaris toxicaria (sd) Antiogenin is the genin of antiogoside, antioside, a-antioside. Antiogoside (Antiogenin-6-deoxy-alloside) Mor. Antiaris toxicaria (sd) Antioside (Antiogenin-rhamnoside) Mor. Antiaris toxicaria (latex, sd); Antiaropsis decipiens (sd); Ogcodeia ternstroemiiflora (latex) cc-Antioside (Antiogenin-6-deoxy-guloside) Mor. Antiaris toxicaria (latex) Apocannoside is a cymaroside of cannogenes, closely related to calotropin. Apocyn. Apocynum cannabinum Ascotuberoside yields ascotuberigenin and 3 x sarmentose. Asclepiad. Asclepias tuberosa Asperoside yields 2,3-di-O-methyl-D glucose and (?). Mor. Streblus asper (rtbk) Beaumontoside Apocyn. Beaumontia grandiflora Beauwalloside Apocyn. Beaumontia grandiflora Bipindaloside (Bipindogenin-ß-D-digitaloside) Apocyn. Strophanthus sarmentosus Bipindogenin is the aglycone of bipindaloside, bipindoside and lokundjoside. Bipindoside (Bipindogenin-a-L-talomethyloside) Apocyn. Strophanthus sarmentosus, thollonii Bogoroside Mor. Antiaris toxicaria (latex) Boistroside (Corotoxigenin-digitoxoside) Apocyn. Roupellina (Strophanthus) boivinii

CARDIOTONIC GLYCOSIDES AND AGLYCONES 729

i7a-Boistroside (i7a-Corotoxigenin-D-digitoxoside ?) Apocyn. Roupellina (Strophanthus) boivinii Calactin is pyrolysed to methyl-reductinic acid and calotropagenin. Asclepiad. Calotropis procera, Pergularia(Daemia) extensa (st. ?, sd) Calotoxin is said to be pyrolysed to hydroxymethyl-reductinic acid and pseudo-anhydro-calotropagenin. Asclepiad. Calotropis gigantea (latex), procera (latex) Calotropagenin is the genin of calactin, calotropin, uscharidin, uscharin? Calotropin is pyrolysed to methyl-reductinic acid and calotropagenin. Asclepiad. Asclepias curassavica (plt), Calotropis procera, Pergularia (Daemia) extensa (sd) Canarien-genin-A (?Canary-genin-A) Scrophulari. Isoplexis canariensis (as glycoside ?) Canarien-glycoside-A (?Canary-glycoside-A) Scrophulari. Isoplexis canariensis (lvs) Canescein Crucif. Erysimum canescens Cannodexoside (Cannogenin-ß-D-digitoxoside) Asclepiad. Pachycarpus distinctus Cannodimethoside yields cannogenol and z,3-di-O-methyl glucose. Mor. Streblus asper (rtbk) Cannogenin (19-Oxo-digitoxigenin) is the genin of cannodexoside, apocannoside, cynocannoside, peruvoside. Asclepiad. Pachycarpus distinctus (free ?) Carpogenin (3-Epi-I9-oxo-digitoxigenin) Asclepiad. Pachycarpus distinctus (free ?) Carpogenol (3-Epi-digitoxigenin-19-ol): occurs naturally? Caudogenin from caudoside. It may be an artefact. Caudoside (Caudogenin-L-oleandroside) is an artefact (Shoppee, 1964). Cerberetin: what is this ? Apocyn. Cerbera odollam (sd) Cerberin (Acetyl-neriifolin; Veneniferin) Apocyn. Cerbera dilatata, floribunda, odollam; Tanghinia venenifera; Thevetia nereifolia (frt) Cerberoside (Thevetin-B; Digitoxigenin-L-thevetoside-[glucoside]z) Apocyn. Cerbera odollam (sd), Thevetia nereifolia (frt) Cerbertatin Apocyn. Cerbera dilatata, floribunda Cerbertin Apocyn. Cerbera dilatata, floribunda Cheiroside-A (Cheiroside-H; Uzarigenin-fucoside-glucoside) Crucif. Cheiranthus cheiri (sd)

730 CHEMOTAXONOMY OF FLOWERING PLANTS

Cheirotoxin (Strophanthidin-6-deoxy-guloside-glucoside) is hydrolysed by strophanthobiase to glucose and the highly toxic degluco-cheirotoxin. Crucif. Cheiranthus cheiri (sd) Christyoside (Corotoxigenin-digitaloside) Apocyn. Roupellina (Strophanthus) boivinii, Strophanthus speciosus Chryseogenin: belongs here? Convallatoxin (Convallatoxoside) yields strophanthidin and L-rhamnose. It may be the most toxic cardenolide. Mor. Antiaris toxicaria (sd, latex) Lili. Convallaria majalis (lvs, fl.), Ornithogalum umbellatum (bulb) Convallatoxol (Strophanthid-ig-ol-rhamnoside) Mor. Antiaris toxicaria (latex) Lili. Convallaria majalis Convallatoxoloside (Strophanthid-I9-ol-rhamnoside-glucoside) Lili. Convallaria majalis Convalloside yields convallatoxin and glucose. Lili. Convallaria majalis (sd), Ornithogalum umbellatum (bulb) Corchorin may be identical with strophanthidin. Tili. Corchorus Corchoroside-A (Strophanthidin-ß-D-boivinoside) Mor. Castilla elastica Crucif. Erysimum perofskianum Till. Corchorus capsularis (sd) Corchoroside-D is hydrolysed to glucose and corchoroside-A. Tili. Corchorus capsularis (sd) Corchoroside-E is hydrolysed to D-glucose and corchoroside-D. Tili. Corchorus capsularis (sd) Corchortoxin: what is this? Tili. Corchorus capsularis (sd) Coroglaucigenin (Uzarigen-I9-ol) is the genin of frugoside, and of coroglaucigenin-sarmentoside. Legum. Coronilla glauca (sd) (free ?) Asclepiad. Asclepias, Calotropis, Gomphocarpus, Xysmalobium (as glycosides ? or free ?) ila-Coroglaucigenin is the genin of ila-Coroglaucigenin-sarmentoside. i7a-Coroglaucigenin-sarmentoside (Glycoside-0) Apocyn. Roupellina (Strophanthus) boivinii Coronillin: belongs here? Legum. Coronilla glauca (sd) Corotoxigenin (19-Oxo-uzarigenin) is the genin of boistroside, christyoside, gofruside, milloside, paulioside, stroboside. It has been obtained (free or as glycoside) from Legum. Coronilla glauca

CARDIOTONIC GLYCOSIDES AND AGLYCONES 731

Apocyn. Strophanthus (2) Asclepiad. Asclepias, Calotropis, Gomphocarpus 17a-Corotoxigenin is the aglycone of 17a-boistroside, and 17u paulioside. Corotoxigenin-glucoside Legum. Coronilla scorpioides Cryptograndoside-A (Oleandrigenin-cymaroside) Apocyn. Nerium oleander (sd) Asclepiad. Cryptostegia grandiflora (lys, st.) Cryptograndoside-B (Oleandrigenin-sarmentoside-glucoside) Asclepiad. Cryptostegia grandiflora (lys, st.) Cymarin (Apocynamarin; x-Strophanthen-a) yields strophanthidin and D-cymarose. Mor. Antiaris toxicaria (sd), Castilla elastica (sd) Ranuncul. Adonis amurensis (rt), vernalis (plt) Apocyn. Apocynum (2), Strophanthus (g) Asclepiad. Pachycarpus schinzianus (rt, sd) I7a-Cymarin Apocyn. Stropanthus eminii Cymarol (Strophanthid-I9-ol-cymaroside) Mor. Antiaris toxicaria (sd) Apocyn. Strophanthus kombe (sd) I7oc-Cymarol Apocyn. Strophanthus eminii Cymarylic Acid (Strophanthidinic acid-cymaroside) Apocyn. Strophanthus hispidus (sd, as glucoside) Cynocannoside (Cannogenin-L-oleandroside) Apocyn. Apocynum cannabinum 16-Deacetyl-i 6-anhydro-cryptograndoside-A yields 16-anhydro gitoxigenin and D-sarmentose. Asclepiad. Cryptostegia grandiflora (lys) i 6-Deacetyl- i 6-anhydro-cryptograndoside-B yields 16-anhydrogitoxigenin, D-sarmentose and glucose. Asclepiad. Cryptostegia grandiflora (Iys) 1 6-Deacetyl-anhydro-hongheloside-A yields anhydro-gitoxigenin and D-cymarOse. Apocyn. Adenium multiflorum (sd, after enzymatic hydrolysis ?) 16-Deacetyl-16-anhydro-oleandrin Apocyn. Urechites lutea (lys) Deacetyl-cerbertatin Apocyn. Cerbera dilatata, floribunda Deacetyl-cerbertin Apocyn. Cerbera dilatata, floribunda

732 CHEMOTAXONOMY OF FLOWERING PLANTS

Deacetyl-hongheloside-A yields gitoxigenin and D-cymarose. Apocyn. Adenium honghel (st., rt), multiflorum (sd) Deacetyl-lanatoside-A (Purpurea-glycoside-A; Digitoxigenin-[digitoxoside]3-glucoside) Scrophulari. Digitalis grandiflora (lvs), lanata (lvs), purpurea (lvs) Deacetyl-lanatoside-B (Purpurea-glycoside-B) Scrophulari. Digitalis lanata (lvs), purpurea (lvs) Deacetyl-lanatoside-C (Deslanoside) Scrophulari. Digitalis lanata (lvs) Deacetyl-lanatoside-D Scrophulari. Digitalis lanata (lvs) Deacetyl-nerigoside Apocyn. Nerium oleander (sd) Deacetyl-oleandrin yields gitoxigenin and L-oleandrose. Apocyn. Nerium oleander (lvs, sd) Deacetyl-tanghinin (Pseudo-tanghinin) : of unknown structure ? Apocyn. Tanghinia venenifera (sd) Decogenin: what is this? Degluco-cheiroside-A yields uzarigenin and D-fucose. Crucif. Cheiranthus cheiri (sd) Degluco-cheirotoxin is highly toxic. It yields strophanthidin and D gulomethylose (antiarose). Mor. Antiaris toxicaria (latex) Crucif. Cheiranthus cheiri (sd) Lili. Convallaria majalis (lvs) Deglucoericordin Crucif. Erysimum cheiranthoides Deglucohyrcanoside Legum. Coronilla hyrcana Desarogenin (i i-Dehydro-sarmentogenin) is the genin of desaroside. Desaroside (I i-Dehydro-sarnovide; Desarogenin-D-digitaloside ?) Apocyn. Strophanthus vanderijstii (sd) 3 , 5-Dianhydro-periplogenin Apocyn. Acokanthera schimperi (sd) ?, ?-Dianhydro-periplogenin (Anhydro-canarygenin-A): is this the same as above ? Scrophulari. Isoplexis canariensis (lvs) Digicorigenin (?3-Acetyl-gitoxigenin) Scrophulari. Digitalis lanata (lvs), purpurea (lvs) Digicorin yields digicorigenin and digicuronic acid. Scrophulari. Digitalis lanata (lvs), purpurea (lvs) Digifucocellobioside yields digitoxigenin, D-fucose and D-glucose. Scrophulari. Digitalis purpurea (sd)

CARDIOTONIC GLYCOSIDES AND AGLYCONES

733

Digilanide-A (Lanatoside-A) yields digitoxigenin, acetic acid, glucose, and 3 x D-digitoxose. Scrophulari. Digitalis ferruginea (lvs), lanata (lvs) Digilanide-B (Lanatoside-B ; Gitoxigenin- [digitoxoside]3-ß-D-glucosideacetate) Scrophulari. Digitalis ferruginea (lvs), lanata (lvs) Digilanide-C (Lanatoside-C) Scrophulari. Digitalis lanata (lvs), orientalis (lvs) Diginatigenin is the aglycone of diginatin. Scrophulari. Digitalis lanata (lvs, free ?) Diginatin: not the original glycoside ? It yields diginatigenin and 3 x D-digitoxose. Scrophulari. Digitalis lanata (lvs) Digiproside yields digitoxigenin and D-fucose. Scrophulari. Digitalis purpurea (lvs, sd) Digistroside (Digitoxigenin-D-sarmentoside) Apocyn. Nerium oleander (sd), Strophanthus vanderijstii (sd) Digitalinum-verum-acetate (Hongheloside-B ?) Apocyn. Adenium (3), Nerium (z) Asclepiad. Cryptostegia? Scrophulari. Digitalis (4) Digitoxigenin (Cerberigenin; Echujetin; Evonogenin; Evonosigenin; Thevetigenin) is said to be the genin of echujin, echubioside, hongheloside-G, odorosides-A and -D, odoroside-G-acetate, odorobioside-G, graciloside, digilanide-A, cerberoside, thevebioside, neriifolin, honghelin, cerberin, evonoside, evobioside, evomonoside, digistroside. It is recorded (free?) from: Celastr. Euonymus (Euonymus) atropurpurea (rt), europaea (sd) Apocyn. Adenium (3), Carissa (2), Nerium (z), Strophanthus (z), Tanghinia, Thevetia Asclepiad. Menabea, Pachycarpus Scrophulari. Digitalis (6 ?) Digitoxin (Digitoxoside): produced secondarily from lanatosides? Scrophulari. Digitalis (6 ?) Digluco-acoschimperoside-P Apocyn. Acokanthera schimperi Digoxigenin (Lanadigigenin; fig. 161) is the genin of the acetyldigoxins, digilanide-C, digoxin. Scrophulari. Digitalis (3, free ?) Digoxin (Digoxoside) yields digoxigenin and 3 x D-digitoxose. Scrophulari. Digitalis grandiflora (lvs), lanata (lvs), orientalis (lvs)

734

CHEMOTAXONOMY OF FLOWERING PLANTS

Dihydro-uscharin (Voruscharin) seems to be a cardenolide which is also a thiazolidin derivative. Asclepiad. Calotropis procera (latex) Divaricoside (Sarmentogenin-a-L-oleandroside) Apocyn. Strophanthus caudatus (sd), divaricatus (sd), wightianus (sd) Divostroside (Sarmentogenin-L-diginoside) Apocyn. Strophanthus divaricatus (sd) Echubioside (Digitoxigenin-cymaroside-glucoside) Apocyn. Adenium boehmianum (arrow-poison) Echujin (Digitoxigenin-cymaroside-[glucoside]2) Apocyn. Adenium boehmianum, lugardii Emicin (Periplogenin-digitaloside-glucoside ?) Apocyn. Strophanthus preussii (sd) Emicymarin (e-Strophanthin) yields periplogenin and D-digitalose. Apocyn. Strophanthus eminii and 8 others 17a-Emicymarin yields 17a periplogenin and D-cymarose. Apocyn. Strophanthus eminii, kombe 3-Epi-corotoxigenin is the aglycone of sadleroside. 3-Epi-l7a-corotoxigenin is the aglycone of 17a-sadleroside. 3-Epi-digitoxigenin AscØiad. Pachycarpus schinzianus Scrophulari. Digitalis lanata 11-Epi-sarmentogenin: what is this ? Ericordin Crucif. Erysimum cheiranthoides Erycorchoside (?Strophanthidin-D-boivinoside-a-D-glucoside) Crucif. Erysimum perofskianum Eryperoside Crucif. Erysimum perofskianum Erysimoside yields strophanthidin, D-digitoxose and D-glucose. Crucif. Erysimum canescens (plt), perofskianum Evatromonoside (Euatromonoside) Celastr. Euonymus(Evonymus) atropurpurea Evatroside (Euatroside; Evobioside ?) Celastr. Euonymus(Evonymus) atropurpurea Evobioside (Digitoxigenin-rhamnoside-glucoside): is this the same as above? Celastr. Euonymus europaea Evomonoside (Digitoxigenin-L-rhamnoside) Celastr. Euonymus europaea Evonoside (Digitoxigenin-rhamnoside-[glucoside]2) Celastr. Euonymus europaea (sd)

CARDIOTONIC GLYCOSIDES AND AGLYCONES

735

Frugoside (Coroglaucigenin-D-6-deoxy-alloside)

Asclepiad. Calotropis, Gomphocarpus, Xysmalobium Gigantin resembles uscharin.

Asclepiad. Calotropis gigantea (latex) Gitaligenin

Scrophulari. Digitalis purpurea (lys) Gitalin yields gitaligenin and a x D-digitoxose. Scrophulari. Digitalis purpurea (lys) Gitaloxigenin (Gitoxigenin-t6-formate; fig. 161) occurs as mono- and di-digitoxosides, and as the digitaloside verodoxin. Gitaloxigenin-bisdigitoxoside Scrophulari. Digitalis purpurea Gitaloxigenin-digitoxoside

Scrophulari. Digitalis purpurea Gitaloxin (i6-Formyl-gitoxin)

Scrophulari. Digitalis purpurea (lys) Gitofucoside yields gitoxigenin and D-fucose. Scrophulari. Digitalis lanata (lys) Gitorin (Gitoxigenin-glucoside) Scrophulari. Digitalis lanata (lys), purpurea (lys) Gitorocellobioside Scrophulari. Digitalis purpurea (lys) Gitoside (Gitoroside) yields gitoxigenin and D-digitoxose. Scrophulari. Digitalis lanata (lys), purpurea (lys) Gitostin yields gitoxigenin, D-digitalose, and cellobiose. Scrophulari. Digitalis purpurea (sd) Gitoxigenin (Anhydro-gitaligenin; Bigitaligenin; Rhodexigenin-B) is the aglycone of: rhodexin-B, gitoxin, hongheloside-B, oridigin, strospeside, gitoxin, deacetyl-lanatoside-B, digilanide-B. It has been obtained from Apocyn. Adenium (3), Nerium (i), Strophanthus (2) Asclepiad. Cryptostegia Scrophulari. Digitalis lanata (lys), orientalis (lys), purpurea (lys) Gitoxin (Bigitalin; Gitoxigenin-[digitoxoside]3) Scrophulari. Digitalis lanata (lys), purpurea (lys, sd) Gitoxin-cellobioside: occurs as a lanatoside?

Scrophulari. Digitalis Glaucorigenin

Legum. Coronilla glauca (sd) Glaucotoxigenin

Legum. Coronilla glauca (sd) Glucocanescein

Crucif. Erysimum canescens

736 CHEMOTAXONOMY OF FLOWERING PLANTS

Glucoconvalloside yields convalloside and D-glucose. Lili. Convallaria majalis (sd) Glucocymarol yields strophanthidol, D-cymarose, and glucose? Apocyn. Strophanthus kombe Glucodigifucoside yields digitoxigenin, D-fucose, and D-glucose. Scrophulari. Digitalis purpurea (sd) Glucogitaloxin (i6-Formyl-purpurea-glycoside-B) yields gitaloxigenin and 3 x digitoxose. Scrophulari. Digitalis purpurea (lvs, sd) Glucogitodimethoside yields gitoxigenin, 2,3-di-O-methyl-v glucose, and D-glucose. Mor. Streblus asper (rtbk) Glucogitofucoside yields gitaloxigenin, D-fucose, and D-glucose. Scrophulari. Digitalis lanata (lvs, sd) Glucogitoroside yields gitoside (gitoroside) and D-glucose. Scrophulari. Digitalis purpurea (sd) Glucohelveticosol yields strophanthidol (?), D-digitoxose and glucose, Apocyn. Strophanthus kombe Glucokamaloside yields periplogenin, 2,3-di-O-methyl-n fucose, and D-glucose. Mor. Streblus asper (rtbk) Glucopanoside Euphorbi. Mallotus paniculatus Glucostrebloside yields strophanthidin, 2,3-di-O-methyl-n fucose, and D-glucose. Mor. Streblus asper (rtbk) Glucoverodoxin (Formyl-digitalinum-verum) Scrophulari. Digitalis grandiflora (lvs), purpurea (lvs, sd) Gofruside (Corotoxigenin-D-6-deoxy-alloside) Asclepiad. Gomphocarpus fruticosus (sd) Gomphocarpin: belongs here? Asclepiad. Gomphocarpus fruticosus (lvs) Gomphoside is a derivative of 2a-hydroxy-uzarigenin (gomphogenin?). Asclepiad. Gomphocarpus fruticosus (plt) Graciloside (Odoroside-F; Digitoxigenin-digitaloside-4-glucoside) Apocyn. Nerium odorum (bk), Strophanthus gracilis (wd) Gypsobioside Crucif. Erysimum gypsaceum Ila-Gypsobioside Crucif. Erysimum gypsaceum Gypsotrioside Crucif. Erysimum gypsaceum

CARDIOTONIC GLYCOSIDES AND AGLYCONES

737

r7a-Helveticoside yields 17a-strophanthidin (?) and D-digitoxose. Apocyn. Strophanthus kombe Helveticosol yields strophanthidol (?) and D-digitoxose. Mor. Castilla elastica Apocyn. Strophanthus kombe Honghelin (Digitoxigenin-D-thevetoside) Apocyn. Adenium honghel (wd) Hongheloside-A (Oleandrigenin-cymaroside) Apocyn. Adenium honghel (st., rt), lugardae (plt), multiflorum (sd) Hongheloside-B (Digitalinum-verum-acetate; Gitoxigenin-acetyldigitaloside-glucoside) Apocyn. Adenium honghel (st., rt), multifiorum (sd) Hongheloside-C (Oleandrigenin-cymaroside-glucoside) Apocyn. Adenium honghel (st., rt), multiflorum (sd) Hongheloside-G (Somalin; Digitoxigenin-cymaroside) Apocyn. Adenium boehmianum (plt), honghel (st., rt), lugardae (plt), somalense (arrow-poison) Hyrcanoside yields hyrcanogenin, xylose, and glucose. Legum. Coronilla hyrcana Indroside yields 6-deoxy-z,3-di-O-methyl-D-galactose and (?). Mor. Streblus asper Inertogenin (fig. 161) is the aglycone of inertoside. Inertoside (Inertogenin-D-diginose ?) Apocyn. Strophanthus amboensis (sd), intermedius, schuchardtii Intermedioside (Sarverogenin-D-diginoside) Apocyn. Strophanthus intermedius and 3 others Interoside (Sarverogenin-D-diginoside-glucoside) Apocyn. Strophanthus intermedius Isoanhydro-calotropagenin Asclepiad. Calotropis gigantea (latex), procera (latex) Isocalotropagenin Asclepiad. Calotropis procera Kabuloside yields strophanthidin (?) and D-z-deoxy gulose. Crucif. Erysimum perofskianum Kamaloside yields 6-deoxy-z,3-di-O-methyl-D galactose and periplogenin. Mor. Streblus asper Krishnoside yields z,3-di-O-methyl-D-glucose and (?). Mor. Streblus asper Kwangoside (Sarmentogenin-D-diginoside) Apocyn. Strophanthus amboensis, vanderijstii Lanatoside-D yields diginatigenin, acetic acid, 3 x D-digitoxose and D-glucose. Scrophulari. Digitalis lanata (lvs) 3

OCO II

738 CHEMOTAXONOMY OF FLOWERING PLANTS

Lanatoside-E (?Gluco-acetyl-gitaloxin; ?16-Formyl-lanatoside-B) Scrophulari. Digitalis lanata (lvs) Ledienoside yields periplogenin and D fucose. Apocyn. Strophanthus ledienii (sd) Leptogenin is the aglycone of leptoside. How does it differ from inertogenin? Leptoside (Leptogenin-D-diginose): is this identical with inertoside? It seems to have the same distribution. Lokundjoside (Bipindogenin-a-L-rhamnoside) Apocyn. Strophanthus sarmentosus, thollonii (sd) Lili. Convallaria keiskei, majalis Madagacoside (Uzarigenin-sarmentoside) Apocyn. Roupellina (Strophanthus) boivinii ila-Madagacoside (I7a-Uzarigenin-D-sarmentoside ?) Apocyn. Roupellina boivinii Majaloside yields L-rhamnose, D-glucose, and (?). Lili. Convallaria majalis (lvs) Malayoside Mor. Antiaris toxicaria Malloside Euphorbi. Mallotus paniculatus Mansonin yields strophanthidin and 2,3-di-O-methyl-6-deoxy-DPlucose. Sterculi. Mansonia altissima (bk) Menabegenin (Ila-Digitoxigenin) Asclepiad. Menabea venenata Milloside (Corotoxigenin-cymaroside) Apocyn. Roupellina boivinii Musaroside (Sarmutogenin-D-digitaloside): secondary? Apocyn. Strophanthus divaricatus, sarmentosus (sd) Neodigoxin: belongs here? Scrophulari. Digitalis lanata (lvs) Neogitostin yields gitoxigenin, gentiobioside and D-digitalose. Scrophulari. Digitalis purpurea (sd) Neriantin (Neriantogenin-glucoside) Apocyn. Nerium oleander (lvs) Neriantogenin (014-Anhydro-gitoxigenin) is the aglycone of neriantin. Nerigoside (Oleandrigenin-D-diginoside) Apocyn. Nerium oleander (sd) Neriifolin (better Nereifolin ?; Digitoxigenin-L-thevetoside ?) Apocyn. Cerbera dilatata, floribunda; Thevetia nereifolia (frt) Neritaloside (Oleandrigenin-D-digitaloside) Apocyn. Nerium oleander (sd)

CARDIOTONIC GLYCOSIDES AND AGLYCONES

739

Nigrescigenin AscØiad. Periploca nigrescens (wd) i 6-O-Acetyl-glucogitodimethoside yields oeandrigenin, 2,3-di-O-methylDglucose and glucose. Mor. Streblus asper (rtbk) Odorobioside-D yields odoroside-A and D-glucose. Apocyn. Nerium oleander (sd) Odorobioside-G (Digitoxigenin-digitaloside-2-glucoside) Apocyn. Nerium odorum (stbk), oleander (sd) Odorobioside-K (Uzarigenin-glucoside-D-diginoside) Apocyn. Nerium odorum (stbk), oleander (sd) Odoroside (Uzarigenin-[glucoside]2-D-diginoside) Apocyn. Nerium odorum Odoroside-A (Digitoxigenin-D-diginoside) Apocyn. Nerium odorum (stbk), oleander (sd); Strophanthus vanderijstii (sd) Odoroside-B (Uzarigenin-D-diginoside) Apocyn. Nerium odorum (stbk), oleander (sd); Strophanthus vanderijstii (sd) Odoroside-D (Digitoxigenin-D-diginoside-glucoside) Apocyn. Nerium odorum (stbk) Odoroside-G-acetate (Odoroside-G; Digitoxigenin-acetyl-digitaloside[glucoside]2) Apocyn. Nerium odorum (stbk ?) Odoroside-H (Digitoxigenin-digitaloside) Apocyn. Carissa lanceolata (rt), ovata v. stolonifera (rt); Nerium (2); Strophanthus (z) Scrophulari. Digitalis purpurea (lys) Odoroside-K: yields uzarigenin and odorotriose? Apocyn. Nerium odorum (stbk) Odorotrioside-G yields odorobioside-G and D-glucose. Apocyn. Nerium odorum (rtbk), oleander (sd) Odorotrioside-K: is this odoroside-K? Apocyn. Nerium oleander (sd) Oleandrigenin (Gitoxigenin-i6-acetate; fig. i6x) is the aglycone of digluco-acoschimperoside-P, acoschimperoside-P, cryptograndosides-A and -B, honghelosides -A and -C, negroside, neritaloside, deacetylnerigoside, i6-anhydro-deacetyl-nerigoside, oleandrin. It has been obtained from Apocyn. Acokanthera; Adenium; Nerium odorum (lys), oleander (lys, sd); Urechites Asclepiad. Cryptostegia Lili. Rohdea 3-2

740 CHEMOTAXONOMY OF FLOWERING PLANTS

Oleandrin (Folinerin; Urechitoxetin; Oleandrigenin-L-oleandroside) Apocyn. Nerium odorum (lys), oleander (lys, sd) ; Urechites lutea (lys) Olitoroside (?Strophanthidin-n-boivinose-ß-n-glucoside) Crucif. Erysimum perofskianum Oridigin yields gitoxigenin, glucose and a 2,6-dideoxy-hexose ? Scrophulari. Digitalis orientalis Ouabagenin (g-Strophanthidin; fig. i61) is the aglycone of ouabain. Ouabain (Acokantherin; g-Strophanthin) yields ouabagenin and Lrhamnose. Apocyn. Acokanthera (q. or 5), Strophanthus (3) Pachygenin (5,6-Anhydro-strophanthidin) Asclepiad. Pachycarpus schinzianus (as glycoside) Pachygenol (5,6-Anhydro-strophanthid-19-ol) Asclepiad. Pachycarpus schinzianus (as glycoside) Pachymonoside yields pachygenin and D-glucose. Asclepiad. Glossostelma spathulatum, Pachycarpus schinzianus, Periploca nigrescens Panoside Euphorbi. Mallotus paniculatus Panstroside (Sarverogenin-n-digitaloside) Apocyn. Strophanthus intermedius (sd) and 3 others Panstrosin yields panstroside and D-glucose. Apocyn. Strophanthus intermedius (sd) Paulioside (Corotoxigenin-sarmentoside) Apocyn. Roupellina boivinii I7a-Paulioside (17x-Corotoxigenin-n-sarmentoside ?) Apocyn. Roupellina boivinii Peripalloside (Periplogenin-6-deoxy-alloside) Mor. Antiaris toxicaria (sd), Streblus asper (rtbk) Periplocin (Periplocoside; Periplogenin-cymaroside-glucoside ?) Apocyn. Strophanthus preussii (sd) Asclepiad. Gomphocarpus?, Periploca graeca (st.) Periplocymarin yields periplogenin and n-cymarose. Mor. Castilla elastica (sd) Apocyn. Strophanthus (7) Asclepiad. Periploca graeca (bk) I7a-Periplocymarin yields 170c-periplogenin and cymarose. Apocyn. Strophanthus (2) Periplogenin (Emicymarigenin; fig. 160 is the genin of emicin, emicymarin, ledienoside, periplocin, periplocymarin, periplogenin-n-digitoxoside, vanderoside. Periplogenin-n-digitoxoside Apocyn. Strophanthus ledienii (sd)

CARDIOTONIC GLYCOSIDES AND AGLYCONES 741

Periplogenin-a-L-rhamnoside Mor. Antiaris toxicaria (sd) Perofskoside yields strophanthidin (?) and D-a-deoxy glucose. Crucif. Erysimum perofskianum Peruvoside (Cannogenin-L-thevetoside) Apocyn. Apocynum cannabinum?, Thevetia nereifolia (sd) Pseudo-anhydro-calotropagenin Asclepiad. Calotropis gigantea (latex), procera (latex) Pseudo-calotropagenin Asclepiad. Calotropis procera Pseudo-caudoside (Sarmutogenin-L-oleandroside) Apocyn. Strophanthus divaricatus Pseudo-caudostroside (Sarmutogenin-L-diginoside) Apocyn. Strophanthus divaricatus Quilengenin: belongs here ? Apocyn. Strophanthus amboensis (sd) Quilengoside yields quilengenin and D-diginose. Apocyn. Strophanthus amboensis (sd) Rhodexin-A (better Rohdexin-A ?) yields sarmentogenin and L-rhamnose. Lili. Ornithogalum umbellatum, Rohdea (Rhodea) japonica (lvs, rt, sd) Rhodexin-B (Gitoxigenin-rhamnoside) Lili. Rohdea japonica (lvs, rt, sd) Rhodexin-C yields rhodexin-B and D-glucose. Lili. Rohdea japonica (lvs, rt, sd) Rhodexoside Lili. Ornithogalum umbellatum Ruvoside: belongs here? Apocyn. Thevetia nereifolia (peruviana) Sadleroside (3-Epi-corotoxigenin-boivinoside) Apocyn. Roupellina boivinii I7x-Sadleroside (3-Epi-17cc-corotoxigenin-boivinoside) Apocyn. Roupellina boivinii Sargenoside (Sarmentogenin-digitaloside-glucoside) Apocyn. Strophanthus sarmentosus (sd) Sargenoside-diacetate (Sarmentoside-B; Sarmentogenin-i 1-acetateacetyl-digitaloside-glucoside) Apocyn. Strophanthus sarmentosus Sarhamnoloside (Sarmentologenin-a-L-rhamnoside) Apocyn. Strophanthus sarmentosus, thollonii (sd) Sarmentocymarin (Sarmentogenin-sarmentoside) Apocyn. Strophanthus (7)

742 CHEMOTAXONOMY OF FLOWERING PLANTS

Sarmentogenin (Hispidogenin; Rhodexigenin-A) is the genin of

divaricoside, divostroside, kwangoside, sargenoside, sarmentocymarin, sarnovide. It has been obtained from Apocyn. Strophanthus (i i) Asclepiad. Pachycarpus distinctus (rt) Lili. Rohdea japonica Sarmentologenin is the genin of sarhamnoloside and sarmentoloside. Sarmentoloside (Sarmentologenin-a-L-talomethyloside)

Apocyn. Strophanthus sarmentosus (sd), thollonii (sd) Sarmentoside-A (Sarmentosigenin-A-a-L-talomethyloside) Apocyn. Strophanthus sarmentosus (sd) (and 3 other spp. ?) Sarmentoside-C Apocyn. Strophanthus sarmentosus (sd) and 3 other spp. Sarmentoside-D: structure unknown (Shoppee, 1964).

Apocyn. Strophanthus sarmentosus (sd), thollonii (sd) Sarmentoside-E (Sarmentosigenin-E-a.-L-talomethyloside) Apocyn. Strophanthus sarmentosus (sd), and 2 other spp. Sarmentosigenin-A (Sarmentogenin-l1-acetate) is the genin of sarmentoside-A and tholloside. Sarmentosigenin-E (fig. 161) is the genin of sarmentoside-E and

thollodiolidoside. Sarmethoside ( ?Sarmenthoside) yields sarmentogenin and 3-0-methyl-

D-glucose. Mor. Streblus asper (rtbk) Sarmutogenin is the genin of amboside, musaroside, pseudo-caudostroside, and sarmutoside. Sarmutoside (Sarmutogenin-sarmentoside)

Apocyn. Strophanthus sarmentosus (sd) Sarnovide (Sarmentogenin-digitaloside)

Apocyn. Strophanthus sarmentosus (sd), and 3 other spp. Sarverogenin is the aglycone of intermedioside, interoside, panstroside, sarveroside, i-strophanthoside. Apocyn. Strophanthus sarmentosus (sd), and 9 other spp. (free ? or as glycoside ?) Sarveroside (Sarverogenin-n-sarmentoside)

Apocyn. Strophanthus sarmentosus (sd), and 6 other spp. Sarvoside: belongs here ?

Apocyn. Strophanthus sarmentosus (sd) Securidaside yields securigenin, D-xylose and glucose.

Legum. Securigera coronilla (securidaca) Sinogenin is an isomer of caudogenin and sarmutogenin. It is the aglycone of sinoside and sinostroside.

Apocyn. Strophanthus divaricatus (sd)

CARDIOTONIC GLYCOSIDES AND AGLYCONES

743

Sinoside (Sinogenin-L-oleandroside) Apocyn. Strophanthus divaricatus (sd) Sinostroside (Sinogenin-L-diginoside) Apocyn. Strophanthus divaricatus (sd) Smalogenin Asclepiad. Xysmalobium undulatum (rt) Spectabilin: belongs here ? Apocyn. Acokanthera spectabilis (lys) Strebloside yields 6-deoxy-z,3-di-O-methyl-D galactose and strophanthidin. Mor. Streblus asper (rtbk) Stroboside (Corotoxigenin-boivinoside) Apocyn. Roupellina boivinii Strophalloside yields strophanthidin and 6-deoxy-D-allose. Mor. Antiaris toxicaria (sd), Streblus asper (rtbk) Sterculi. Mansonia altissima Strophanolloside yields strophanthidol and 6-deoxy-D-allose. Mor. Streblus asper (rtbk) Strophanthidin (Apocynamarin; Convallatoxigenin; Corchorgenin; Corchorin?; Corchsularin; Cymarigenin; Cynotoxin; Erysimidin; fig. 161) is the genin of alleoside-A, cheirotoxin, convallatoxin, the corchorosides, cymarin, degluco-cheirotoxin, erycorchoside?, erysimoside, mansonin, olitoroside?, perofskoside?, strophanthidin-D-digitaloside, syreniotoxin. It has been obtained (free in some cases ?) from Mor. Antiaris, Castilla Crucif. Cheiranthus, Erysimum, Syrenia Ranuncul. Adonis Tili. Corchorus Sterculi. Mansonia Apocyn. Apocynum, Strophanthus Asclepiad. Pachycarpus, Periploca Lili. Convallaria, Ornithogalum Strophanthidin-D-digitaloside Apocyn. Strophanthus ledienii Strophanthidin gulomethyloside Mor. Castilla elastica Strophanthidinic acid Strophanthid-19-ol is the aglycone of cymarol. It has been obtained from Apocyn. Strophanthus (I I ?) Asclepiad. Periploca nigrescens (free ?) Lili. Convallaria majalis

744

CHEMOTAXONOMY OF FLOWERING PLANTS

k-Strophanthidol-y yields strophanthidol (19 ?), D-cymarose and 2 x glucose. Apocyn. Strophanthus kombe h-Strophanthin yields cymarin and D-glucose. Apocyn. Strophanthus hispidus (sd), letei (bk) k-Strophanthin-ß yields cymarigenin and strophanthobiose. Apocyn. Strophanthus courmontii (sd), kombe (sd) Strophanthojavoside (Strophanthidin-ß-D javoside) Mor. Antiaris toxicaria (sd) i-Strophanthoside (Sarverogenin-D-diginoside-[glucoside]2) Apocyn. Strophanthus intermedius k-Strophanthoside (K-Strophanthoside-y) yields x-strophanthin-ß and D-glucose. Apocyn. Strophanthus arnoldianus (sd), kombe (sd) Strophothevoside yields strophanthidin and 3-O-methyl-D glucomethylose. Strospeside (Degluco-digitalinum-verum; Gitoxigenin-digitaloside) Apocyn. Adenium multiflorum ?, Nerium (2), Strophanthus (2) Asclepiad. Cryptostegia Scrophulari. Digitalis (4) Syreniotoxin yields strophanthidin and (?). Crucif. Syrenia (Erysimum) angustifolia (plt) Tanghiferigenin Apocyn. Tanghinia venenifera (sd) Tanghiferin: of unknown structure (Shoppee, 1964). Apocyn. Tanghinia venenifera (sd) Tanghinigenin (fig. 161) is the aglycone of deacetyl-tanghinin, tanghiferin and tanghinin. Tanghinin (Tanghinigenin-acetyl-thevetoside) Apocyn. Tanghinia venenifera (sd) Tanghinoside: yields tanghinin and gentiobiose? Apocyn. Tanghinia venenifera (sd) Thevebioside yields neriifolin and D-glucose. Apocyn. Thevetia nereifolia Thevefolin yields an isomer of digitoxigenin and L-thevetose? Apocyn. Thevetia nereifolia? Theveneriin yields (?) and L-thevetose. Apocyn. Thevetia nereifolia? Thevetigenin (Cerberigenin) has been obtained from Apocyn. Cerbera, Thevetia Thevetin-A (Cannogenin-L-thevetoside-[glucoside]2) Apocyn. Thevetia nereifolia

CARDIOTONIC GLYCOSIDES AND AGLYCONES

HO

HO Acovenosigenin-A

745

HO

OH Antuarigenin

Digoxigenin

0 O.C.CH3 II 0 HO

HO Gitaloxigenin

HO

OH

Inertogenin

HO

Periplogenin

Ouabagenin

HO

OH Strophanthidin

OH

Oldeandrigenin

HO

OH

Sarmentosigenin-E

HO

HO Tanghinigenin

Uzarigenin

Fig. i6i. Some cardenolide genins.

Thevetoidin Apocyn. Thevetia gaumeri (sd) Thollodiolidoside (Sarmentosigenin-E-a.-L-rhamnoside) Apocyn. Strophanthus thollonii (sd) Tholloside (Sarmentosigenin-A-oc-L-rhamnoside) Apocyn. Strophanthus sarmentosus, thollonii (sd) Urechitoxin yields oleandrin and D-glucose. Apocyn. Urechites lutea (lvs), suberecta (Ivs)

746 CHEMOTAXONOMY OF FLOWERING PLANTS

Urezigenin (3-Epi-usarigenin) is the aglycone of urezin. Asclepiad. Xysmalobium undulatum (rt) Urezin (Urezigenin-[glucoside]2) Asclepiad. Xysmalobium undulatum (rt) Uscharidin is pyrolysed to calotropagenin and methyl-reductinic acid.. Asclepiad. Calotropis (z) Uscharin yields uscharidin and 2,5-dihydroxy-p-dithane (does this tally with a formula C31H9108NS ?). Asclepiad. Calotropis (a) Uzarigenin (5-Allo-digitoxigenin?; Odorogenin-B; Uzaridin; fig. 161) is the genin of cheiroside-A, madagacoside, odorobioside-K, odoroside, odoroside-B, uzarin, uzaroside, nettoside. It has been obtained from Apocyn. Nerium, Strophanthus Asclepiad. Asclepias, Gomphocarpus, Pachycarpus, Xysmalobium 17a-Uzarigenin is the aglycone of 17a-madagacoside and 17a-zettoside. Uzarin (Uzarigenin-[glucoside]Z) Asclepiad. Asclepias, Gomphocarpus, Pachycarpus, Xysmalobium Uzaroside (Uzarigenin- [glucoside] 3) Asclepiad. Xysmalobium? (` Uzara-root') Vallarotoxin yields (?) and L-rhamnose. Lili. Convallaria majalis (lvs) Vanderoside yields periplogenin and D-diginose. Apocyn. Strophanthus vanderijstii Vernadigin yields strophandogenin and diginose. Ranuncul. Adonis vernalis Verodoxin (16-Formyl-strospeside; Gitaloxigenin-digitaloside) Scrophulari. Digitalis purpurea Xysmalogenin (5,6-Anhydro-periplogenin; Y-Uzarigenin) is the aglycone of xysmalorin. It has been obtained from Asclepiad. Pachycarpus schinzianus, Xysmalobium undulatum Xysmalorin yields xysmalogenin and a x D-glucose. Asclepiad. Xysmalobium undulatum Zenkoside is of unknown structure (Shoppee, 1964.). Apocyn. Strophanthus sarmentosus (sd) Zettoside (Uzarigenin-boivinoside) Apocyn. Roupellina boivinii 17a-Zettoside (17a-Uzarigenin-n-boivinoside) Apocyn. Roupellina boivinii

CARDIOTONIC GLYCOSIDES AND AGLYCONES

747

HO Digacetigenin

Diginane

o,

OH

OH

HO HO

HO Purpnigenin

Digifologenin

Fig. 162. Diginane and some digitenolide genins.

III . 2 Digitenolides GENERAL Only a handful of digitenolides are known, all I think confined to a few species of Digitalis. They may be considered to be derivatives of diginane (5a,14ß,17apregnane; fig. 162). Digitenolides are said to be physiologically inactive. List and Occurrence Digacetigenin (fig. 162) is the aglycone of digacetinin. Digacetinin (Digacetigenin-[digitoxoside]3-acetate) Scraphulari. Digitalis purpurea var. Digifolein (Digifologenin-D-diginoside) Scrophulari. Digitalis purpurea Digifologenin (Lanafologenin; 2ß-Hydroxy-diginigenin; fig. 162) is the aglycone of digifolein and lanafolein. Diginigenin is the aglycone of digitalonin and diginin. Diginin (Diginigenin-D-diginoside) Scrophulari. Digitalis purpurea (lvs) 14a,I7e-Digiprogenin (y-Genin) is the aglycone of 14a-digipronin.

748 CHEMOTAXONOMY OF FLOWERING PLANTS

i4a-Digipronin (I4oc-17e-Digiprogenin-digitaloside) Scrophulari. Digitalis lanata, purpurea Digipurpurin is easily converted to purpurin. Scrophulari. Digitalis purpurea Digitalonin (Diginigenin-digitaloside) Scrophulari. Digitalis purpurea (lvs) Lanafolein (Digifologenin-D-oleandroside) Scrophulari. Digitalis lanata Purpnigenin (fig. 162) is the aglycone of digipurpurin and purpnin. Purpnin yields purpnigenin and 3 x digitoxose. Scrophulari. Digitalis purpurea Purprogenin is the aglycone of purpronin. Purpronin yields purprogenin and 3 x digitoxose. Scrophulari. Digitalis purpurea

I1I.3 Scilladienolides (bufadienolides) GENERAL These occur as glycosides in plants. In toads they may be free or conjugated with suberyl-arginine. They are physiologically active, resembling digitalis. In place of the 5-membered lactone ring found in the cardenolides, the scilladienolides have a 6-membered ring (fig. 163). They are numerous in the Liliaceae—Bowiea, Urginea (Scilla), and have been found also in the Ranunculaceae—Helleborus. List and Occurrence Altoside (Scilliglaucosidin-ß-D-glucoside) Lili. Urginea altissima (bu.) Anhydro-scilliphaeosidin Lili. Urginea scilla (maritima) (bu.) Bovocryptoside (Bovokryptoside) is a hydroxy-bovogenin-A-thevetoside. Lili. Bowiea volubilis (bu.) Bovocyanotoxin Lili. Bowiea volubilis (bu.) Bovoeolotoxin (Bovogenin-E) Lili. Bowiea volubilis (bu.) Bovoerythrotoxin Lili. Bowiea volubilis (bu.)

CARDIOTONIC GLYCOSIDES AND AGLYCONES

749

Bovogenin-A (Bowiea-substance-G; fig. 163) is the aglycone of bovosides-A and -B and of glucobovoside-A. Lili. Bowiea (free ?) Bovopurpuroside: an isomer of bovoside-D? Lili. Bowiea volubilis (bu.) Bovoruboside is closely related to bovocryptoside. Lili. Bowiea volubilis (bu.) Bovoside-A (Bovogenin-A-thevetoside) Lili. Bowiea kilimandscharica (bu.), volubilis (bu.) Bovoside-B is a bovogenin-thevetoside. Lili. Bowiea volubilis (bu.) Bovoside-C Lili. Bowiea volubilis (bu.) Bovoside-D is probably i 6ß-hydroxy-bovogenin-A-thevetoside. Lili. Bowiea volubilis (bu.) Bovoside-E Lili. Bowiea volubilis (bu.) Bovosidol-A may be seconda ry. Lili. Bowiea volubilis (bu.) ? Bovoxanthotoxin Lili. Bowiea volubilis (bu.) Glucobovoside-A (Bovogenin-A-L-thevetoside-glucoside) Lili. Bowiea volubilis (bu.) Glucoscillaren-A (Scillarenin-rhamnoside-[glucoside]2) Lili. Urginea scilla (bu.) Glucoscilliphaeoside (Scillarenin-rhamnoside-glucoside ?) Lili. Urginea scilla (bu.) Hellebrigenin (Bufotalidin; fig. 163) is the aglycone of hellebrin. It occurs in toad (Bufo) secretions, and has been obtained from Ranuncul. Helleborus niger (rt, rhiz.), purpurascens (rhiz.) Lili. Urginea depressa (bu.) Hellebrin (Corelborin-P ?; Hellebrigenin-rhamnoside-glucoside) Ranuncul. Helleborus niger (rt, rhiz.), purpurascens (rhiz., as corelborin-P), viridis (rt, as corelborin-P) Kilimandscharogenin-A Lili. Bowiea kilimandscharica (bu.), volubilis (bu.) Prorubilidin Lili. Urginea rubella (bu.) Proscillaridin-A (Degluco-transvaalin; Scillarenin-L-rhamnoside) Lili. Urginea burkei (bu.), scilla (bu.) Scillaren-A (Transvaalin; Scillarenin-rhamnoside-glucoside) Lili. Urginea burkei (bu.), scilla (bu.)

750 CHEMOTAXONOMY OF FLOWERING PLANTS

HO

HO

Bovogeni n -A

Hel lebrigenin

Scillarenin

HO OAC

Scillirosidin Fig. z63. Some scilladienolide genins.

Scillaren-F: of unknown structure ? Lili. Urginea stilla (bu. of red var.) Scillarenin (Scillaridin-A; fig. 163) is the aglycone of glucoscillaren-A, glucoscilliphaeoside, proscillaridin-A, stillaren-A, and scilliphaeoside. Scillarenin-di-L-rhamnoside Lili. Urginea indica (Stilla i.) Scillicoeloside Lili. Urginea svilla (bu.) Scillicyanoside: of unknown structure? Lili. Urginea scilla (bu.) Scilliglaucoside (4,5-Anhydro-hellebrigenin-a-n-glucoside) Lili. Urginea altissima (bu.), stilla (bu.) Scilliglaucosidin (4,5-Anhydro-hellebrigenin) is the aglycone of scilliglaucoside. Lili. Bowiea volubilis (bu., free?); Urginea altissima (bu.), stilla (bu.) Scillicryptoside: of unknown structure? Lili. Urginea stilla (bu.) Scilliphaeoside (Scillarenin-glucoside ?) Lili. Urginea stilla (bu.) Scilliroside Lili. Urginea scilla (bu. of red var.) Scillirosidin (fig. 163) is the aglycone of scilliroside.

STEROIDAL SAPONINS AND SAPOGENINS 751

IV STEROIDAL SAPONINS AND SAPOGENINS GENERAL This is a comparatively small group of substances. They have been discussed by Stoll and Jucker (in Paech and Tracey, 1955) and by Shoppee (1964). They are based on the ring-system of spirostan (fig. 164). Their distribution is interesting. They occur in some families of dicotyledons: Legum. (Trigonella); Zygophyll. (Balanites); Fouquieri. (Idria); Solan. (Cestrum, Solanum); and Scrophulari. (Digitalis); but they are particularly prominent in 3 closely related families of monocotyledons : Lili. (Acrospira, Agapanthus, Albuca, Allium, Anemarrhena, Asparagus, Aspidistra, Chamaelirion, Chlorogalum, Clintonia, Heloniopsis, Herreria, Hosta, Lilium, Liriope, Metanarthecium, Narthecium, Rohdea, Ruscus, Smilacina, Smilax, Tofieldia, Trillium, Zigadenus); Agay. (Agave, Cordyline, Doryanthes, Dracaena, Furcraea, Hesperaloe, Manfreda, Nolina, Polianthes, Samuela, Yucca); and Dioscore. (Dioscorea). Isolated members have also been reported from Bromeli. (Hechtia) and Palmae (Pseudophoenix). How much of the apparent frequency of the occurrence in the Liliales is due to the more adequate investigation of these plants ? List and Occurrence Acrospirin is said to yield gitogenin, rhamnose, xylose, glucose, galactose, and perhaps something else! Lili. Acrospira asphodeloides (bu.) Agapanthagenin Lili. Agapanthus sp. (as saponin?) Agavogenin Agay. Agave huachucensis (as saponin ?) Amolonin yields tgogenin, D-galactose, 3 x D-glucose, and a x L-rhamnose. Lili. Chlorogalum pomeridianum Balanites-saponin yields diosgenin and 4 molecules of sugar. Zygophyll. Balanites aegyptica Bethogenin Lili. Trillium erectum (as saponin ?) Cacogenin (I2-Oxo-magvgenin) Agay. Agave sp. ? Chiapagenin Dioscore. Dioscorea chiapensis (as saponin?)

752 CHEMOTAXONOMY OF FLOWERING PLANTS

Chlorogenin (z) (fig. 164) is the aglycone of chloronin. It has been obtained from (saponins of ?) Agay. Agave (3), Manfreda, Yucca Lili. Chlorogalum, Trillium Chloronin yields chlorogenin (z) and 6 molecules of sugar. Agay. Agave utahensis Lili. Chlorogalum pomeridianum, Trillium erectum Corellogenin (Neobotogenin; 12-Oxo-yamogenin) Agay. Agave mexicana (as saponin?) Dioscore. Dioscorea spiculiflora (as saponin?) 9-Dehydro-hecogenin Agay. Agave (ii spp., as saponin ?), Manfreda (as saponin?) 9-Dehydro-manogenin Agay. Agave (many spp., as saponin?) Digitogenin (fig. 164) is the aglycone of digitonin. Solan. Cestrum (as saponin?) Scrophulari. Digitalis purpurea (free and as saponin) Digitonin yields digitogenin, 2 X glucose, 2 x galactose, and xylose (Shoppee, 1964). Scrophulari. Digitalis lanata, purpurea Dioscin yields diosgenin, rhamnose?, and glucose? Dioscore. Dioscorea tokoro Dioscorea-sapotoxin yields diosgenin, glucose, and rhamnose. Dioscore. Dioscorea tokoro Diosgenin (Dioscorea-sapogenin; Nitogenin; fig. 164) is the aglycone of several saponins, including the above and trillarin and trillin. It occurs widely (but chiefly as saponins?): Agay. Agave, Manfreda, Nolina, Yucca Lili. Aletris, Aspidistra, Chamaelirion, Clintonia, Liriope, Smilacina, Tofieldia, Trillium (many spp.) Dioscore. Dioscorea (many spp.) Palmae Pseudophoenix Legum. Trigonella Zygophyll. Balanites (in saponin) Fouquieri. Idria Solan. Solanum Fesogenin: does not occur as such ? Lili. Trillium erectum (as saponin?) Furcogenin Agay. Furcraea selloa, Yucca flaccida Gentrogenin (Botogenin; 1z-Oxo-diosgenin) Dioscore. Dioscorea mexicana, spiculiflora

STEROIDAL SAPONINS AND SAPOGENINS

753

Gitogenin (Digin) is like diosgenin, widely distributed, but chiefly (?) as saponins. It is the aglycone of gitonin.

Agay. Agave, Furcraea, Hesperaloe, Manfreda, Yucca Lili. Albuca, Chlorogalum, Herreria, Hosta Legum. Trigonella Solan. Cestrum (as glycoside) Scrophulari. Digitalis purpurea Gitonin yields gitogenin, 4 x galactose, and xylose? Scrophulari. Digitalis lanata, purpurea Gracillin: an isomer of dioscin? It yields diosgenin, glucose and rhamnose. Dioscore. Dioscorea gracillima Hecogenin (fig. 164) is said to occur in 3 polymorphs. It has been obtained from (saponins of ?) the following Agay. Agave (many), Furcraea, Hesperaloe, Manfreda, Yucca

Bromeli. Hechtia texensis 0°(")-Hecogenin has the same distribution as hecogenin, says Shoppee (1964). Heloniogenin is an aglycone of heloniopsis-saponin. Heloniopsis-saponin: yields 3 genins ?

Lili. Heloniopsis orientalis Isochiapagenin

Lili. Heloniopsis orientalis (as saponin) Dioscore. Dioscorea chiapensis (as saponin?) Isorohdeasapogenin (Isorhodeasapogenin)

Lili. Rohdea (Rhodea) japonica Kammogenin (12-Oxo-yuccagenin) is the aglycone of kammonin. Kammonin yields kammogenin and 6 sugar molecules. Agay. Samuela carnerosa, Yucca (3) Kappogenin

Lili. Trillium erectum Kogagenin

Dioscore. Dioscorea tokoro Kryptogenin

Lili. Trillium erectum and 7 other spp. (as saponins?) Dioscore. Dioscorea (I 2 spp., as saponins?) Zygophyll. Balanites aegyptica (as saponin?) Lilagenin

Lili. Lilium humboldtii, rubrum magnificum Luvigenin has an aromatic A-ring.

Lili. Metanarthecium luteoviride Magogenin

Agay. Agave sp. ?

754

CHEMOTAXONOMY OF FLOWERING PLANTS

Manogenin (i2-0xo-gitogenin): occurs in 3 polymorphs? Agay. Agave (many), Furcraea, Manfreda (2), Yucca (as saponins ?) A9(n)-Manogenin Agay. Agave huachucensis Markogenin is said to be very like texogenin (but see Shoppee, 1964). Agay. Yucca faxoniana (lvs), schidigera (lvs) Metagenin Lili. Metanarthecium luteoviride Mexogenin (12-0xo-samogenin) Agay. Samuela carnerosa, Yucca schottii Neochlorogenin Scrophulari. Digitalis purpurea Neodigitogenin has been obtained from commercial digitonin. Neogitogenin Agay. Yucca schottii Neokammogenin may be an artefact. Dioscore. Dioscorea mexicana Neomanogenin may be an artefact. Agay. Yucca schottii (frt) Neomexogenin may be an artefact. Agay. Agave roezliana Neoruscogenin Lili. Ruscus aculeatus Neotigogenin: the C25-epimer of tigogenin? Lili. Chlorogalum pomeridianum Agay. Agave, Yucca Nogiragenin Lili. Metanarthecium luteoviride Nologenin is the aglycone of nolonin. Nolonin yields nologenin and (?). Lili. Trillium erectum Dioscore. Dioscorea mexicana Parillin yields sarsasapogenin, 3 x D-glucose, and L-rhamnose. Lili. Smilax aristolochiaefolia (rt) Pennogenin has been obtained from heloniopsis-saponin. Lili. Trillium erectum (as saponin?) Rockogenin is very like hecogenin. Agay. Agave gracilipes Rohdea-sapogenin (Rhodea-sapogenin) Lili. Rohdea (Rhodea) japonica (as saponin?) Ruscogenin Lili. Asparagus maritimus (rt); Ruscus aculeatus (lvs, rt), hypoglossum (lvs, rt)

STEROIDAL SAPONINS AND SAPROGENINS

755

Samogenin Agay. Samuela carnerosa, Yucca schottii Sarsasapogenin (Parigenin; fig. 164) is the C25-epimer of smilagenin. It is the aglycone of sarsasaponin. It is recorded (sometimes as saponin?) from Agay. Agave (z), Cordyline, Doryanthes, Samuela, Yucca (18 ?) Lili. Anemarrhena, Asparagus, Narthecium, Smilax (5) Dioscore. Dioscorea Sarsasaponin yields sarsasapogenin, 2 x glucose and rhamnose? Lili. Yucca schottii Sisalagenin (Neohecogenin) is the z5fF-epimer of hecogenin. Agay. Agave sisalana Smilagenin (Isosarpogenin) is the aglycone of smilonin. Agay. Agave (4), Dracaena, Samuela (z), Yucca (17?) Lili. Smilax ornata, Zigadenus (2) Smilonin yields smilagenin and 5 molecules of sugar. Agay. Agave (2), Yucca schottii Lili. Smilax ornata Texogenin is of doubtful existence (Shoppee, 1964). Agay. Yucca schottii Tigogenin is the genin of amolonin and tigonin. It is widely distributed. Agay. Agave (s), Furcraea, Hesperaloe, Manfreda, Polianthes, Yucca Lili. Albuca, Allium tricoccum, Chlorogalum pomeridianum (as amolonin) Legum. Trigonella Solan. Solanum dulcamara Scrophulari. Digitalis lanata, purpurea Tigonin yields tigogenin, 2 x galactose, 2 x glucose, and xylose (or rhamnose ?) Scrophulari. Digitalis lanata Tokorogenin Dioscore. Dioscorea tokoro Trillarin yields diosgenin and 2 x glucose. Lili. Trillium erectum Trillin yields diosgenin and glucose. Lili. Trillium erectum Trillogenin: what is this? Lili. Trillium erectum Willagenin (Iz-Oxo-sarsasapogenin ?) Agay. Yucca ftlifera Yamogenin Agay. Agave? Dioscore. Dioscorea testudinaria (and II other spp. ?)

756 CHEMOTAXONOMY OF FLOWERING PLANTS 21

20 22

0

S O

U 14

0

Spirostan

HO

HO

Sarsasapogenin

Diosgenin

Digitogenin

Hecogenin

HO OH Chlorogenin

Fig. 164. Spirostan and some steroidal sapogenins. Yonogenin Dioscore. Dioscorea tokoro Yuccagenin is the genin of yucconin. Agay. Agave, Nolina, Yucca (3) Lili. Agapanthus Yucconin yields yuccagenin, 3 x galactose and a pentose. Agay. Yucca (3)

SULFUR COMPOUNDS GENERAL Kjaer (in Swain, 1963) has written: `The sulfur-containing protein amino acids, as well as coenzymes and vitamins having sulfur in their molecules, are of decisive importance in life-controlling processes, but provide little help in taxonomic studies because of their ubiquitous occurrence.' We shall exclude these primary sulfur compounds from the present discussion, and concentrate on the secondary sulfur compounds. These have been considered in general articles by Kjaer (1958, 1963, 1966) and we have followed him more or less closely in the following notes.

SULFUR COMPOUNDS

757

We may distinguish: I. II. III. IV. V. VI.

Thiols (Mercaptans) Sulfides and sulfonium compounds Di- and polysulfides Sulfoxides and sulfones Isothiocyanates (mustard oils) and their glucosides Thiophene derivatives

I THIOLS (MERCAPTANS) GENERAL Most thiols are easily oxidized, even by atmospheric oxygen, and those of low molecular weight are volatile and with more or less unpleasant odours. Kjaer (in Swain, 1963) says that most of the thiols reported from plant sources probably arise during preparation from precursors present in the tissues. Thus when ground seeds of Albizia lophantha are soaked in water an onion-like odour results. The substrate for the production of this odour is said to be djenkolic acid, a sulfur-containing amino-acid. Is the volatile product methanedithiol ? Some acetylenic compounds have mercapto-groups. We have considered these with the other acetylenes (p. loo). List and Occurrence Butyl-mercaptan (CH3CH2CH2CH2. SH) has been reported from the stink-badger of the Philippine Islands, but not yet, I think, from higher plants, though it may well occur. 3,3'-Dimercapto-isobutyric acid ((HS . CH2)2CH . COOH) Lili. Asparagus officinalis Ethyl-mercaptan (Ethane-thiol; CH3CH2 . SH) has not, I think, been recorded from higher plants. This is strange, since methyl- and propyl-mercaptans occur. Methane-dithiol (CH2. (SH)2) Legum. Albizia lophantha (sd, secondarily from djenkolic acid?) Methyl-mercaptan (Methane-thiol; CH3SH) has been reported from Cruciferae and from Rubiaceae (which see for discussion). Many foetid plants have yet to be investigated; some, at least, of them are likely to have mercaptans. Cruciferae. Brassica napus var. oleifera (sd-oil), Raphanus sativus (radish, rt)

758 CHEMOTAXONOMY OF FLOWERING PLANTS

Rubi. Coprosma foetidissima ; Lasianthus bracteolatus, lucidus, purpureus, stercorarius (but not? in laevigatus); Paederia foetida, scandens? Propyl-mercaptan (Propane-thiol; CH3CH2CH2 . SH) Lili. Allium cepa (bu.)

II SULFIDES AND SULFONIUM COMPOUNDS GENERAL Some of the antibiotics produced by lower organisms belong here. So, too, do the sulfides produced (secondarily in all cases ?) by algae. These substances are not discussed here. Hydrogen sulfide (H—S—H) may be thought of as the `parent' substance. If the hydrogens are replaced by organic radicals then sulfides (thio-ethers) are obtained, R—S—R1. Oxidation of sulfides leads to sulfoxides, R—SO—R1, and to sulfones, R—S02 R1. Some of the a-amino-acids (such as S-methyl-l-cysteine, menthionine, djenkolic acid and lanthionine) are sulfides. They are considered with the other amino-acids. Some other sulfides may be classed as vitamins. Yet other cyclic compounds are said to be related biogenetically to the acetylenes (qq.v.). Finally, several sulfides arise from enzymatic fission of the mustard-oil glycosides. List and Occurrence Diallyl-sulfide ((CH2=CH . CH2)2S) is probably not primary. Crucif. Armoracia lapathifolia (rt), Diplotaxis tenuifolia (lvs) Lili. Allium ursinum (occurrence not confirmed) Dimethyl-sulfide ((CH3)2S) arises in some cases, at least, from Smethyl-methionine. Gerani. Pelargonium (oil) Labiatae. Mentha (peppermint-oil) Lili. Asparagus officinalis (from S-methyl-methionine) Divinyl-sulfide ((CH2=CH)2S) Lili. Allium sativum, ursinum (major constituent of oil) Methyl-3-methyl-thiopropionate (H3C—S—CH2CH2COOCH3) Bromeli. Ananas sativus (oil) 3-Methyl-thioacrylic acids, cis- and trans- forms H—C—COOH H—C—COOH and II H—C—SCH 3 H3CS-C-H do not occur free but arise from petasolesters and petasitolides?

SULFIDES AND SULFONIUM COMPOUNDS

759

3-Methyl-thiopropanol (Methionol; H3C—S—CH2CH2CH2OH) Legum. Glycine max (secondarily in soya-sauce ?) Petasolesters: yield 3-methyl-thioacrylic acids? Comp. Petasites officinalis (petasolesters -B and -C) S-Petasitolides A- and -B yield cis- and trans-3-methyl-thåoacrylåc acids (above). Comp. Petasites officinalis (? hybridus)

III DISULFIDES AND POLYSULFIDES GENERAL The disulfides are related to the thiols (mercaptans): z x R—S—HER—S—S—R+zH Several simple disulfides are known to occur in chopped onions, garlics, leeks, etc. (Allium spp.). These substances are largely responsible for the odours of these plants. They are said to be produced secondarily (or even tertiarily) from more complicated precursors such as allåån. Relatively little is known of such odoriferous constituents of plants. They are so immediately obvious that it is hard to believe that they all arise secondarily or tertiarily as a result of damage. We are reminded of the old arguments about the occurrence of free HCN in plant tissues. From the chemotaxonomic point of view the production of ill-smelling di- and polysulfides may give significant evidence of the presence of characteristic substances in some groups of plants. The genus Allium may be an example. List and Occurrence Diallyl-disulfide Lili. Allium (secondary ?) Diallyl-tetrasulfide Lilå. Allium? Diallyl-trisulfide Lili. Allium (secondary ?) Dipropyl-disulfide Lili. Allium (secondary ?) Methyl-allyl-disulfide Lili. Allium (secondary ?) Methyl-disulfide Lili. Allium (secondary ?)

760 CHEMOTAXONOMY OF FLOWERING PLANTS CH2 n CH Allinase CH2 I 2x S=0 I CH2 1 CH.NH2 COOH

Alliin

2x

CH2 II CH

CH2 CH2 II II CH CH

CH2 I H-S=0

CH2 CH2 S — S=0

+

Allicin

CH2 (+2XH2O) C-NH2 > 2x I COOH (Unstable)

C H3 I C=0 + 2xNH3 COOH pyruvic acid

Fig. i65. Alliin and allicin. Methyl-propyl-disulfide Lili. Allium (secondary ?) i -Pentenyl-z-butyl-disulfide Rut. Agathosma apiculata (ess. oil) i-Propenyl-z-sec-butyl-disulfide Umbell. Ferula foetida (ess. oil) Propyl-allyl-disulfide Lili. Allium (secondary ?)

IV SULFOXIDES AND SULFONES GENERAL The organic sulfides (above) may be oxidized to sulfoxides, R—SO—R1i and to sulfones, R—S02—R1. Only a few are considered here. The glucosides of the sulfoxides are dealt with in the next section. List and Occurrence Allicin (fig. 165) is a monosulfoxide of diallyl-disulphide. It is derived from alliin. Alliin (fig. 165) is (+)-S-allyl-l-cysteine sulfoxide. It is hydrolysed by alliinase to allicin, NH3, and pyruvic acid. Lili. Allium sativum, ursinum Sulfoxide of S-methyl-l-cysteine is said to be produced from Crucif. Brassica campestris (juice), oleracea (juice)

ISOTHIOCYANATES AND THEIR GLUCOSIDES 761

V ISOTHIOCYANATES (MUSTARD OILS) and their GLUCOSIDES GENERAL Again, we owe much of our collected information on this subject to Kjaer (1960, 1963 a, 1968). We now know that isothiocyanate-producing glucosides occur in goodly number. Many of these are glucosinolates, which Kjaer (1968) refers to as: a uniform class of thioglucoside anions [fig. 166] [which] are typical constituents of members of the families Capparidaceae, Cruciferae, Moringaceae, and Resedaceae, composing, together with Papaveraceae, and the monotypic families Tovariaceae and Bretschneideraceae, the order Rhoeadales sensu Engler and Gilg. Glucosinolates are seemingly absent in [sic] Papaveraceae, a family recently separated from Rhoeadales on botanical and biochemical evidence, whereas little is known about their presence in the two monotypic families. But Kjaer then describes a glucosinolate from Tovaria pendula. In the treatment by Melchior of the Rhoeadales (as Papaverales) in Syll.lz (1964) the family Bretschneideraceae is excluded. It is transferred to the Sapindales, an order devoid, I believe, of glucosinolates. The presence or absence of these compounds in Bretschneidera becomes, then, of great importance. If we separate the Papaveraceae also from the remaining families we have a group of five—Capparidaceae, Cruciferae, Tovariaceae, Resedaceae, and Moringaceae—all known to possess glucosinolates. Gmelin and Kjaer (1970) point out that methylglucosinolate is typical of the Capparidaceae but has not been found in the Cruciferae.

List and Occurrence

Allyl-isothiocyanate (CH, =CH . CH2NCS) arises by the enzymic fission of sinigrin (fig. 166). Alyssin (CH3SO(CH2)5NCS; 5-Methylsulfinyl-pentyl-iso-thiocyanate) arises by enzymic cleavage of glucoalyssin. Arabin (CH3SO(CH2)9NCS; 9-Methylsulfinyl-nonyl-isothiocyanate) is derived from glucoarabin. Aubrietin (p-Methoxybenzyl-isothiocyanate) arises by enzymic cleavage of glucoaubrietin. It has a taste which is pungent, yet like anis. Barbarin (fig. 166) arises by cyclization of 2-hydroxy-2 phenylethylisothiocyanate.

762 CHEMOTAXONOMY OF FLOWERING PLANTS

Benzosisymbrin, from glucobenzosisymbrin, cyclizes to (+)-4-methyl-2oxazolidin-ethione. Benzyl-isothiocyanate (Tropaeolin; C6H5CH2NCS) arises from glucotropaeolin. Berteroin (5-Methylthiopentyl-isothiocyanate; CH3(CH2)5NCS) arises from glucoberteroin. 3-Butenyl-isothiocyanate (CH2=CHCH2CH2NCS) arises from gluconapin. (+ )-z-Butyl-isothiocyanate arises from glucocochlearin. Camelinin (io-Methylsulfinyl-decyl-isothiocyanate; CH3SO(CH2)10NCS) arises from glucocamelinin. Carposide is a `sinigrin-like glycoside'. Caric. Carica papaya (lys, st., rt) Cheirolin (3-Methylsulfonyl-propyl-isothiocyanate; CH3S02(CH2)3NCS) arises from glucocheirolin. Crucif. Rapistrum rugosum (free ?) Cleomin ((—)-5-Ethyl-5-methyl-z-oxazolidinethione) arises (with cyclization ?) from glucocleomin. Erucin (4-Methylthiobutyl-isothiocyanate; CH3S(CH2)4NCS) arises by enzymic cleavage from glucoerucin. Erypestrin (Methyl-4-isothiocyanato-butyrate; CH, .O.00(CH2)3NCS) from glucoerypestrin. Erysolin (4-Methylsulfonylbutyl-isothiocyanate; CH3. S02(CH2)4NCS): from glucoerysolin? Ethyl-isothiocyanate (CH3CH2NCS) arises by enzymic cleavage of glucolepidiin. Glucoalyssin yields alyssin. Crucif. Alyssum, Berteroa Glucoarabin yields arabin. Crucif. Arabis Glucoaubrietin yields aubrietin. Crucif. Aubrietia spp., Lepidium bonariense (sd, minor constit.) Glucobarbarin yields (after cyclization ?) barbarin. Crucif. Barbarea Resed. Reseda? Glucobenzosisymbrin yields benzosisymbrin, which cyclizes to (+ )-4methyl-z-oxazolidinethione. Crucif. Sisymbrium austriacum (sd) Glucobenzsisaustricin is the benzoate of glucosisaustricin. Crucif. Sisymbrium austriacum (sd) Glucoberteroin yields berteroin. Crucif. Alyssum, Berteroa, Lunaria

ISOTHIOCYANATES AND THEIR GLUCOSIDES 763

Glucobrassicanapin (R= CH2=CH(CH2)3)

Crucif. Alyssum, Brassica

Glucobrassicin

Crucif. Brassica napus v. napobrassica Glucocamelinin yields camelinin.

Crucif. Camelina (3) Glucocapangulin

Capparid. Capparis Glucocapparin (fig. 166) is the simplest glucosinolate? Capparid. Boscia (1), Capparis (u), Cleome (12), Crataeva (z),

Gynandropsis (2), Maerua (2), Ritchiea (1), Thylachium (z) Crucif. Matthiola? (Gmelin and Kjaer, 197o, say probably not) Glucocappasalin

Capparid. Capparis (I) Glucocaulorapin: belongs here ? Glucocheirolin yields cheirolin.

Crucif. Cheiranthus, Erysimum, Malcolmia Clucocleomin yields (by cyclization ?) cleomin.

Capparid. Capparis (1), Cleome (Io), Crataeva (1), Maerua (1 ?) Euphorbi. Putranjiva roxburghii (sd) Glucocochlearin (R=(+)—CH3CH2CH(CH3)—) Gyrostemon. Codonocarpus cotinifolius (lvs, etc.)

Capparid. Capparis (3) Crucif. Arabis?, Cardamine (2), Cochlearia (3), Draba, Erysimum, Eutrema, Lunaria, Sisymbrium Euphorbi. Putranjiva roxburghii (sd) Glucoconringin (R= (CH3)2C(OH)CH2) Crucif. Cochlearia spp., Conringia orientalis Glucoerucin yields erucin.

Crucif. Brassica?, Cheiranthus?, Diplotaxis, Eruca, Farsetia, Hesperis?, Iberis, Matthiola?, Vesicaria Glucoerypestrin yields erypestrin. Crucif. Erysimum Glucoerysolin: yields erysolin? Crucif. Erysimum Glucohirsutin yields hirsutin. Crucif. Arabis hirsuta Glucoiberin yields iberin. Crucif. Brassica?, Iberis amara Glucoibervirin (R= CH3SCH2CH2CH2—)

Crucif. Cheiranthus; Iberis amara, sempervirens Glucojiaputin yields C2H5. CH(CH3)CH2NCS. Euphorbi. Putranjiva roxburghii (sd)

764 CHEMOTAXONOMY OF FLOWERING PLANTS

Glucolepidiin (R = CH3CH2) Crucif. Lepidium Glucolimnanthin yields limnanthin. Limnanth. Limnanthes douglasii (sd) Glucomalcolmin yields malcolmiin. Crucif. Malcolmia maritima (sd) Glucomatronalin Crucif. Hesperis matronalis (sd) Gluconapin (R= CH2=CHCH2CH2) Crucif. Brassica Gluconasturtiin (R= C6H5. CH2CH2—) Crucif. Brassica, Nasturtium officinale Resed. Reseda (3) Gluconorcappasalin Capparid. Capparis (3) Glucoputranjivin (R= CH3CH(CH3)—) Capparid. Capparis (3) Crucif. Cochlearia (3), Dentaria pinnata, Lunaria, Matthiola, Raphanus (z), Sisymbrium Tovari. Tovaria pendula (lvs, sd—probably this is the glucoside present) Euphorbi. Putranjiva roxburghii (sd) Glucoraphanin (R= CH3SO(CH2)4) Crucif. Brassica oleracea, Lepidium draba (lvs, etc.) Glucoraphenin (R= CH3SOCH=CH . CH2CH2—) Crucif. Matthiola annua, bicornis (sd), incana, fruticulosa (tristis) (sd); Raphanus sativus var. (rt) Plantagin. Plantago (major ?) (lvs, etc). Glucorapiferin (Progoitrin) (R= CH2=CH . CHOH . CH2) Crucif. Brassica rapa (sd) Glucosinalbate ion (p-Hydroxy-benzyl-glucosinolate ion) Crucif. Lepidium bonariense (sd, major glucosinolate) Glucosisaustricin yields (after cyclization ?) sisaustricin. Crucif. Sisymbrium austriacum (sd) Glucosisymbrin (R= HOCH2CH(CH3)—) Crucif. Sisymbrium austriacum (sd) Glucotropaeolin (R= C6H5. CH2). This glucosinolate seems to be very widely distributed. Capparid. Capparis fiexuosa (lvs) Crucif. Cardamine, Coronopus, Draba?, Lepidium (5), Sisymbrium Moring. Moringa oleifera? Tropaeol. Tropaeolum majus (lvs, sds) Euphorbi. Jatropha multifida (latex) ?

ISOTHIOCYANATES AND THEIR GLUCOSIDES 765

Caric. Carica cauliflora, chilensis, papaya, pennata, quercifolia ; arilla chocola (sds; Gmelin & Kjaer, 197o a) Salvador. Salvadora oleoides (sd) Hirsutin (8-Methyl-sulfinyloctvl-isothiocyanate) Crucif. Arabis hirsuta (sd, free ?) p-Hydroxybenzyl-isothiocyanate arises by enzymic cleavage of sinalbin. 2-Hydroxy-isobutyl-isothiocyanate arises from glucoconringiin. 2-Hydroxy-isopropyl-isothiocyanate arises from glucosisymbrin. It cyclizes to sisymbrin. 2-Hydroxy-2-phenylethyl-isothiocyanate arises by enzymic cleavage of glucobarbarin. It cyclizes to barbarin. Iberin (3-Methylsulfinylpropyl-isothiocyanate) arises from glucoiberin. Ibervirin (3-Methylthiopropyl-isothiocyanate) arises from glucoibervirin. Isopropyl-isothiocyanate is formed by enzyme action from glucoputranjivin. It is reported (free in some cases ?) from

Crucif. Cheiranthus, Cochlearia, Lunaria, Matthiola Tropaeol. Tropaeolunz Euphorbi. Putranjiva Limnanthin (m-Methoxybenzyl-isothiocyanate) arises from gluco-

limnanthin. Malcolmiin (3-Benzoyloxypropyl-isothiocyanate) arises from gluco-

malcolmiin. Methyl-isothiocyanate arises from glucocapparin. Napoleiferin ((— )-5-Ally1-2-thio-oxazolidone) is probably present in the original material as 2-hydroxy-4 pentenyl glucosinolate.

Crucif. Brassica campestris, napus v. oleifera Neo-glucobrassicin (N-Methoxy-glucobrassicin) Crucif. Brassica spp. 4-Pentenyl-isothiocyanate (CH2=CH(CH2)3NCS) arises from gluco-

brassicanapin. z-Phenylethyl-isothiocyanate arises from gluconasturtiin. Phenyl-isothiocyanate has been obtained (free ?) from

Euphorbi. Putranjiva Rapiferin (z-Hydroxy-3-butenyl-isothiocyanate) arises from glucorapi-

ferin. Sinalbin (fig. 166) is a very complicated substance. It is said to occur in Crucif. Aubrietia (3), Brassica napus, Lepidium campestre (plt), Sinapis alba (sd) Sinigrin (fig. 166 ; R = CH2=CH . CH2—) has been reported (correctly ?) from many crucifers. I have the following records:

Crucif. Armoracia, Barbarea, Brassica (4), Cakile, Capsella, Crambe, Diplotaxis (2), Draba, Erucastrum, Erysimum, Eutrema, Raphanus, Sinapis?, Sisynzbrium (2), Thlaspi

766 CHEMOTAXONOMY OF FLOWERING PLANTS

N.0.5020 CH2OH il 0 S —C —R

O

N.O.5020 S- C-CH3 GLUC.

HO ~~/ H H HO Glucocappari n

Barbarin

A GIucosinolate

N.O S020 ~K u S•C-CH2CH=CH2

N.O5020e U S-C-CH2

GLUC.

GLUC.

® N(CH3)3CH2CH2O (Sinapine)

CH CH

N Sinigrin

C=0

H H3CO

OCH3 OH

Sinalbin

Fig. 166. Mustard oil glucosides.

Sisymbrin arises by cyclization of 2-hydroxy-isopropyl-isothiocyanate (from glucosisymbrin). Sulforaphene (4-Methylsulfinyl-3-butenyl-isothiocyanate; CH3. SO . CH=CH . CH2NCS) arises from glucoraphenin.

VI THIOPHENE DERIVATIVES Plants produce many thiophene derivatives, most of which we have dealt with as acetylenic compounds. The few non-acetylenic thiophenes may be considered here though they are derived, presumably, from acetylenes (p. 96). If this is so they `should' occur only in plants that are known to produce acetylenes, and this does seem to be the case. List and Occurrence 5-(Buta-I,3-dienyl-I)-bithienyl-2,2' (fig. 167) Comp. Bidens 5-Methyl-5'(buta-I,3-dienyl-I )-bithienyl-2,2' Comp. Bidens radiatus 4-(5-Methylthienylid-2-en)-but-2-en-I ,4-olide Comp. Chamaemelum nobile (rt)

THIOPHENE DERIVATIVES 767

5' '$' Thiophene

o(-TerthienyI

S"

S"

CH:CH-CH=CH2 S'

5- (Bu t-1,3-dienyl)-2,2'-bi thienyl

A spiroketal

Fig. 167. Some thiophene derivatives. . Spiroketal (name ?) (fig. 167 ) Comp. Artemisia ludoviciana a.-Terthienyl (fig. 167) Comp. Berkheya (1), Echinops (1), Flaveria (1), Tagetes (its of 3) 6-(z-Thienyl)-hexa-2,4-dienoic acid-l-isobutylamide Comp. Chrysanthemum frutescens (rt) Thiophene (fig. 167) occurs in coal-tar, but not, I think, free in plants.

TANNINS Nierenstein, in his book The Natural Organic Tannins (1934), defined tannins as `amorphous, rarely crystalline substances which are widely distributed in the vegetable kingdom. They are remarkable for their astringent. ..taste, and for their ability to form coloured solutions and precipitates with iron and other metals. They are also precipitated from solution by albumin, gelatin, and other proteins, as well as by alkaloids. Their ability to combine with proteins is the basis of the process known as vegetable tannage.' Much work has been done on tannins since the appearance of Nierenstein's book, and we are fortunate in having a recent small volume by Haslam, Chemistry of Vegetable Tannins (1966). His definition is: `The vegetable tannins are polyphenols with a molecular weight in the range 500-3000...'. Would this exclude some of the simpler substances which may yet enter into the tanning process ? I think it would. The old classification into hydrolysable tannins and condensed tannins would still seem to hold. If we adopt this distinction then we have:

768 CHEMOTAXONOMY OF FLOWERING PLANTS

I HYDROLYSABLE TANNINS These are readily hydrolysed by acids or by enzymes into a sugar or sugar alcohol and a phenolic carboxylic acid. A further breakdown of this group may be made into: 1. Gallotannins, which yield gallic acid (fig. 93). 2. Ellagitannins, which give hexahydroxy-diphenic acid. This readily forms the more stable lactone ellagic acid (fig. rot). II CONDENSED TANNINS These are not hydrolysable with acids, but form more highly polymerized products known as phlobaphenes or tannin reds. The ' building bricks' of the condensed tannins may be such fiavonoid substances as flavan-3-ols and flavan-3,¢-diols. We have already met with dimers of such units—the biflavonyls. Hillis (1958) suggested that leucoanthocyanins, with or without catechin, may condense to form condensed tannins. Hathway and Seakins (1959) have isolated resveratrol (a stilbene) and resveratrol-3-13-n glucoside from the heartwood of Eucalyptus wandoo. It seems likely that such substances may contribute to the formation of the condensed tannins of this plant. Tannins may occur in various tissues of the plant. It has long been known that young leaves and stems may be rich in tannin or tannin-like substances. Howes, whose book Vegetable Tanning Materials (1953) appeared between those of Nierenstein and Haslam already referred to, says that the young, red leaves and twigs of Anogeissus latifolia may have 5o% tannin on a dry-weight basis! The occurrence of tannins in young tissues, and the obvious presence of other tannins in barks of many species, have led plant physiologists to speculate on the roles played by these substances. It was supposed that the Ieaf-tannins are active metabolites, used in some way in the growing tissues, while those of barks are post-mortem, but not necessarily 'waste' products. The astringency of tannins may well make them protective: compare the production of tannin in great quantities in some galls, and the presence of tannin in astringent form in unripe bananas and persimmons and in non-astringent form in the ripe fruits (Lloyd, 1911, etc.). Bate-Smith and Metcalfe (1957) made a study of the distribution of tannins in higher plants, basing their conclusions on chemical and morphological investigations. They produced essentially the following list:

TANNINS 769

1. Families with all species tanniniferous Acer., Actinidi., Anacardi., Annon., Balsamin., Begoni., BetuL, Bix., Casuarin., Cercidiphyll., Corn., Clethr., Corynocarp., Cunoni., Daphniphyll., Diapensi., Dilleni., Droser., Eben., Elaeocarp., Eric., Erythroxyl., Eucommi., Eucryphi., Eupomati., Fag., Frankeni., Guttiferae., Halorag., ,hugland., Lardizabal., Laur., Lee., Limnanth., Lythr., Magnoli., Melastomat., Meli., Monimi., Mor., Myopor., Myric., Myrsiv., Myrt., Nepenth., Nyss., Onagr., Oxalid., Plumbagin., Polygon., Prote., Punic., Rhizophor., Ros., Sabi., Sapind., Sapot., Sarraceni., Saurur., Saxifrag., Schisandr., Simaroub., Stachyur., Staphyle., Sterculi., Styrac., Tamaric., Tetracentr., The., Thymelae., Till., Trochodendr., Ulm., Urtic., Vit., Winter. 2. Families with most species without tannins Arali., Aristolochi., Asclepiad., Bignoni., Comp., Legum. (Faboideae), Nyctagin., Nymphae., Ole., Piper., Ranuncul., Scrophulari., Umbellif. 3. Families with all species without tannins Acanth., Aizo., Amaranth., Basell., Bux., Cact., Campanul., Capparid., Caryophyll., Chenopodi., Chloranth., Cneor., Convolvul., Crucif., Cucurbit., Datisc., Dipsac., Garry., Gesneri., Hippurid., Hydrophyll., Lab., Lentibulari., Lin., Loas., Papaver., Phytolacc., Plantagin., Polygal., Portulac., Resed., Solan., Tropaeol., Valerian., Verben., Viol., Zygophyll. Bate-Smith and Metcalfe compared their lists with the `advancement indices' of Sporne (1954.) and found that the `advancement indices' of of the families in list I lie between 14 and 75, with only 24. families over 5o; those of list 2 lie between 32 and 93, with only 4 families below 5o; and those of list 3 lie between 36 and loo, with only 8 (of a much longer list) below 5o. They concluded: 'These facts indicate conclusively that the capacity to synthesize tannins decreases as the advancement index numbers for the families go up. It thus seems that the capacity to synthesize tannin is a primitive character that tends to become lost with increasing phylogenetic specialization.' This is interesting speculation, and the conclusions of Bate-Smith and Metcalfe may well be justified, but our knowledge is still fragmentary, and it would be helpful to break down tannins into the ` hydrolysable' and ' condensed' groups when making phylogenetic studies. Perhaps this will be done in the future. In my own work I have used only a simple test, Tannin Test A (p. 77), on leaf-material. The results obtained are relatively few (I adopted the 4

GCO II

770 CHEMOTAXONOMY OF FLOWERING PLANTS

test rather late in my studies), but they are included in my tables, along with the results of others. Where discrepancies are obvious they may sometimes be due to the fact that reports of presence of tannins by others are often for bark, roots, or other parts of plants, while mine are (with very few exceptions) for mature leaves only. We are not sure that all positive results obtained by using Tannin Test A are for true tannins, but it seems likely that most of them are reliable indications of the presence of tannins. Negative results almost certainly indicate absence of tannins in appreciable amount.

TERPENOIDS GENERAL The terpenoids elaborated by higher plants are very numerous and varied. We may distinguish: I. II. III. IV. V. VI. VII. VIII.

Hemiterpenes, based on C5H8 Monoterpenes, based on (C5H8)2 Sesquiterpenes, based on (C5H8)3 Diterpenes, based on (C5H8)4 Triterpenes, based on (C5H8)8 Tetraterpenes, based on (C5H8)8 Pentaterpenes, based on (C5H8)10 Polyterpenes (or Polyisoprenes), based on (C5H8)>10

The following notes, based largely on a paper by Weissmann (in Swain, 1966), are concerned with the biosynthesis of terpenes (fig. 168). (a) Acetic acid + acetoacetic acid give rise to ß-hydroxy-ß-methyl glutaric add which by reduction gives mevalonic acid (which can also be formed from leucine). (b) Mevalonic acid-5-pyrophosphate gives isopentenyl pyrophosphate (IPP; `active isoprene'—a hemiterpene, the `true structural unit of all terpenoids'). (c) IPP gives rise to dimethylallyl pyrophosphate. (d) IPP+ dimethylallyl pyrophosphate give geranyl pyrophosphate (GPP; a monoterpene). Weissmann says (italics mine): The monoterpenes arise from geranyl pyrophosphate (GPP) by cyclization, rearrangement, or oxidation. The addition of another IPP unit gives farnesyl pyrophosphate which leads to the sesquiterpenes. The diterpenes are derived from geranylgeranyl pyrophosphate

TERPENOIDS 771 Leucine OH rv~OH

--i

~

OPP - -

^/COOH HOOC H

HOOC O

p -Hy droxy-ß- methyl -glutaric acid "-L----.'OPP

Mevalonic acid

).. —OPP

+ (IPP) Dimethyl al lyl-pyrophosphate ( DPP)

Isopentenyl pyrophosphate (IPP)

OPP

OPP

PPO

),..,..( DPP) Geranyl - pyrophosphate (GPP)

Fig. 168 Biosynthesis of terpenoids.

which is produced by the condensation of two GPP units ... the condensation of polyterpene chains does not stop at the stage of farnesyl pyrophosphate. The biosynthesis of the polyprenes, rubber and gutta-percha, can be envisaged as proceeding in a similar manner... In addition to the `head-to-tail' condensation of the isoprenoid units which leads to the above compounds, nature possesses a further system of building at the stage of farnesyl-PP and geranylgeranyl-PP. Tri- and tetra-terpenes can be formed by the `tail-to-tail' dimerization of the C15 and C20 units. Thus, the dimerization of farnesyl-PP forms squalene (C80), from which the cyclic triterpenes and steroids are derived. Tetraterpenes (C40), the dimerization products of geranylgeranyl-PP, are also widely distributed in the plant kingdom, for example the carotenoids. It is, as usual, difficult to place many compounds. We have discussed elsewhere the furan compounds (furans, benzofurans, dibenzofurans); the monoterpenoid alkaloids; the diterpenoid alkaloids; and some other substances, such as the coumarins and quinones, which are said to be `essentially hemiterpenoid'.

4-2

772 CHEMOTAXONOMY OF FLOWERING PLANTS I HEMITERPENOIDS GENERAL Terpenoids, with the formula C5H8 or near it, are by no means common. Isoprene (fig. 188), which may be obtained by the dry distillation of the polyterpenoid substance rubber, may formally be considered to be the unit of the higher terpenoids but it does not occur free,' nor can more complex terpenoids be resolved easily into isoprene units. Not all 5-carbon substances are believed to be biosynthetically related to the terpenoids.

II MONOTERPENOIDS GENERAL The monoterpenoid substances are legion! It seems that plants, and higher plants in particular, have learned to try every possible variation that can be derived from two hemiterpenoid units. Some monoterpenes are so common that it would require pages to list the plants known to produce them. Others are so rare that each is known only from a single plant, but this apparent rareness is sometimes deceptive, careful search revealing a more widespread occurrence. Some groups of plants are prodigal in their production of these substances. The air may be scented by the volatile compounds escaping from leaves, stems, and/or flowers. Rasmussen and Went (1964) have written: `Whereas in cities gasoline and other man-produced organic vapors constitute the bulk of the organic volatiles in the air, in the countryside...plant products predominate. Among these, a- and ßpinene, myrcene and isoprene were identified...during summer usually more than 10-8 organic volatiles occur in country or forest air; during winter this decreases to 2 x 10-92 Many of the monoterpenoids have characteristic odours, and some species have been named for their obvious constituents: Carvone Verbena carviodora, Orthodon carvoniferum Citral Backhousia citriodora, Cymbopogon citratus Incomplete as the records for monoterpenes are, some striking conclusions are evident: 1 Or does it ? I have seen a title 'Light-dependent excretion of molecular isoprene by leaves', but not the paper, by Sanadze (in Proceedings of the International Congress of Photosynthesis Research, 1968).

MONOTERPENOIDS

773

(a) The separation of the Magnoliales from the Ranunculales would seem to be supported by the prevalence of monoterpenoids in the former order: their absence from the latter. My list has been prepared without prejudice yet we find monoterpenoids in: Magnoliales I. Magnoliaceae Magnolia sp.: d-a phellandrene 5. Annonaceae Cananga odorata: 2 monoterpenoids, Monodora grandiflora: 2 monoterpenoids, M. myristica: l-a phellandrene 7. Myristicaceae Myristica fragrans: 6 monoterpenoids 8. Canellaceae Canella alba: myrcene io. Illiciaceae Illicium spp.: 4 monoterpenoids 14. Monimiaceae Peumus boldus: 3 monoterpenoids 17. Lauraceae Cinnamomum (3 spp.), Laurus, Lindem, Litsea (3 spp.), Nectandra, Sassafras between them have numerous monoterpenoids. Ranunculales one record! For further discussion see under the orders mentioned. (b) Within the Myrtales most families, to judge from my records, lack monoterpenoids in noticeable amounts. The Myrtaceae itself, however, is noteworthy for the number and variety of these substances. Thus we have: No records from any families but Myrtaceae. The following records of monoterpenoids from Myrtaceae: Agonis (I), Backhousia spp. (5), Baeckia (z), Calythrix (4), Darwinia (2), Eucalyptus spp. (at least 32!), Homoranthus (I), Leptospermum (4), Melaleuca spp. (at least Iz), Myrcia (1), Myrtus (6), Pimenta (4). (c) Few families of the Tubiflorae have appreciable numbers of monoterpenoids. The highly aromatic Labiatae, however, stand out as having many of these substances, often in very large amounts. A few members of the closely related Verbenaceae are known to have many of the same monoterpenoids. Thus we have: 7. Verbenaceae Lippia spp. (at least 13), Premna (I), Vitex (I) 9. Labiatae Agastache (z), Bystropogon (4), Calamintha (4), Elsholtzia (3), Epimeredi (I), Hedeoma (5), Hyptis (3), Hyssopus (3), Lavandula spp. (at least zo), Melissa (z), Mentha spp. (about zo), Meriandra (I), Micromeria (4), Monarda spp. (4), Mosla (I), Nepeta (I), Ocimum (at least 15), Origanum spp. (7), Orthodon spp. (6), Perilla (I), Poliomintha (I), Prunella (3), Pycnanthemum (3), Rosmarinus (z), Salvia (7), Satureia (4), Thymus (6). In the Izth syllabus the little family Callitrichaceae is placed between Verbenaceae and Labiatae. It `should' have some of these substances!

774

CHEMOTAXONOMY OF FLOWERING PLANTS

(d) Within the Umbellales (Apiales) only the Umbelliferae itself is conspicuous for its many monoterpenoids. I have records of them from more than zo genera of that family. I have a record of but i monoterpenoid from i genus of the Araliaceae; and no records from the other families. List and Occurrence Actinidiolide: belongs here ? Actinidi. Actinidia polygama (lvs) Actinidol: belongs here ? Actinidi. Actinidia polygama (lys) Artemisia-ketone (fig. 169) Comp. Artemisia annua Artemisol Comp. Artemisia tridentata (up to zo% of the ess. oil) Ascaridole (fig. 169) is a most unusual monoterpenoid. Chenopodi. Chenopodium ambrosioides var. anthelminticum (oil of lys, frt, to 77%), hircinum (sd), multifidum (plt) Borneo' (Borneo camphor; Bornyl alcohol; a-Camphol; fig. 169) in its d- and I- forms, and free or esterified, has been found in more than 15o spp. (Karrer). d-Borneol (Borneo camphor) occurs in conifers and Myristic. Myristica fragrans (sd) Dipterocarp. Dryobalanops camphora Myrt. Eucalyptus Lab. Lavandula spica, vera; Rosmarinus officinalis Valerian. Valeriana officinalis Zingiber. Elettaria cardamomum, Zingiber officinalis l-Borneol (Ngai-camphor; Linderol) occurs free and/or as esters in conifers and Aristolochi. Asarum Laur. Lindera strychnifolia Umbell. Coriandrum Valerian. Valeriana officinalis (rt) Comp. Blumea balsamifera (lvs), Matricaria parthenium Gram. Andropogon nardus Bornyl acetate is said to be a characteristic constituent of many conifers. I have no specific record of it from higher plants, but I am sure it occurs. Bupleurol Umbell. Bupleurum fruticosum Camphene (fig. 169) occurs in d- and l- forms.

MONOTERPENOIDS

775

d-Camphene (Austracamphene) occurs in conifers and Laur. Cinnamomum camphora Myristic. Myristica fragrans Monimi. Atherosperma moschatum (d- or 1-?) Dipterocarp. Dryobalanops Rut. Citrus (fl.-oil) Myrt. Eucalyptus Umbell. Foeniculum Lab. Lavandula Zingiber. Curcuma aromatica, Zingiber officinalis 1-Camphene (Terecamphene) occurs in conifers and Laur. Cinnamomum camphora Annon. Monodora grandiflora (sd-oil) Rut. Citrus bergamia, bigaradia Lab. Lavandula Valerian. Valeriana officinalis Gram. Andropogon nardus Camphor (fig. 169) occurs in d-, dl-, and 1- forms. d-Camphor Aristolochi. Aristolochia indica (rt-oil) Laur. Cinnamomum camphora, zeylanicum; Sassafras albidum Lab. Lavandula spp., Meriandra spp., Ocimum spp., Prunella Comp. Artemisia spp. Zingiber. Alpinia spp. dl-Camphor occurs in conifers and Lab. Ocimum canum Comp. Chrysanthemum sinense var. japonicum 1-Camphor Verben. Lippia adoensis Comp. Achillea moschata, Artemisia herba-alba, Matricaria parthenium, Tanacetum vulgare d- s3-Carene (?a-Carene; Isodiprene; fig. 169) occurs in conifers and Rut. Citrus reticulata? l-A3-Carene Zingiber. Kaempferia galanga (rhiz. or rt-oil) d-z 4-Carene (d-z2-Carene; ß-Carene; Dacrydene; Pinonene) occurs in conifers and Piper. Piper cubeba (frt-oil) Myrt. Eucalyptus micrantha var. (ess. oil), rariflora (1f-oil) 1-i3-Carene-5, 6-epoxide Rut. Zieria smithii (ess. oil) Carvacrol (fig. 169) occurs in conifers and Rut. Ruta spp.

776 CHEMOTAXONOMY OF FLOWERING PLANTS

Lab. Satureia hortensis, Origanum spp. (to 8o% of ess. oil), Orthodon spp. (to 6o% of ess. oil), Thymus vulgaris (to 7o% of ess. oil) Gram. Zea mays (stigmas ?) Carveol Umbell. Carum carui l-Carvomenthone Comp. Blumea eriantha, malcolmii (to 16% of ess. oil) Carvone (Carvol) : d-, dl-, and /-forms occur. d-Carvone Umbell. Anethum gravsolens (frt), Carum carvi (frt, to 85% of ess. oil) Verben. Lippia adoensis, carviodora Lab. Orthodon carvoniferum (plt, to 32% of ess. oil) dl-Carvone Laur. Litsea guatemalensis 1-Carvone Laur. Lindera sericea (1f-oil) Myrt. Eucalyptus spp. Lab. Mentha crispa (to 72% of ess. oil), Satureia montana Comp. Chrysanthemum balsamita d-Carvotanacetone (z 1 p-Menthenone-6) Comp. Blumea eriantha, malcolmii (to 82% of ess. oil); Pulicaria mauritanica (to 8t% of ess. oil) 1,4-Cineole (Cineole; Isocineole; fig. 169) Piper. Piper cubeba (unripe frt) Monimi. Daphnandra (or is it 1,8-cineole?, below), Peumus boldus (1f-oil) Rut. Zanthoxylum rhetsa (frt-oil) Comp. Ormenis multicaulis 1,8-Cineole (Cajeputol; Cineol; Cyneol; Eucalyptol; fig. 169) seems to be widely spread. Karrer says it has been found in more than 260 spp. Myric. Comptonia Laur. Cinnamomum camphora, Litsea guatemalensis (to 5o% of ess. oil) Illici. Illicium verum Piper. Piper betle Myrothamn. Myrothamnus flabellifolius? Rut. Luvunga scandens (frt, to 56% of ess. oil), Ruta Meli. Aglaia odoratissima? Myrt. Eucalyptus spp. (to 92% of ess. oil), Melaleuca spp. (to 56% of ess. oil), Myrtus communis, Pimenta

MONOTERPENOIDS

777

Lab. Lavandula, Mentha piperita, Rosmarinus officinalis, Salvia triloba (to 62% of ess. oil) Verben. Lippia Comp. Achillea micrantha (to 49% of ess. oil), Artemisia tina, Blumea lacera (to 66% of ess. oil) Trid. Crocus sativus Zingiber. Elettaria cardamomum, Zingiber officinalis Citral (Citriodoraldehyde; Geraniumaldehyde; fig. 169) exists in several forms: a-, ß-, and as citral-A (geranial) and citral-B (neral). Many of the records merely say `citral' so we have not attempted a separation in our list. Piper. Piper nigrum Laur. Sassafras albidum (1f--oil) Ros. Rosa Gerani. Pelargonium spp. Melt*. Aglaia odoratissima Rut. Citrus limetta, medica; Phebalium nudum Myrt. Backhousia citriodora (If-oil, to 97%), Eucalyptus, Leptospermum citratum (to 5o% of ess. oil), Pimenta acris Lab. Lavandula vera; Melissa officinalis; Ocimum canum (to 7o% of ess. oil), menthaefolium (to 56% of ess. oil) Gram. Andropogon spp.; Cymbopogon citratus (both citral-A and citral-B, to 75% of ess. oil) and other species Zingiber. Zingiber officinalis d-Citronellal (Citronell-aldehyde; Citronellon(e); fig. 169) Rut. Aegle marmelos Myrt. Eucalyptus spp. (to 85% of ess. oil) Lab. Lavandula, Melissa officinalis, Ocimum gratissimum Gram. Andropogon nardus l-Citronellal Myrt. Backhousia citriodora var. (to 8o% of ess. oil) Citronellic acid (fig. 569) exists as d-, dl-, and 1- forms. 1-citronellic acid has not been found in angiosperms ? d-Citronellic acid Rut. Barosma pulchellum, Citrus aurantium v. amara (If-oil, as esters), Zanthoxylum piperitum (frt-oil, free and as esters) Myrt. Calythrix virgata (1f-oil) Gram. Cymbopogon citratus dl-Citronellic acid Laur. Cinnamomum camphora Citronellol (fig. 569): the naturally occurring citronellol is mostly the fl-form. Both d- and i- forms occur, but often no indication of the form is included.

778 CHEMOTAXONOMY OF FLOWERING PLANTS

Myrt. Backhousia Verben. Lippia Gram. Andropogon, Cymbopogon d-Citronellol (Yacarol) Ros. Rosa Gerani. Pelargonium Rut. many ? l-Citronellol (Rhodinol) occurs in conifers and in Ros. Rosa Gerani. Pelargonium Myrt. Calythrix tetragona (ess. oil) Xanthorrhoe. Xanthorrhoea preissii (resin) Citronellol-ß-n-glucoside Ros. Rosa Cosmene (fig. 169) Comp. Ambrosia, Amellus strigosus, Ammobium, Coreopsis (2), Cosmos (3), Dahlia merckii, Felicia, Helianthus, Pulicaria Cryptal (4.-Isopropeny1-02-cyclohexenal): Penfold and Simonsen (193o) say: `The occurrence in admixture with each other of the 3 aldehydes cuminaldehyde, phellandral and cryptal is not without biogenetic interest, since they can all 3 arise very simply from a phellandrene, the chief hydrocarbon constituent of the oils in which they occur.' Myrt. Eucalyptus hemiphloia, etc. Cryptotaenine: belongs here ? Umbell. Cryptotaenia japonica (ess. oil) Cuminic alcohol seems to be rather widely distributed. Laur. Cinnamomum camphora Myrt. Eucalyptus bakeri (If-oil) Umbell. Cuminum cyminum (frt-oil) Eric. Ledum palustre v. dilatatum Lab. Lavandula vera Cuminic aldehyde (Cuminal; Cuminol) Monimi. Peumus boldus (1f-oil) Legum. Acacia farnesiana (fl.-oil) Rut. Aegle marmelos, Ruta spp., Zanthoxylum rhetsa Myrt. Eucalyptus Umbell. Cicuta virosa (sd-oil), Cuminum cyminum Comp. Artemisia annua, Pectis papposa (to 5o% of ess. oil) Curcumone: derived secondarily from dehydro-turmerone? Zingiber. Curcuma longa (rhiz.) ß-Cyclo-lavandulal Umbell. Seseli indicum (oil)

MONOTERPENOIDS

779

ß-Cyclo-lavandulic acid Umbell. Seseli indicum (oil) p-Cymene (Camphene; Camphogene; p-Cymol; fig. 169) is very widely spread. Laur. Litsea zeylanica Rut. Aegle marmelos, Citrus reticulata (oil) Myrt. Melaleuca linariifolia (lvs) Umbell. Cuminum cyminum (sd) Eric. Ledum palustre v. dilatatum (lvs) Lab. Elsholtzia Comp. Eupatorium Dehydro-geranic acid occurs in a conifer, but not (?) in angiosperms. Dihydro-actinidiolide: belongs here? Actinidi. Actinidia polygama (lvs) Dihydro-carveol (p-Menthen-8,9-o1-(z) ) Umbell. Carum carvi Lab. Mentha crispa, longifolia (to 25% of ess. oil), viridis var. saliva l-Dihydro-carvone Umbell. Anethum graveolens var. sowa, Carum carvi d-Dihydropinol Umbell. Carum carvi (and perhaps secondarily) z, 6-D imethylo eten-7-one(4) Comp. Tagetes minuta (glandulifera) (plt) Diosphenol (Bucco-camphor) Myrothamn. Myrothamnus flabellifolius (If-oil) Rut. Barosma betulinum (1f-oil), and other spp. Lab. Mentha Dipentene (Cajeputene; Cinene; Cynene; Diisoprene; Isoterebenthene; dl-Limonene; fig. 169) occurs in conifers and in many angiosperms. Laur. Cinnamomum camphora, Litsea zeylanica Mid. Illicium sp. Myristic. Myristica fragrans Piper. Piper nigrum Pittospor. Pittosporum tenuifolia Rut. Barosma spp., Citrus spp. Burser. Boswellia carteri, Canarium luzonicum Myrt. Baeckea, Eucalyptus, Melaleuca, Pimenta Umbell. Carum, Coriandrum, Daucus, Foeniculum Lab. Mentha crispa, Origanum spp., Salvia Verben. Lippia spp. Valerian. Valeriana officinalis Comp. Solidago

780 CHEMOTAXONOMY OF FLOWERING PLANTS

Ethyl fenchol Umbell. Foeniculum vulgare Eucarvone (Eucarvol; fig. 169): belongs here ? Aristolochi. Asarum sieboldii var. seoulensis Fenchol (I) (Fenchyl alcohol): dl- and i- forms occur in conifers. Myrt. Baeckea frutescens (dl-) Lab. Prunella Fenchone (Fenchol (z)): d- and l- forms occur, but my records do not always specify the form. Umbell. Foeniculum piperitum (frt) Lab. Lavandula burmannii Comp. Artemisia santolinaefolia, verlotorum d-Fenchone Umbell. Foeniculum vulgare (frt) Lab. Lavandula stoechas, Prunella vulgaris Comp. Blumea lacera (If-oil, to io%) l-Fenchone occurs in conifers and Comp. Artemisia frigida (to Io% of ess. oil) FilifiIone: d- and l-(enantiomer of d-) forms occur. Rut. Zieria smithii (d-) Comp. Artemisia filifolia (1-, I I % of ess. oil) Geranic acid (fig. 169) Rut. Citrus, Clausena willdenowii (1f--oil) Myrt. Calythrix virgata (to 70% of ess. oil), Eucalyptus dives Lab. Anisomeles (Epimeredi) malabarica Gram. Cymbopogon citratus Geraniol (Geranyl alcohol; Lemonol; Rhodinol) is a very common constituent of essential oils. Laur. Cinnamomum camphora Gerani. Pelargonium spp. (` Geraniums') Burser. Bursera dalpecheana Rut. Citrus bigaradia Myrt. Darwinia, Eucalyptus, Myrtus Lab. Elsholtzia, Lavandula vera, Ocimum canum Verben. Lippia citriodora Ole. Jasminum grandiflorum Gram. Cymbopogon citratus, martini Geranyl acetate Myrt. Eucalyptus Umbell. Coriandrum, Daucus carota (to 5o% of ess. oil) Geranyl cinnamate Myrt. Leptospermum lanigerum

MONOTERPENOIDS 781

Geranyl formate Myrt. Leptospermum lanigerum Geranyl-ß-glucoside Ros. Rosa Gerani. Pelargonium Hymenatherene: Karrer has hymentherene but it is named for Comp. Hymenatherum tenuifolium Isoartemisia-ketone: belongs here ? Comp. Artemisia annua l-Isodihydro-carveol is an optical isomer of dihydrocarveol. Umbell. Carum carvi Isolimonene Chenopodi. Chenopodium d-Isomenthone Gerani. Pelargonium tomentosum Lab. Bystropogon mollis; Hedeoma pulegioides; Mentha arvensis, pulegium; Micromeria abyssinica (to 42% of ess. oil) l-Isomenthone Gerani. Pelargonium capitatum (to 75% of ess. oil), tomentosum Isopiperitenone Lab. Mentha pulegium var. villosa (young plt) Isopulegol (p-Menthen-8,9-o1-(3)) Gerani. Pelargonium Myrt. Backhousia citriodora var. (d-), Leptospermum liversidgei var. B Gram. Cymbopogon citratus d-Isopulegone (a-Pulegone) Lab. Mentha pulegium, rotundifolia, timija l-Isopulegone Lab. Agastache formosanum Lavandulol Lab. Lavandula vera (free and as esters) Limonene exists in d-, dl- (see dipentene), and l- forms. d-Limonene (Carvene; Citrene; Hesperidene) is very widely distributed. It occurs in conifers and in Lour. Litsea cubeba Pittospor. Pittosporum tenuifolium Rut. Citrus spp. Umbell. Seseli indicum (sd-oil), Siler trilobum Lab. Hyptis, Ocimum Verben. Lippia turbinata, Premna tomentosa (1f-oil, d- and dl-, to 57% of ess. oil) Comp. Solidago odora (1f-oil)

782 CHEMOTAXONOMY OF FLOWERING PLANTS

Gram. Cymbopogon polyneuros l-Limonene occurs in conifers and in Myrt. Melaleuca Lab. Bystropogon mollis, Calamintha umbrosa Verben. Lippia citriodora Gram. Cymbopogon nervatus Linalool (fig. 17o) occurs as d- and 1- forms. Comp. Artemisia (cited without prefix) d-Linalool (Coriandrol) Myristic. Myristica fragrans Rut. Citrus Burser. Bursera delpechiana Umbell. Coriandrum sativum (frt-oil) Ole. Jasminum grandiflorum (fl.-oil) Lab. Elsholtzia, Lavandula vera, Ocimum kilimandscharica, Origanum majorana Gram. Cymbopogon citratus Pandan. Pandanus odoratissimus (fl.-oil) 1-Linalool (Licareol) Mor. Humulus lupulus Laur. in wood of one member Annon. Cananga odorata Rut. Atalantia; Citrus bergamia, bigaradia Lab. Lavandula vera, Mentha crispa (to 65% of ess. oil), Ocimum basilicum (to 5o% of ess. oil) Linalool epoxide (linalool monoxide) Rut. Citrus paradisi (juice) Lab. Lavandula vera (free and as esters) l-Linalyl acetate Rut. Atalantia Loliolide: belongs here ? Gram. Lolium perenne Lyratol (fig. 17o) is said `to violate the isoprene rule and must have special biogenetic features'. Comp. Cyathocline lyrata (ess. oil) Macropone (4-Isopropyl-salicyl-aldehyde) Myrt. Eucalyptus cneorifolia 1-Menthol (Peppermint camphor) Lab. Calamintha, Hedeoma, Hyptis, Mentha piperita and other spp. (to go% of ess. oil), Pycnanthemum d-Menthone Rut. Barosma pulchellum Lab. Nepeta japonica

MONOTERPENOIDS 783

1-Menthone Gerani. Pelargonium Lab. Bystropogon mollis, origanifolius; Calamintha macrostema (to 65% of ess. oil); Hedeoma pulegioides; Mentha arvensis (to 35% of ess. oil), piperita, pulegium, timija; Micromeria japonica; Pycnanthemum miticans, pilosum Gram. Andropogon fragrans 1-Methyl-4-isopropenyl-benzene Mor. Cannabis sativa (ess. oil) Mullilam-diol Rut. Zanthoxylum rhetsa Myrcene (fig. 17o) occurs in conifers and in Mor. Humulus lupulus Laur. Cinnamomum oliven Canell. Canella alba (to 9o% of ess. oil) Pittospor. Pittosporum tenuifolium Burser. Commiphora mukul (to 64% of ess. oil) Anacardi. Rhus cotinus (1f-oil, to sz%) Rut. Agathosma; Barosma; Citrus; Empleurum; Medicosma; Phellodendron amurense (to 92% of ess. oil), japonicunz Myrt. Myrcia, Pimenta acris Arali. Nothopanax simplex Umbell. Coriandrum sativum; Prangos ferganensis, pabularia (to 48% of ess. oil) Lab. Salvia sclarea Myrcenone Verben. Lippia asperifolia (fl.-oil) d-Myrtenal Myrt. Calythrix tetragona, Eucalyptus globulus (d- and dl-) d-Myrtenol (Benihinol; Darwinol) occurs in at least one conifer and in Rut. Eriostemon coxii Myrt. Darwinia grandiflora, Leptospermum lanigerum, Myrtus communis (lvs, chiefly as the acetic ester) /-Myrtenol Myrt. Myrtus communis (lvs) i-Neodihydro-carveol is an optical isomer of dihydrocarveol. Umbell. Carum carvi d-Neomenthol differs only spatially from menthol. It occurs in most of the oils containing 1-menthol. Nerol occurs as the Å-form. Ros. Rosa Rut. Citrus spp. Burser. Bursera delpechiana

784 CHEMOTAXONOMY OF FLOWERING PLANTS

Myrt. Myrtus Primul. Cyclamen europaeum Lab. Lavandula vera Verben. Lippia citriodora Agay. Polianthes tuberosa Gram. Andropogon nardus Nerol- J3-n-glycoside Ros. Rosa (fl.) Ocimene seems to be widely distributed. Laur. Litsea zeylanica (1f-oil) Rut. Boronia, Citrus, Eriostemon, Evodia, Phebalium Myrt. Agonis luehmanni, Homoranthus Umbell. Heracleum mantegazzianum (If-oil) Lab. Lavandula, Ocimum gratissimum (to 19% of ess. oil), Salvia sclarea Verben. Lippia asperifolia Gram. Cymbopogon martini Ocimenone Verben. Lippia asperifolia (fl.-oil) Orthodene Lab. Orthodon lanceolatus (1f-oil) Paeoniflorin is a monoterpene glucoside which seems to be characteristic of Paeonia. Paeoni. Paeonia japonica, lactiflora, ofacinalis, suffruticosa Perilla alcohol (Mentha-I,8(9)-dien-7-ol): d- and l- forms are known to occur. Rut. Citrus bergamia Umbell. Carum carvi Lab. Mentha trispa, Monarda fistulosa, Satureia montana Gram. Andropogon connatus (to 35% of ess. oil) ; Cymbopogon caesius, nervatus, polyneuros d-Perilla aldehyde Umbell. Siler trilobum (frt, to 40% of ess. oil), Sium latifolium (frt) l-Perilla aldehyde Lab. Perilla nankinensis d-Phellandral Umbell. Oenanthe phellandrium (frt) l-Phellandral Burser. Bursera microphylla (lvs) Myrt. Eucalyptus spp. Umbell. Anethumgraveolens var. sova (plt), Oenanthe phellandrium (frt) Comp. Haplopappus laricifolius, Parthenium argentatum

MONOTERPENOIDS 785

Phellandrenes: a- and ß phellandrenes are known, and these occur as d- and 1- forms. d-a-Phellandrene is very widely spread. It has been found in conifers and in Magnoli. Magnolia sp. Illici. Illicium Laur. Cinnamomum camphora, zeylanicum; Laurus nobilis (lvs); Sassafras albidum (lvs) Piper. Piper nigrum Gerani. Pelargonium Burser. Boswellia carteri, Bursera microphylla, Canarium luzonicum Anacardi. Schinus molle Rut. Aegle marmelos; Citrus reticulata? (as a-Ph) Umbell. Anetlium graveolens, Angelica archangelica, Foeniculum vulgare Lab. Mentha piperita Comp. Artemisia absinthium Zingiber. Curcuma longa, Zingiber officinale l-a-Phellandrene Annon. Monodora grandflora (sd-oil) Illici. Illicium Myrt. Eucalyptus (to 2o% of ess. oil), Melaleuca spp., Pimenta acris Eric. Ledum Lab. Lavandula vera Zingiber. Zingiber o,cinale d-ß-Phellandrene occurs in conifers and in Illici. Illicium Rut. Citrus reticulata? (as 13-Ph. without prefix), Skimmia laureola Burser. Bursera microphylla Myrt. Eucalyptus Umbell. Bupleurum fruticosum, Oenanthe phellandrium l-ß-Phellandrene occurs in conifers and in Annon. Monodora myristica Myrt. Eucalyptus Comp. Haplopappus laricifolius Phellandrinic acid (Tetrahydro-cuminic acid) Burser. Bursera microphylla (lvs, st.) d-a-Pinene (Australene; fig. 17o) Laur. Cinnamomum camphora Annon. Cananga odorata Myristic. Myristica fragrans (sd-oil) Monimi. Atherosperma, Daphnandra (both just as `pinene') ?

786 CHEMOTAXONOMY OF FLOWERING PLANTS

Myrt. Eucalyptus, Melaleuca, Myrtus Umbell. Coriandrum, Crithmum maritimum, Ferula galbaniflua, Foeniculum vulgare Lab. Lavandula, Ocimum Gram. Andropogon /-a-Pinene (Terebinthene) Aristolochi. Asarum europaeum Rut. Citrus bigaradia Cist. Cistus Myrt. Eucalyptus, Melaleuca Umbell. Petroselinum Lab. Hedeoma, Lavandula, Mentha, Salvia, Thymus Valerian. Valeriana officinalis Arac. Acorus calamus ß-Pinene (Nopinene; Pseudopinene; fig. 17o) in its d- and 1- forms has been found in about ioo species (Karrer). d-ß-Pinene Laur. Nectandra elaiophora (to 20% of ess. oil) Pittospor. Pittosporum tenuifolium (If-oil) Umbell. Ferula badra-kema (frt-oil), foliosa (frt-oil), Peucedanum graveolens (rt-oil) /43-Pinene has been found in conifers and in Aristolochi. Asarum Rut. Citrus aurantium var. amara, bergamia Dipterocarp. Dryobalanops camphora Umbell. Coriandrum, Cuminum Lab. Hyssopus officinalis, Thymus Comp. Amphiachyris dracunculoides (to S3% of ess. oil) Gram. Andropogon nardus l-Pinocampheol Lab. Hyssopus officinalis Pinocamphone (fig. 17o) Lab. Hyssopus ambiguus (l-), officinalis (l-, to 52% of ess. oil) l-Pinocarvenl Myrt. Eucalyptus globulus l-Pinocarvone (Isocarvone) Chenopodi. Chenopodium ambrosioides (to 57% of ess. oil) Myrt. Eucalyptus globulus Piperitenone Lab. Mentha pulegium var. villosa (young plt), piperita Piperitenone epoxide (?Lippione; fig. 17o) Lab. Mentha rotundifolia (to 5o% of ess. oil) Verben. ?Lippia turbinata (` lippione')

MONOTERPENOIDS 787

d-Piperitol Gram. Andropogon /-Piperitol Myrt. Eucalyptus spp. Piperitol caproic ester Myrt. Eucalyptus Piperitone (z1-Menthenone-(3)) occurs in d- and 1- forms Lab. Mentha piperita and other spp. (d-) Myrt. Eucalyptus piperita and other spp. (1-) Gram. Andropogon iwarancusa (d-, to 8o% of ess. oil), sennaarensis l-Piperitone epoxide Lab. Mentha silvestris (to 68% of ess. oil) d-Pulegone (ß-Pulegone) Lab. Bystropogon spp., Calamintha spp., Hedeoma pulegioides, Mentha pulegium and other spp., Micromeria abyssinica, Origanum dictamnus, Poliomintha incana, Pycnanthemum spp., Satureia odora l-Pulegone Lab. Agastache formosanum (to 80% of ess. oil) Sabinene occurs in conifers and in Urtic. Pilea sp. (d-) Piper. Piper cubeba (frt-oil, d-) Saxifrag. Ribes nigrum (lvs, st., 1-) Pittospor. Pittosporum eugenioides (1f--oil, d-) Rut. Atalantia monophylla (1f-oil, to 38%), Zanthoxylum rhetsa Lab. Hyptis suaveolens (i-), Ocimum canum (d-), Orthodon spp. (d-) Verben. Vitex negundo (1-) Comp. Artemisia Zingiber. Curcuma longa (rhiz.-oil, d-) Salvene Lab. Salvia jurisicii, officinalis Santene: belongs here ? Santal. Santalum album Lab. Mentha rotundifolia Agay. Furcraea gigantea (fl.-oil) a-Santolinenone Comp. Santolina chamaecyparissus ß-Santolinenone Comp. Santolina chamaecyparissus Sylvestrene (fig. 17o) : d-, dl-, and 1- forms are known. d-Sylvestrene does not occur naturally, says Karrer, it arises from tarene?

788 CHEMOTAXONOMY OF FLOWERING PLANTS

dl-Sylvestrene (Carvestrene) is known from conifers. Tagetone is said to occur in 2 forms (I and II). Comp. Tagetes minuta (glandulifera) (fl. plt), patula (fl.) (as a mixture of I and II in each case ?) Teresantalic acid (fig. 17o): belongs here? Santal. Santalum album (wd, free and as esters) Teresantalol Santal. Santalum album trans-Terpin Anacardi. Schinus molle (frt) a-Terpinene (z 1'3 p-Menthadiene; fig. 17o) Rut. Citrus reticulata, Zanthoxylum spp. Meli. Aglaia Myrt. Eucalyptus, Melaleuca Umbell. Coriandrum sativum Lab. Ocimum spp., Origanum majorana Comp. Artemisia cina ß-Terpinene (i 3.1(7> p-Menthadiene) Pittospor. Pittosporum tenuifolium y-Terpinene (Crithmene; Moslene) Rut. Citrus reticulata Myrt. Eucalyptus, Melaleuca Umbell. Coriandrum sativum, Crithmum maritimum; Cuminum cyminunt Lab. Mosla grosseserrata, japonica; Ocimum viride; Thymus Terpinenol-(i) Laur. Cinnamomum camphora d-Terpinenol-(4) (Origanol) occurs in conifers and in Myristic. Myristica fragrans (sd-oil) Piper. Piper cubeba (frt) Myrt. Eucalyptus australiana; Melaleuca alternifolia, linariifolia, raphiophylla Lab. Origanum majorana, Thymus vulgaris Zingiber. Elettaria cardamomum 1-Terpinenol-(4) Rut. Zanthoxylum rhetsa (frt) Myrt. Eucalyptus dives Terpineols: a-, ß- and y- forms are known. d-a-Terpineol occurs in conifers and in Illici. Illicium veruro Rut. Citrus aurantium (peel), bigaradia Umbell. Levisticum officinale (rt-oil) Lab. Origanum majorana

MONOTERPENOIDS 789

Verben. Lippia citriodora Zingiber. Elettaria cardamomum dl-a-Terpineol Laur. Cinnamomum camphora var. glaucescens (If-oil) Monimi. Peumus boldus Gerani. Pelargonium spp. (1f-oils) Myrt. Melaleuca leucadendron l-a-Terpineol seems to be quite widely spread. It is found in conifers and in Laur. Cinnamomum zeylanicum (1f-oil), Laurus nobilis (?lf-oil) Aristolochi. Asarum canadense Guttif. Hypericum spp. (or is it dl-?, unripe frt) Rut. Citrus Timetta Burser. Bursera delpechiana Dipterocarp. Dryobalanops camphora Ole. Jasminum grandiflorum (fl.) Comp. Artemisia Gina Gram. Cymbopogon caesius ß-Terpineol: does not occur in higher plants ? y-Terpineol has been found in at least one conifer and in Laur. Cinnamomum zeylanicum (1f-oil) Terpinolene has been found in many conifers and in Umbell. Cachrys alpina Lab. Ocimum canum, kilimandscharicum oc-Thujene (Origanene) has been found in conifers, including Thuja, as the name suggests, and in Burser. Boswellia serrata (resin) Myrt. Eucalyptus dives (d- and dl-), Melaleuca linariifolia Lab. Origanum (d- ?), Orthodon spp. Thujones (Absinthol; Absinthone; Salviol; Salvone; Tanacetone; Thujol; fig. 170) occurs in cc- and ß- forms. a-Thujone (1-Thujone) is in Thuja and Verben. Lippia ß-Thujone (d-Isothujone) Lab. Salvia officinalis Comp. Artemisia spp., Tanacetum vulgare and other spp. Thujyl alcohol (Tanacetyl alcohol; Thujol) occurs free and as esters. Comp. Artemisia arborescens (to zo% of ess. oil), eucina, scoparia, transiliensis Thymohydroquinone (fig. 17o) occurs in conifers and in Umbell. Foeniculum vulgare Lab. Monarda citriodora, futulosa, punctata

790 CHEMOTAXONOMY OF FLOWERING PLANTS

O' C a mphene

Borneo)

Ascaridole

Artemisia-ketone

OH

dD0 Camphor

CHO

æ3 Carene

CHO

Car vac rot

COON

1,4-Cineole

COON

1,8-Cineole

CHZOH

and

CH2OH

and ß-

eOCitral

Citronellal

Citronellic acid

Citronellol

COOH

? Cosmene

p-Cymene

pentene

Eucarvone

Geranic acid

Fig. 169 Some monoterpenoid substances.

Thymohydroquinone-dimethyl ether Comp. Artemisia montana (rt-oil); Eupatorium capillifolium (If-oil), triplinerve (If-oil) Thymol (Isopropyl-m-cresol; fig. 17o) is said to be used by Elodea as a precursor of lignin (Siegel, 1 954). Umbell. Carum copticum (Ptychotis ajowan) (sd-oil) Lab. Monarda punctata; Ocimum gratissimum, viride; Thymus vulgaris (to 45% of ess. oil) Thymol-methyl ether Umbel). Crithmum maritimum

MONOTERPENOIDS 791

HO

HO

HOH2C OH

Linalool

Linalool epoxide

Lyratol

Myrcene

(r°

ß-

ß-

Phellandrenes

Pinenes

COOH

6Y.

OH

Pinocamphone

Piperitenoneepoxide

Terpinenes

« OH

HO OH

OH ßTerpin eols

k~

B-

a-

Teresantalic acid

d-Sylvestrene

L-Menthol

OH

Y-

Thujone Thymohydroquinone

Thymol

Fig. 17o Some monoterpenoid substances. Lab. Monarda punctata?, Orthodon hadai Comp. Eupatorium Thymoquinone is both a monoterpene and a benzoquinone: it occurs in

conifers and in Ranuncul. Nigella sativa (sd) Umbell. Carum Lab. Monarda (perhaps secondary)

Umbellulone (Oreodaphnol; Umbellol) Laur. Umbellularia (Oreodaphne) californica

792 CHEMOTAXONOMY OF FLOWERING PLANTS

d-Verbenol Burser. Boswellia carteri Verbenone Burser. Boswellia carteri Verben. Lippia citriodora

III SESQUITERPENOIDS GENERAL An enormous amount of work is going on in this field. New sesquiterpenes are being discovered almost daily, it would seem, and new plants are being investigated for occurrence of known members of this big group. Some of this work is very detailed indeed, being carried down to the population level, with interesting results which we must exclude from our treatment, however. Toribio and Geissman (1968) discuss the origins of sesquiterpene lactones and other sesquiterpenes and say: The presence of costunolide in H[ymenoclea] monogyra and of ilicic acid in H. salsola and H. monogyra supports the view, which is generally held, that the sesquiterpene lactones of the Compositae owe their origin to an initial cyclization of farnesyl pyrophosphate to a cyclodecadiene, followed by the formation of the —C(COOH)=CH2 side-chain and eventual lactonization after introduction of oxygen at an adjacent position. .. Clearly ilicic acid is close to the origin of this sequence, costunolide and parthenolide following closely, and the more elaborate eudesmolides, guaianolides and pseudo-guaianolides being formed by later cyclizations to bicyclic ring systems ... [fig. 171]. We shall have something to say about the taxonomic value of these substances elsewhere. We may note one or two points here, however. (a) Just as a clear distinction could be drawn between Magnoliales and Ranunculales, using distribution of monoterpenoids (above), so we find a sharp difference in occurrence of sesquiterpenoids in the two orders (numbers of sesquiterpenoids bracketed): Magnoliales 1. Magnoli. Michelia champaca (t) 4. Winter. Drimys winteri (1) 5. Annon. Annona sp. (t), A. squamosa (I) ; Cananga odorata (I) 8. Canell. Cinnamosma fragrans (3), Warburgia ugandensis (3) I o. Illici. Illicium anisatum (7-8)

SESQUITERPENOIDS

793

O(PP )

A cyclodecadiene Farnesyl pyrophosphate

Ilicic acid

Eu desmanol i des Guaianol i des and Pseudo guaianol ides

Parthenol ide

Costunolide

Fig. 171. Possible origins of some sesquiterpenoids.

17. Laur. Aniba rosaeodora var. (I) ; Cinnamomum camphora (1), kanahirai (I); Lindera strychnifolia (.); Litsea zeylanica (I); Machilus kusanoi (1); Nectandra elaiophora (3); Neolitsea zeylanica (z) Ranunculales—none! (b) Novotny et al. (1966), in a paper on the chemotaxonomy of some species of Petasites (Compositae), say: `The occurrence of sesquiterpenoid lactones (compounds of the santonine, guaianolide, ambrosanolide, germacranolide and eremophilanolide type) may be taken for a new taxonomic character.' At least one plant, Eremophila freelingii (Myopor.), contains an acetylenic sesquiterpene (freelingyne, considered under acetylenic compounds). It is probable that others occur. We may discuss and list the sesquiterpenoids as several more or less distinct groups: 1. Bisabolene group, about a dozen . 2. Cadinene group, about 3o. 3. Drimenol group, about 8. 4. Eremophilone group, over 3o. 5. Germacranolide group, probably larger in number than my list of 9. 6. Guaianolide group, nearly 6o. 7. Pseudoguaianolide group, about 5o. 8. Selinene (Eudesmol) group, nearly 5o. 9. Dilactone group, an unnatural group of about 8.

794

CHEMOTAXONOMY OF FLOWERING PLANTS

III. i Bisabolene group GENERAL Although a small group in numbers, these compounds are widely spread in plants, occurring in many dicotyledonous families and in the monocotyledonous Zingiberaceae. The very widely distributed bisabolene (fig. 172) may be considered to be the type substance of the group. List and Occurrence Anymol (?Animol) is a diastereomer of bisabolol. Myopor. Myoporum crasszfolium (wd, chief sesquiterpene) Atlantones (a.-, ß-, and y-) occur in conifers and in Zingiber. Curcuma longa (tr., which one ?) Bisabolene (Limene; fig. 172) is widely distributed. Salic. Populus balsamifera (buds) Piper. Piper volkensii (lvs, oil, 25%) Laur. Cinnamomum kanahirai Legum. Dalbergia sissoo (htwd) Erythroxyl. Erythroxylum monogynum (wd) Burser. Commiphora erythraea (resin) Meli. Lansium annamalayanum (wd) Rut. Murraya exotica (lvs, oil) Umbell. Daucus carota (sd, oil), Seseli tortuosum Lab. Lavandula; Ocimum gratissimum (ess. oil, 54%), and other spp.; Orthodon spp. Bisabolol Salic. Populus balsamifera (buds, d-) Legum. Myrocarpus spp. (wd) Rut. Citrus Myopor. Myoporum crassifolium (wd) Comp. Matricaria chamomilla (ess. oil) a-Curcumene (fig. 172) Zingiber. Curcuma aromatica (rhiz.) ß-Curcumene Lour. Nectandra elaiophora (d-, 15% of ess. oil) Zingiber. Curcuma aromatica (rhiz., l-a- and l-ß-) Dehydro-turmerone (ar-Turmerone) Laur. Nectandra elaiophora Lanceol Santal. Osyris tenuifolia (ess. oil), Santalum lanceolatum (wd)

SESQUITERPENOIDS

Bisabolene

a - Curcumene

795

Zi ng i berene

Fig. I72 Some sesquiterpenes of the bisabolene group.

Turmerone Laur. Nectandra elaiophora Zingiber. Curcuma ( ?longa) Zingiberene (fig. 172) Lab. Thymus serpyllum (lis) Zingiber. Curcuma longa (rhiz. oil, 25%), zedoaria (rhiz. oil); Zingiber officinale (rhiz. oil)

III.2 Cadinene group List and Occurrence Acorone Arac. Acorus calamus Cadinene (fig. 173) is, say Campbell and Soifer (1942), `the most widely distributed sesquiterpene found in Nature'. We have records from conifers and from Piper. Piper Salic. Populus balsamifera (buds, d-) Legum. Hardwickia pinnata (l-«-) Dipterocarp. Dryobalanops camphora Comp. Anthemis (Z-) y-Cadinene Illici. Illicium anisatum 5-Cadine Illici. Illicium anisatum C-Cadinene Annon. Cananga odorata (fl.-oil) Cadinol (a-, /3-, and y- forms; a-Amyrol; Sesquigoyol (y-form)) Piper. Piper lowong (frt, l-) Legum. Myroxylon balsamum and other spp. (bk and wd-oils, Z-) Rut. Amyris Meli. Cedrela toona (wd-oil, 1-)

796 CHEMOTAXONOMY OF FLOWERING PLANTS

Myrt. Eucalyptus maculata Umbell. Ferula (d-) Calamendiol (Calameone) Arac. Acorus calamus Carotol: belongs here ? Umbell. Daucus carota (sd), Seseli tortuosum (sd, to 39% of oil ?) Copaene Illici. Illicium anisatum (a- and ß-) Legum. Sindora inermis, wallichii Dipterocarp. Anisoptera (9—Io), Cotylelobium (2), Dipterocarpus (42 ?), Doona, Dryobalanops, Upuna Meli. Cedrela toona (wd), Dysoxylum fraserianum (wd) Lab. Orthodon methylisoeugenoliferum Cyper. Cyperus rotundus (ess. oil) (+)-Copadiene Cyper. Cyperus rotundus (ess. oil) a-Cubebene Illici. Illicium anisatum Cubenol Piper. Piper cubeba (ess. oil) Epi-cubenol: differs only spatially from cubenol? Piper. Piper cubeba (ess. oil) Epi-khusinol Burser. Canarium strictum (resin) 3-Hydroxy-8-isopropyl-7-methoxy-5-methyl-z-naphthaldehyde (fig. 173): belongs here? Ulm. Minus carpinifolia, glabra (wd), rubra; but absent from U. laevis, thomasi 3-Hydroxy-8-isopropyl-5-methyl-z-naphthaldehyde: belongs here ? Ulm. Ulmus carpinifolia, glabra (wd), rubra; but absent from U. laevis, thomasi (wd) 3-Hydroxy-8-isopropyl-5-methyl-5, 6,7,8-tetrahydro-2naphthaldehyde: belongs here ? Ulm. Ulmus carpinifolia, glabra (wd), rubra; but absent from U. laevis, thomasi (wd) 5-Isopropyl-3,8-dimethyl-z-naphthol (7-Hydroxy-cadalene; fig. 173) Ulm. Ulmus carpinifolia, glabra (wd), rubra; but absent from U. laevis, thomasi (wd) I -Isopropyl-4-methylen-7-methyl-1,2,3,6,7,8,9-heptahydronaphthalene Piper. Piper cubeba (frt) Khusinoxolide Grain. Vetiveria zizanioides (oil; N. India)

SESQUITERPENOIDS

797

H3CO

Cadinene

3-Hydroxy-8-isopropyl-7-methoxy-5-methyl - 2- naphthaldehyde

5-Isopropyl-3,8-di methyl-2-naphthol (7-Hydroxy-cadalene)

HO

O Mansonone-A

Oplopanone

Fig. 173. Some sesquiterpenes of the cadinene group.

Mansonone-A (fig. 173) is also a 1,z-naphthaquinone. Sterculi. Mansonia altissima (htwd) Mansonone-B Sterculi. Mansonia altissima (htwd) Mansonone-C is also a 1,z-naphthaquinone. Sterculi. Mansonia altissima (htwd) Mansonone-D is also a 1,z-naphthaquinone. Sterculi. Mansonia altissima (htwd) Mansonone-E is also a 1,z-naphthaquinone. Sterculi. Mansonia altissima (htwd) Mansonone-F is also a 1,z-naphthaquinone. Sterculi. Mansonia altissima (htwd) Mansonone-G is also a 1,z-naphthaquinone. Sterculi. Mansonia altissima (htwd) Mansonone-H is also a 1,z-naphthaquinone. Sterculi. Mansonia altissima (htwd) Metrosiderene Myrt. Metrosideros umbellata (ess. oil) Oplopanone (fig. 173) : belongs here ? Arali. Oplopanax japonicus (rt)

798

CHEMOTAXONOMY OF FLOWERING PLANTS

OCO.CH3 Drimenol

Cinnamodial

Cinnamolide

HO Farnesiferol-A

Farnesiferol-C

Fig. 174 Sesquiterpenoids of the drimenol group.

I11.3 Drimenol group GENERAL Appel, Brooks and Overton (1959) reported the isolation of drimenol (fig. 174). A few years later Brooks and Draffan (1966) wrote: `The isolation of drimenol provides an interesting chemotaxonomic link between the Winteraceae and Canellaceae, confirming their relationship despite the considerable morphological and geographical gap between the families.' Drimenol is said to constitute a biogenetic link between its own group of sesquiterpenoids and the di- and triterpenoids. Several other sesquiterpenoids seem to belong to this same group, some occurring in the Canellaceae. List and Occurrence Cinnamodial (fig. 174) Canell. Cinnamosma fragrans (bk) Cinnamolide (fig. 174) Canell. Cinnamosma fragrans (bk) Cinnamosmolide Canell. Cinnamosma fragrans (bk)

SESQUITERPENOIDS

799

Drimenol (fig. 174) Canell. Warburgia ugandensis (htwd) Winter. Drimys winteri (bk) Farnesiferol-A (fig. 174) has a coumarin group. Umbell. Ferula asafoetida Farnesiferol-B resembles farnesiferol-A but has only one ring in its drimenol section. Umbell. Ferula asafoetida Farnesiferol-C (fig. 174) is very like farnesiferol-B. Umbell. Ferula asafoetida Iresin is very like cinnamolide. It has been described as `an important link in the terpene biogenetic scheme'. Amaranth. Iresine celosioides (plt)

III.4 Eremophilone group List and Occurrence Albopetasin Comp. Petasites albus Albopetasol Comp. Petasites albus z-Angelyl-furo-eremophilane Comp. Petasites albus, kablikianus Angelyl-japonicin Comp. Petasites albus, kablikianus, japonicus, spurius Calarene (B-Gurjunene): belongs here? Dipterocarp. Dipterocarpus (42?) Diangelyl-japonicin Comp. Petasites albus, kablikianus, japonicus, spurius Dimethoxy-dihydro-furano-eremophilane Comp. Petasites hybridus Eremophilene Comp. Petasites albus, hybridus, kablikianus Eremophilenolide (fig. 175) is a lactone. Comp. Petasites hybridus Eremophilone (fig. 175) Santal. Fusanus? Myopor. Eremophila mitchelli (wd-oil) Euryopsol: belongs here ? Comp. Euryops floribundus (resin)

800

CHEMOTAXONOMY OF FLOWERING PLANTS

Euryopsonol (3a-Hydroxy-9-oxo-furano-eremophilane) Comp. Euryops floribundus (resin) a-Ferulene Umbell. Ferula communis Furano-eremophilane Comp. Petasites hybridus Furano-petasin Comp. Petasites hybridus Hydroxy-dihydro-eremophilone (Santal-camphor) Santal. Santalum preissianum Myopor. Eremophila mitchelli 6-Hydroxy-eremophilenolide Comp. Petasites albus Hydroxy-eremophilone Myopor. Eremophila mitchelli Jatamansone: belongs here ? The formula I have is not exactly that of an eremophilone sesquiterpene. Valerian. Nardostachys jatamansi (rhiz.) Kablicin Comp. Petasites kablikianus Ligularone is a dehydro petasalbin ? Comp. Ligularia sibirica Nardostachyone Valerian. Nardostachys jatamansi Nootkatone Rut. Citrus paradisi (frt, peel-oil) Petasalbin Comp. Ligularia sibirica, Petasites albus Petasin (fig. 175) Occurrence ? Petasitolide Comp. Petasites hybridus S-Petasitolide-A Comp. Petasites hybridus S-Petasitolide-B Comp. Petasites hybridus Valencene Rut. Citrus (oil) Valerianol Valerian. Valeriana officinalis (rt) a-Vetivone (Isonootkatone) Gram. Vetiveria zizanioides (rt)

SESQUITERPENOIDS 80I

II

0 E remophi lone

Eremophilenolide

Petasin

Fig. 175. Some sesquiterpenes of the eremophilone group.

Warburgiadione Canell. Warburgia ugandensis (htwd) Warburgin Canell. Warburgia ugandensis (htwd) Zerumbone: belongs here ? Zingiber. Zingiber zerumbet (rhiz.)

III .5 Germacranolide group GENERAL I am by no means sure that all of the sesquiterpenes listed here should be called germacranolides. List and Occurrence Bachanolide: belongs here? Comp. Artemisia balchanorum Costunolide Comp. Hymenoclea monogyra Elephantin is said to be tumour-inhibiting. Comp. Elephantopus elatus (plt) Elephantopin is very like elephantin. Comp. Elephantopus elatus (plt) Eupatoriopicrin Comp. Eupatorium cannabinum Germacrone Gerani. Geranium Parthenolide (fig. 176) Magnoli. Michelia champaca (rt) Comp. Ambrosia dumosa (diploid and polyploid), confertiflora (some populations); Chrysanthemum parthenium s

GCO II

802 CHEMOTAXONOMY OF FLOWERING PLANTS

,O or HO

HO u O

Vernot i de

Parthenolide

Fig. 176 Two germacranolides.

Tamaulipin-B Comp. Ambrosia confertiflora (lvs) Vernolide (fig. 176) is said to be a germacranolide. Comp. Vernonia colorata

III . 6 Guaianolide group GENERAL These have essentially the structure of guaiane (fig. 177). A few of them, such as absinthin and anabsinthin, are sesquiterpene dimers. They are most frequent in the Compositae. Steelink and Spitzer (1966) say: `The guaianolides, a class of sesquiterpene lactones with the guaiane skeleton (I) appear to possess potential application in the chemotaxonomy of higher plants.' They list no less than 4z lactones of which 27 occur in Gaillardia and Helenium, and have the `pseudoguaianolide' skeleton (II), while the remaining 15, which occur in Achillea, Artemisia, and Matricaria, possess skeleton (III). Since the first 2 genera are placed in the Helenieae, and the 3 last in the Anthemideae, Steelink and Spitzer are tempted to speculate as follows: `Thus, the above chemical features may be characteristic of the two tribes rather than just the above genera. If this is true, as these results suggest, the two classes of sesquiterpene lactones might originate from a precursor common to both tribes. The divergence from the precursor should be explicable on the basis of one or two simple gene-controlled steps.' List and Occurrence Absinthin (fig. 178) is a guaianolide dimer. Comp. Artemisia Acetoxy-achillin Comp. Achillea

SESQUITERPENOIDS 803

Achillin (fig. 178) is a stereoisomer of deacetoxy-matricarin. Comp. Achillea lanulosa Allo-aromadendrene Illici. Illicium anisatum Dipterocarp. Anisoptera (4-5), Cotylelobium (2 ?), Dipterocarpus (24 ?), Dryobalanops Anabsinthin is a guaianolide dimer. Comp. Artemisia Arbiglovin Comp. Artemisia Arborescin Comp. Artemisia arborescens, Matricaria Aromadendrene is widely spread. It occurs in conifers and in Laur. Litsea zeylanica (lvs) Meli. Aglaia odoratissima (ess. oil, to 5o%) Myrt. Agonis, Eucalyptus (many), Leptospermum, Metrosideros Arali. Nothopanax simplex (ess. oil) Lab. Perovskia spp. Artabsin Comp. Artemisia Artilesin is isomeric with matricarin. Comp. Artemisia tilesii Calocephalin Comp. Calocephalus brownii (lys, st.) Carpesia-lactone: belongs here? Occurrence ? Chamissonin: belongs here? It is a near-guaianolide. Comp. Ambrosia acanthicarpa and chamissonis (which are said to be very closely related) a-Chigadmarene Meli. Lansium annamalayanum (wd-oil) Cumambrin-A (Cumambrin-B-8-acetate) Comp. Artemisia nova, tripartita subsp. rupicola; but absent from A. tridentata Cumambrin-B (Artenovin) Comp. Ambrosia acanthicarpa, cumanensis; Artemisia nova, tripartita subsp. rupicola; but absent from A. tridentata Cyperene: belongs here ? Dipterocarp. Dipterocarpus (42 ?), Dryobalanops oblongifolia Cyper. Cyperus Cyperenol: belongs here ? Cyper. Cyperus scariosus (tuber) 5-2

804 CHEMOTAXONOMY OF FLOWERING PLANTS

Cyperotundone: belongs here? Cyper. Cyperus articulatus, rotundus, scariosus Deacetoxy-matricarin (Leucodin; Leukodin) Comp. Artemisia leucodes, tridentata subsp. tridentata; but absent from A. nova, and tripartita subsp. rupicola Deacetyl-matricarin Comp. Achillea lanulosa; Artemisia tilesii; but absent from A. nova, and tripartita subsp. rupicola Dehydro-costus-lactone: belongs here? 8-Deoxy-cumambrin-B Comp. Artemisia nova, tripartita subsp. rupicola; but absent from A. tridentata Dihydro-pseudoivalin Comp. Iva microcephala (+ )-Epoxy-guaiene Cyper. Cyperus rotundus (ess. oil) Estafiatin Comp. Artemisia mexicana (` Estafiate'), Cotula coronopifolia (ab. gd) Eupatorin Comp. Eupatoria rotundifolium Eupatorin-acetate is said to be a tumour-inhibitor. Comp. Eupatorium rotundifolium Globicin Comp. Matricaria Globulol Myrt. Eucalyptus globulus Guaiazulene (Eucazulene; Gurjunazulene; Kessazulene; S-Guaiazulene) is said to be widely distributed, but I have few records. Laur. Cinnamomum camphora Myrt. Eucalyptus globulus (—)-a-Guaiene Cyper. Cyperus rotundus (ess. oil) S-Guaiene exists in two forms. Lab. Pogostemon patchouly (mixture of z forms) Irid. Iris germanica (oil) Guaiol (Champacol; Guajol; fig. 178) Zygophyll. Bulnesia sarmienti (wd), Guaiacum officinale (resin; wd-oil) Myrt. Eucalyptus maculata Umbell. Meum a-Gurjunene Gutt. Hypericum perforatum? Dipterocarp. Cotylelobium (3), Dipterocarpus (42 ?), Upuna

SESQUITERPENOIDS 805

ß-Gurjunene: belongs here? Dipterocarp. Dipterocarpus? y-Gurjunene Dipterocarp. Dipterocarpus (42?) 8-Hydroxy-achillin is a stereoisomer of deacetyl-matricarin. Comp. Achillea lanulosa, Artemisia Jacquinelin Comp. Sonchus jacquinii (st.), pinnatus (st), radicatus (st.) Kesso-glycol-diacetate: belongs here ? Valerian. Valeriana officinalis cc-Kessyl-alcohol: belongs here ? Valerian. Valeriana japonica (rt-oil, chiefly as acetate), officinalis v. angustifolia (rt-oil, as acetate) Lactucin: belongs here ? Comp. Lactuca virosa Ledol (Ledum-camphor) : belongs here ? Aristolochi. Aristolochia indica Cist. Cistus (a) Rut. Eriostemon, Phebalium Eric. Ledum (3) Lab. Sphacele Leucomysin is a stereoisomer of deacetoxy-matricarin. Comp. Artemisia Matricarin (Artilesin-A; fig. 178) Comp. Achillea lanulosa; Artemisia tilesii (but absent from A. nova, and tripartita subsp. rupicola); Matricaria chamomilla Matricin Comp. Artemisia, Matricaria chamomilla Partheniol Comp. Parthenium argentatum (free, and as the cinnamyl ester) Patchoulenol: belongs here ? Cyper. Cyperus scariosus (tu.) Patchouly alcohol (Patchouly camphor) Lab. Pogostemon patchouly Pro-chamazulenogen Comp. Artemisia absinthium Pseudo-ivalin Comp. Calocephalus brownii (lvs, stem), Iva microcephala Pseudo-ivalin-acetate Comp. Calocephalus brownii (lvs, st.) (— )-Rotundone Cyper. Cyperus rotundus (ess. oil)

8o6

CHEMOTAXONOMY OF FLOWERING PLANTS

Mexicanin-C

I.Guaiane skeleton

OH

.1. HO Pulchellin

II. Pseudoguaianolide skeleton

0Il 0 Il O

II O

Achillin Fig. 177 Guaianolides and pseudo-guaianolides.

DI.

0

ii 0 Achillin

Guaiane

OH Guaiol

OAc II

0

Absinthin

II 0

0

II

0 Matricarin

Fig. 178 Guaiane, guaiol and guaianolides.

SESQUITERPENOIDS 807

Virginolide Comp. Helenium virginicum Zaluzanin-A: belongs here? Comp. Zaluzania augusta Zaluzanin-A-3-acetate (Zaluzanin-B) Comp. Zaluzania augusta Zaluzanin-C Comp. Zaluzania augusta, triloba Zaluzanin-C-acetate (Zaluzanin-D) Comp. Zaluzania triloba

III.7 Pseudoguaianolide group GENERAL These sesquiterpenes are quite numerous—my list has 5o or so—but they seem to be restricted to the Compositae. In that great family they occur in at least 9 genera, almost all of which are in the Heliantheae and Helenieae. List and Occurrence Amaralin Comp. Helenium tenuifolium (amarum) Ambrosin (fig. 179) Comp. Ambrosia maritima; Helenium tenuifolium (amarum); Hymenoclea monogyra, salsola (pit); Parthenium hysterophorus, incanum Ambrosiol Comp. Ambrosia dumosa (diploid), psilostachya Apoludin Comp. Ambrosia dumosa (polyploid) Aromaticin Comp. Helenium aromaticum, tenuifolium (amarum) Aromatin (6-Deoxy-helenalin) is a stereoisomer of aromaticin. Comp. Helenium aromaticum Balduilin Comp. Balduina unifiora Bigelovin Comp. Helenium bigelowii Burrodin Comp. Ambrosia dumosa (polyploid)

Sob

CHEMOTAXONOMY OF FLOWERING PLANTS

Confertiflorin Comp. Ambrosia acanthicarpa, confertiflora Coronopilin (1,z-Dihydro-parthenin; fig. i79) Comp. Ambrosia dumosa (lys, etc., diploid), psilostachya; Hymenoclea salsola (plt) Cumanin Comp. Ambrosia psilostachya Cumanin-3-acetate Comp. Ambrosia psilostachya Cumanin-diacetate Comp. Ambrosia psilostachya Damsin Comp. Ambrosia maritima Deacetyl-confertiflorin Comp. Ambrosia acanthicarpa, confertiflora Dihydro-coronopilin Comp. Hymenoclea salsola (plt) Dihydro-mexicanin-E Comp. Helenium autumnale Fastigilin-A, -B, -C Comp. Gaillardia fastigiata (plt) Flexuosin-A and -B Comp. Helenium flexuosum Gaillardilin (fig. 179) Comp. Gaillardia arizonica, pinnatifida Helenalin (Helenic acid; Helenin (2); fig. 179) Comp. Balduina angustifolia; Gaillardia megapotamica, multiveps; Helenium aromaticum, autumnale, macrocephalum, mexicanum, microcephalum, quadridentatum; Leptopoda Hymenin (1-Epiparthenin) Comp. Hymenoclea salsola Hymenolin (II,13-Dihydro-parthenin) Comp. Hymenoclea salsola Isohelenalin Comp. Helenium microcephalum Isotenulin Comp. Helenium tenuifolium Linifolin-A and -B Comp. Helenium Mexicanin-A Comp. Helenium mexicanum Mexicanin-C (fig. 177) Comp. Helenium

SESQUITERPENOIDS 809

II

0 Ambrosin

Helenalin

Coronopilin

Tenulin

Gaillardilin

Mexicanin-E

Fig. x79. Some pseudoguaianolides. Mexicanin-E (fig. 179) lacks one -CH3 group. Comp. Helenium mexicanum, ooclinium Mexicanin-H `may represent an intermediary step in the transformation of pseudoguaianolides to norguaianolides'. Comp. Helenium Mexicanin-I is a stereoisomer of helenalin. Comp. Gaillardia; Helenium aromaticum, mexicanum Neoambrosin Comp. Hymenoclea monogyra, salsola Neohelenalin (Mexicanin-D) Comp. Helenium Odoratin is a `bitter principle'. Comp. Hymenoxis odorata Parthenin Comp. Ambrosia psilostachya, Parthenium hysterophorus Peruvinin Comp. Ambrosia peruviana Pulchellin Comp. Gaillardia pulchella (S.E. var.) Pulchellin-B (fig. 177) Comp. Gaillardia pulchella (New Mexico) Pulchellin-C Comp. Gaillardia pulchella (New Mexico) Pulchellin-D may be dihydro-pulchellin-B. Comp. Gaillardia pulchella (New Mexico)

810 CHEMOTAXONOMY OF FLOWERING PLANTS

Pulchellin-E Comp. Gaillardia Salsolin (Apoludin-2-acetate) Comp. Hymenoclea salsola Spathulin Comp. Gaillardia Stevin Comp. Stevia rhombifolia Tenulin (fig. 179) Comp. Helenium badium, elegans, montanunt, tenuifolium, thurberi; Leptopoda Thurberilin Comp. Helenium thurberi

III.8 Selinene (Eudesmol) group List and Occurrence Arglanine (I i,13-Dehydro-vulgarin) Comp. Artemisia douglasiana Artemisin (fig. 18o) Comp. Artemisia maritima Atractylon Comp. Atractylis japonica, ovata Canarone Burser. Canarium strictum (resin) Carissone Apocyn. Carissa lanceolata (rt) oc-Caryophyllene (Didymocarpene; Humulene): belongs here ? Karrer (1958) says that next to cadinene the caryophyllenes are the most widely spread sesquiterpenes. Salic. Populus nigra (buds) Mor. Humulus lupulus Illici. Illicium anisatum Dipterocarp. Anisoptera (9), Cotylelobium (3), Dipterocarpus (42 ?), Doona, Dryobalanops (2), Upuna Myrt. Agonis Gesneri. Didymocarpus pedicellata (lvs) Cyper. Gyperus Zingiber. Zingiber zerumbet (rhiz. oil, 32%) ß-Caryophyllene: belongs here? Myric. Comptonia?

SESQUITERPENOIDS 81I

Illici. Illicium anisatum ? Annon. Annona Dipterocarp. Anisoptera (9—Io), Cotylelobium (3), Dipterocarpus, Dryobalanops (a) Verben. Lippia (d-) ß-Caryophyllene-epoxide: belongs here ? Rut. Citrus (juice?) Dipterocarp. Dipterocarpus zeylanicus Myrt. Eugenia caryophyllata (cloves) Lab. Lavandula? Comp. Artemisia absinthium Costic acid Comp. Saussurea lappa (`costus root') a-Costol (Sesquibenihol) occurs in a conifer and in Comp. Saussurea lappa (rt) Cyperol: belongs here ? Cyper. Cyperus Cyperolone: belongs here ? Cyper. Cyperus rotundus (ess. oil) a-Cyperone (fig. 18o) Cyper. Cyperus rotundus (rhiz., 3o-5o% of ess. oil), scariosus (dl-) Dihydro-isohelenine (Dihydro-isoalantolactone) Comp. Inula helenium (rt) Douglanine Comp. Artemisia douglasiana ß-Elemene: belongs here ? It is a near-selinene sesquiterpene. Illici. Illicium anisatum Dipterocarp. Cotylelobium (a), Doona Comp. Inula Arac. Acorus calamus (ess. oil) Elemol: belongs here ? It is a near-selinene sesquiterpene. Burser. Canarium luzonicum Eudesmol (Atractylol; Cryptomeradol; Machilol; Sagittol; Selinenol; Uncineol; fig. 18o) Laur. Machilus kusanoi Myrt. Baeckea brevifolia (ess. oil, to 45%), gunniana v. latifolia (6o%); Eucalyptus (some spp.); Leptospermum flavescens (lvs); Melaleuca uncinata Comp. Atractylis ovata (rt), Balsamorhiza sagittata (rtbk) Helenine (Alantic acid anhydride; Alantolactone) Comp. Inula helenium (rt) Ilicic acid Comp. Ambrosia ilicifolia; Hymenoclea monogyra, salsola (plt)

812 CHEMOTAXONOMY OF FLOWERING PLANTS

oc-Selinene

oc- Eudesmol

oc-Cyperone

OH

oc-Santonin

Artemisin

Cyperolone?

Fig. i 80. Some selirene (eudesmol) sesquiterpenes.

Isohelenine (Isoalantolactone) Comp. Inula helenium (+ )-Jujenol Burser. Canarium strictum (resin) Lindera-lactone is a near-selinene sesquiterpene. Laur. Lindera strychnifolia (rt), Neolitsea zeylanica (rt) Linderane is a near-selinene sesquiterpene. Laur. Neolitsea zeylanica (rt) Linderene: belongs here ? (I have more than one formula for it.) Laur. Lindera strychnifolia (rt) Linderoxide Laur. Lindera strychnifolia (rt) Lindestrene Laur. Lindera strychnifolia (rt) Neolinderane is a near-selinene sesquiterpene. Laur. Neolitsea zeylanica (rt) Oplodiol (Selin-7-ene-1ß,443-diol) Arali. Oplopanax japonicus (rt) Pinnatifidin Comp. Helenium pinnatifidum Pseudo-santonine Comp. Artemisia spp. Santalenes (a- and ß-) are near-selinene sesquiterpenes. Santal. Santalum album (wd-oil)

SESQUITERPENOIDS 813

Santalols (a- and fl-) are near-selinene sesquiterpenes. Santal. Eucarya (Fusanus) acuminata?; Santalum album (wd-oil), cygnorum (F. spicatus), and other spp. ? Erythroxyl. a- and fl-forms may occur ? Santamarine Comp. Chrysanthemum parthenium a-Santonin (l-Santonin; fig. 18o) Comp. Artemisia brevifolia, tina, gallica, kurramensis, maritima, mexicana, paucifiora, ramosa, wrightii ß-Santonin: differs only spatially from a-Santonin ? Comp. Artemisia finta, monogyna, salina Selina-3,ß(I I)-diene Mor. Humulus lupulus Selinene (a- is a-Eudesmene; fl-; fig. 18o) Laur. Aniba rosaeodora v. amazonica (a-) Umbell. Apium graveolens (sd, mostly ß-), Libanotis transcaucasica (ess. oil, fl-), Seseli indicum (ess. oil, (3-) Tuberiferine Comp. Sonchus tuberifer (rt) Vulgarin (Tauremesin) Comp. Artemisia vulgaris

111.9 Dilactones GENERAL A few dilactones are listed here for convenience. Perhaps most of them should be distributed among the other groups. They seem to be restricted to the Compositae.

List and Occurrence Dihydro-mikanolide Comp. Mikania cordata (lvs, st.), scandens Mikanolide (fig. 181) Comp. Gaillardia fastigiata (plt); Mikania cordata (lvs, st.), scandens Psilostachyin Comp. Ambrosia dumosa (lvs, etc., diploid), psilostachya; Hymenoclea monogyra Psilostachyin-B Comp. Ambrosia psilostachya

814 CHEMOTAXONOMY OF FLOWERING PLANTS

Vernolepin

Mikanolide

Fig.

181

Some sesquiterpene dilactones.

Psilostachyin-C Comp. Ambrosia acanthicarpa, deltoidea, dumosa (lvs, etc., polyploid), peruviana, psilostachya; Hymenoclea monogyra Vermeerin Comp. Geigeria africana, aspera Vernolepin (fig. 181) is `a novel sesquiterpene dilactone' which is said to be a `reversible plant growth inhibitor' (Sequeira et al. 1968). Comp. Vernonia hymenolepis (plt) Vernomenin is related to vernolepin. Comp. Vernonia hymenolepis (plt)

IV DITERPENOIDS

GENERAL Briggs (1937), in a review of the diterpenes, says that they are rare in the essential oils of dicotyledons. This may well have been thought to be true thirty or more years ago, but my list, which has been compiled from that of Karrer (1958) and many others, includes about 90 such compounds! Few of them are known from more than one, or a very few species, but this probably reflects our ignorance rather than their extreme restriction. The diterpenoid alkaloids of Aconitum and Delphinium (Ranuncul.), of Garrya (Garry.), of Erythrophleum (Legum.), and of Inula royleana (Comp.), are included in our section on alkaloids. So few records of distribution of diterpenes in angiosperms are available that it is unwise to make generalizations. We may note, however: (a) Within the Umbellales we have diterpenoid alkaloids in the Garryaceae and a few diterpenes in the Araliaceae. My list has not a single record from the Umbelliferae. Contrast this with the records of monoterpenes in the order. (b) Within the Tubiflorae I list two diterpenes from the Convolvulaceae, one from the Verbenaceae, several from half a dozen genera in the Labiatae, and two from Andrographis of the Acanthaceae.

DITERPENOIDS 815

List and Occurrence Abbeokutone is of phyllocladene type. Rubi. Didymosalpinx abbeokutae (bk) Andrographolide (fig. 182) is a bitter principle. Acanth. Andrographis paniculata Atisirene Erythroxyl. Erythroxylum monogynum ((—)-) Atractyligenin is the aglycone of atractyloside. Comp. Atractylis gummifera (rt, free ?) Atractyloside Comp. Atractylis gummifera (rt) Caesalpins (cc-, Å-, y-, 8-, C-) are bitter principles. Legum. Caesalpinia bonducella (sd) Cafestol Rubi. Coffea sp. (sd-oil) cc-Camphorene (Dimyrcene; fig. 182) occurs in at least one conifer and in Laur. Cinnamomum camphora Burser. Commiphora mukul (resin) Arali. Nothopanax simplex Gram. Cymbopogon citratus Carnosol (Picrosalvin) is a bitter principle. Lab. Rosmarinus of cinalis; Salvia carnosa, of cinalis, triloba Cascarillin Euphorbi. Croton cascarilla (` cascarilla bk') Cascarillin-A Euphorbi. Croton cascarilla (bk) Cassainic acid is an acid component of the alkaloids of Legum. Erythrophleum Cativic acid Legum. Prioria copaifera (resin, cativo') Columbin: belongs here ? It is a bitter principle. Menisperm. Jateorhiza palmata (rt), Sphenocentrum jollyanum (sd) Corymbol Convolvul. Turbina corymbosa Crocetin (Gardeninin; Nyctanthin) is often placed among the carotenoids Legum. Mimosa pudica (lvs) Meli. Cedrela toona (fl.) Rubi. Gardenia grandiflora (cc-, frt, from crocin fgardenin) Verben. Nyctanthes arbor-tristis (cc-, fl.) Irid. Crocus luteus (cc-, fl.), neapolitanus (cc-, fl.) Crocetin-dimethyl ether Aristolochi. Aristolochia cymbifera (rt)

816 CHEMOTAXONOMY OF FLOWERING PLANTS

Crocin (Gardenin) is crocetin-digentiobioside. Rubi. Gardenia grandiflora (frt), lucida Irid. Crocus sativus (fl.) Darutigenol is said to be a tricyclic diterpene-triol. Darutigenol-fl-D-glucoside Comp. Siegesbeckia orientalis Dehydro-cassainic acid Legum. Erythrophleum guineense (bk) Devadarene Erythroxyl. Erythroxylum monogynum Devadarool Erythroxyl. Erythroxylum monogynum i 5,16-Dihydroxy-eperu-8(2o)-en-l8-oic acid Euphorbi. Ricinocarpos muricatus 6ß,8ß-Dihydroxy-enantio-labdan-l5-oic acid Sapind. Dodonaea lobulata 7a,8ß-Dihydroxy-enantio-labdan-I5-oic acid Sapind. Dodonaea lobulata Dodonaea-diterpene (fig. 182) Sapind. Dodonaea attenuata Enmein is a bitter principle. Lab. Isodon japonicus, trichocarpus Enmein-3-acetate Lab. Isodon japonicus Eperuane-8ß,15-diol Euphorbi. Ricinocarpos muricatus Eperuane-8ß,i 5,18-triol Euphorbi. Ricinocarpos muricatus Eperu-7,13-dien-15-oic acid Legum. Oxystigma oxyphyllum (wd) Eperu-8(2o)-en-15,18-dioic acid Euphorbi. Ricinocarpos muricatus Eperu-7-en-15-oic acid Legum. Oxystigma oxyphyllum (wd) Eperuic acid (fig. 182) Legum. Eperua falcata (resin, chief constituent) and other spp. 8ß,I 3-Epoxy-eperuan-14,15,18-triol Goodeni. Goodenia ramelii (14R-) Erythroxytriol-P and -Q Erythroxyl. Erythroxylum monogynum Fibraurin Menisperm. Fibraurea chloroleuca (bk)

DITERPENOIDS 817

Geranyl-geraniol Lin. Linuro usitatissimum Meli. Cedrela toona (wd) Geranyl-linalool occurs in conifers and Ole. Jasminum (jasmin-oil) Grayanotoxin-II Eric. Leucothoe grayana Hardwickiic acid: belongs here ? Legum. Copaifera officinalis (htwd, (+)-), Hardwickia pinnata (resin, (—)-) Hautriwaic acid occurs with, and is very like, dodonaea-diterpene. It is a member of the cascarillin group. Sapind. Dodonaea attenuata, viscosa Hautriwaic acid-lactone Sapind. Dodonaea attenuata )-Hibaene (+ Erythroxyl. Erythroxylum monogynum (+ )-Hibaene-epoxide Erythroxyl. Erythroxylum monogynum (wd) Hydroxy-devadarol Erythroxyl. Erythroxylum monogynum 18-Hydroxy-epimanool Legum. Trachylobium verrucosum (resin) enantio-8ß-Hydroxy-labdan-15-oic acid Legum. Trachylobium verrucosum (resin) enantio-8ß-Hydroxy-labd-13-en-I5-oic acid Legum. Trachylobium verrucosum (resin) enantio-18-Hydroxy-labd-8(zo)-en- 15-oic acid Legum. Trachylobium verrucosum (resin) Incensole Burser. Boswellia carteri (`frankincense) (— )-Isoatisirene Erythroxyl. Erythroxylum monogynum Isodonal is of enmein type. Lab. Isodon japonicus (— )-Kaur-15-en-17,19-diol Comp. Helichrysum dendroideum — )-Kaur-16-en-3x,19-diol (fig. 182) Euphorbi. Beyeria leschenaultii Comp. Helichrysum dendroideum Kaur-16-en-19-oic acid Arali. Aralia cordata (rt), racerrosa (rt)

818 CHEMOTAXONOMY OF FLOWERING PLANTS

Kaur-i6-en-3a-ol Euphorbi. Beyeria leschenaultii enantio-Labda-8(zo),13-dien- i5-oic acid Legum. Oxystigma oxyphyllum, Trachylobium verrucosum Labdanolic acid Cist. Cistus ladaniferus (resin) enantio-Labd-8(2o)-en- 1 5,18-dioic acid Legum. Trachylobium verrucosum (resin) enantio-Labd-8(zo)-en-15,18-diol Legum. Trachylobium verrucosum (resin) enantio-Labd-8(zo)-en-l 5-oic acid Legum. Trachylobium verrucosum (resin) Marrubiin Lab. Ballota foetida, Marrubium vulgare (lys, fl., etc.) 2-Methyl-6-methylene-10 p-tolylundec-z-ene Comp. Artemisia absinthium (ess. oil) Methyl-vinhaticoate is a diastereoisomer of methyl-vouacapenate. Legum. Plathymenia reticulata (wd) Methyl-vouacapenate Legum. Vouacapoua americana, macropetala Monogynol Erythroxyl. Erythroxylum monogynum Olearin: belongs here ? Comp. Olearia heterocarpa Olearyl-oxide Comp. Olearia (Shawia) paniculata Oridonin is a bitter principle. Lab. Isodon japonicus (lvs), trichocarpus (lvs) Panicolide is a bitter principle which belongs here ? Acanth. Andrographis paniculata Phorbol (fig. 182) has, if the formula given is correct, a close resemblance to the pseudoguaianolide sesquiterpenes, which seem, however, to be confined to the Compositae. Euphorbi. Croton tiglium Phyllocladene (Dacrene; Sciadopitene; fig. 182) occurs, as its names suggest, in several conifers. It has not, I think, been found in any angiosperm but the configurations of the diterpenoid alkaloids such as garryfoline and veatchine have been correlated with phyllocladenetype diterpenes by Vorbrueggen and Djerassi (1962). Picropoline Lab. Teucrium polium Picropoline-acetate Lab. Teucrium polium

DITERPENOIDS 819

COON

6C0 CH2OAc CH2OH Eperuic acid

Andrographolide

Oodonaea-diterpene

j 9,H2OH

HO HOH2C «-Camphorene

Stach 15-ene-3x-19-diol

? Kaur-16-ene 3c ,19-diol

?Steviol (Stevioside has sophorose at x,glucose at xx ? )

Q67' Phyllocladene

P imara-8(14),15-d ien -19-oic acid

OH OH

OH

CH2OH

Phorbol

Vouacapenic acid

Fig. 182 Some diterpenoids.

(— )-Pimaradiene Erythroxyl. Erythroxylum monogynum (— )-Pimara-8(14),15-dien-19-oic acid (fig. 182) Arali. Aralia cordata (rt), racemosa (rt) Plathyterpol Legum. Plathymenia reticulata (htwd) Psiadol Comp. Psiadia altissima (lys)

8zo

CHEMOTAXONOMY OF FLOWERING PLANTS

Sclareol is related to manool, etc., occurring in conifers. Lab. Salvia sclarea (+)-Stach-15-en-3a,i9-diol (fig. 182) Comp. Helichrysum dendroideum )-Stachi 5-en-17,19-diol (17-Hydroxy-monogynol) (+ Erythroxyl. Erythroxylum monogynum Comp. Helichrysum dendroideum Steviol (fig. 18z) is the aglycone of stevioside. I find more than one formula for it. It is said to be `related both structurally and in biological activity to the gibberellins'. Stevioside (fig. 182) is said to be 30o times as sweet as sucrose! Comp. Stevia rebaudiana (lvs) Tinophyllone: belongs here? Menisperm. Tinomiscium philippinense (rt, bk) Trichokaurin Lab. Isodon trichocarpus 4,4,r o-Trimethyl-l5-methylene-8,13-cyclopentano-perhydrophenanthrene Erythroxyl. Erythroxylum monogynum (wd-oil) Turbincorytin Convolvul. Turbina corymbosa (as glucoside ?) Vinhaticoic acid is an epimer of vouacapenic add. Legum. Plathymenia reticulata (htwd, as methyl vinhaticoate ?) Vouacapenic acid (fig. 182) Legum. Vouacapoua americana (Andira excelsa) Vouacapenol Legum. Vouacapoua macropetala? Vouacapenyl-acetate Legum. Vouacapoua macropetala

V TRITERPENOIDS GENERAL A recent (1967) article by Basu and Rastogi is a useful review of this large group of compounds. Another review that has yielded much information is that by Hiller, Keipert and Linzer (1966). We learn that triterpenoids are virtually restricted to the plant kingdom; that they are found in several hundred genera; that they occur chiefly as saponins—glycosides with -0-sugar linkages; and that the sugars, unlike those of the cardenolides, are the relatively common ones such as n glucose, D-galactose; D-galacturonic acid, D-glucuronic acid,

TRITERPENOIDS

821

D-xylose, L-arabinose, L-fucose and L-rhamnose. The molecules, as they occur in the plant, may be quite large, with up to iz sugar units. We may distinguish:

1. Triterpenoid Saponins and Sapogenins—a very large group. 2. Triterpenoids other than those of group 1. In the following lists the substitution patterns are given in brackets thus: acacic acid is a ß-amyrin derivative substituted (16,21-OH; z8-COOH). In some cases saponins have been described without names. I have then made up lettered names including the generic name of the plant where possible. Some examples of the chemotaxonomic usefulness of these substances will be found in the appropriate places, but an example or two may be given here. (a) The genus Luffa (Cucurbitaceae) has 6-8 species, most of which have been examined. Each seems to have a different triterpenoid mixture: L. acutangula seeds yield oleanolic acid. Cucurbitacins-B, -D, -G and -H are present. L. aegyptiaca (cylindrica) has luffa-saponin-C, yielding oleanolic acid, a neutral genia and (?). L. echinata has lulla-saponin-A, yielding oleanolic acid, glucose and rhamnose. L. graveolens has luffa-saponin-B, yielding oleanolic acid, glucose, arabinose and rhamnose. Cucurbitacins-B and -E are present. L. operculata (purgans) has luffa-saponin-D, yielding gypsogenin and (?). Cucurbitacins-B and -D are present.

(b) The small order Primulales (p. 1552) has 3 families all of which seem to produce triterpenoid saponins: Theophrastaceae (s/r ro): Jacquinia has jacquinia-saponin, two of whose sapogenins appear to be primulagenins. Myrsinaceae (35/1000): Aegiceras has aegiceras-saponin and kujalgin. Primulaceae (20/600): Anagallis has anagallis-saponin; Cyclamen has cyclamen-saponin and cyclamin (1); Primula spp. have primulasaponins-A and -B.

But what a minute sampling we have!

822 CHEMOTAXONOMY OF FLOWERING PLANTS

V. Triterpenoid Saponins and Sapogenins GENERAL I have found this to be a very difficult group. Chemotaxonomic usefulness is discussed where appropriate elsewhere, but we may note: (a) In the neighbourhood of the Centrospermae (numbers of compounds bracketed): Polygonales Polygon.: none recorded Centrospermae 1. Phytolacc. Phytolacca (i) 5. Mollugin. Glinus (I), Mollugo (2) 9. Caryophyll. Agrostemma (ca. 5), Gypsophila (z), Herniaria (I), Saponaria (3), Silene (I), Spergularia (I) 11. Chenopodi. Anabasis (ca. 5), Atriplex (2), Beta (z), Chenopodium (i) 12. Amaranth. Achyranthes (3) Cactales Cact.: Escontria (3), Heliabravoa (2), Lemaireocereus (ca. 13), Lophocereus (1), Machaerocereus (ca. 5), Myrtillocactus (ca. 8) This is in line with other chemical evidence (occurrence of betalains, for example) linking the Cactaceae with the Centrospermae, but excluding the Polygonaceae. (b) Umbellales (Apiales) 4. Corn. Cornus (I), Griselinia (I) 6. Arali. Acanthopanax (1), Aralia (several), Fatsia (2 or 3), Hedera (ca. 5), Kalopanax (4), Panax (several), Polyscias (2) 7. Umhell. Bupleurum (z), Centella (several), Eryngium (I), Hydrocotyle (several), Sanicula (I or more) This would seem to support those who consider the Araliaceae and Umbelliferae to be closely related, rather than Hutchinson (1969), for example, who would see separate origins for them. List and Occurrence Abrus-saponin yields a mixture of genins. Legum. Abrus precatorius (rt) Acacia-saponin yields acacic acid and (?). Legum. Acacia concinna Acacic acid is a derivative of ß-amyrin (16,21-OH; z8-COOH). It occurs in acacia-saponin and in a saponin from Albizia (below).

TRITERPENOIDS 823

Achras-saponin yields bassic acid (achras-sapogenin), glucose, z x rhamnose and 2 x arabinose. Sapot. Achras sapota (latex, frt); Mimusops elengi (sd, latex), heckelii (wd), hexandra (sd) Achyranthes-saponin-A yields oleanolic acid, glucose, galactose, xylose and rhamnose. Amaranth. Achyranthes aspera (sd ?) Achyranthes-saponin-B: is this distinct from achyranthes-saponin-A? Amaranth. Achyranthes bidentata (sd ?) Actaea-saponin yields cymigenol and xylose. Ranuncul. Actaea racemosa (rtstk) Actein (better Actaein ?) yields acteol (better actaeol?) and xylose. Is it identical with actaea-saponin? Ranuncul. Actaea racemosa (rtstk) Acteol—see actaein. Aegiceradiol is said to arise from aegiceras-saponin(s). It is 3ß,28dihydroxy-olean- i 2, i 5-diene. Aegiceras-saponin(s) yield(s) aegicerin, aegiceradienol, aegiceradiol, kujalgin, etc. ? Myrsin. Aegiceras majus Aegicerin (C30H4803) is said to arise from aegiceras-saponin(s). Aescigenin (Escigenin) is a ß-amyrin derivative (22-OH; 16 -4- 2I-oxo; 24,28-CH2OH)—see under aescin. Aescin (Escin) yields protoaescinigen, aescigenin, aescinidin (as angelic or tiglic salts), D-glucose, D-xylose and D-glucuronic acid. Hippocastan. Aesculus hippocastanum Aescinidin—see aescin. Agrostemma-sapotoxin Caryophyll. Agrostemma githago Agrostemmic acid: a saponin? Caryophyll. Agrostemma githago Agrostemmin (Agrostemin): a saponin? Caryophyll. Agrostemma githago Akebiagenin: is hederagenin+oleanolic acid? Akebin yields hederagenin, oleanolic acid and (?). Lardizabal. Akebia quinata (lvs) Albigenic acid is a ß-amyrin derivative. Legum. Albizia lebbek (as saponin) Albigenin is a ß-amyrin derivative. Legum. Albizia lebbek (as saponin) Albitocin yields an acid genin, glucose, arabinose, xylose and rhamnose. Legum. Albizia gummifera

824 CHEMOTAXONOMY OF FLOWERING PLANTS

Albizia amara-saponin yields echinocystic acid, a neutral genin and (?). Legum. Albizia amara Albizia-saponin-A yields echinocystic acid, a neutral genin, oleanolic acid and (?). Legum. Albizia lucida Albizia-saponin-B: is this identical with albizia-saponin-A? Legum. Albizia lebbek (sd ?) Albizia-saponin-C yields acacic acid and (?). Legum. Albizia lebbek (bk ?) Albizia-saponin-D yields albigenic acid, oleanolic acid, echinocystic acid and albigenin. Legum. Albizia lebbek (sd ?) Albizia-saponin-E yields machaerinic acid, an acid genin and (?). Legum. Albizia odoratissima Albizia-saponin-F yields an acid genin, rhamnose, arabinose and glucuronic acid. Legum. Albizia adiantifolia Albizia-saponin-G yields proceric acid and (?). Is this proceranin? Legum. Albizia procera Alphitonia-saponin yields betulinic acid and (?). Rhamn. Alphitonia excelsa a-Amyrin (a-Amyrenol; Urs-12-en-3ß-ol; fig. 183): only a few sapogenins (asiatic acid, brahmic acid, centoic acid, quinovic acid) are derivatives of a-amyrin. However, free or combined it seems to be widely distributed. I have Mor. Artocarpus Euphorbi. Aporusa chinensis (lvs), Euphorbia pulcherrima Aquifoli. Ilex (1) Burser. Canarium strictum (resin) Apocyn. Ervatamia, Plumeria Asclepiad. Hemidesmus Caprifoli. Viburnum Lab. Salvia Comp. Calendula officinalis (fl.) (3-amyrin (ß-Amyrenol; Olean-rz-en-3ß-ol; a-Viscol?; fig. 183): many sapogenins are based on the structure of ß-amyrin. It is very widely distributed, free or in combination. I have Loranth. Viscum? Cact. ? Euphorbi. Euphorbia (3), Phyllanthus Balsamin. Impatiens Burser. Canarium strictum (resin) Aquifoli. Ilex (2)

TRITERPENOIDS 825

Celastr. Celastrus Dipterocarp. Doona Apocyn. Alstonia, Plumeria Asclepiad. Gymnema, Hemidesmus Lab. Salvia? Comp. Calendula officinalis (fl.) Anabasis-saponins-A, -B, -C, and -D yield genins A-D respectively, glucose and glucuronic acid. -A yields anabasic acid glucuronate. Chenopodi. Anabasis articulata (plt), setifera (-A, -B, and -C) Anagallis-saponin yields a genin, glucose, arabinose and a pentose. Primul. Anagallis arvensis (plt) Anemone-saponin-A yields anemosapogenin, glucose, rhamnose and another sugar. Ranuncul. Anemone chinensis Anemone-saponin-B yields a sapogenin (C30H4804), glucose, rhamnose and arabinose. Is this distinct from anemone-saponin-A? Ranuncul. Anemone nemorosa Anemosapogenin, from anemone-saponin-A, is incompletely known. Aralia-saponins—see also below. Arali. Aralia bipinnatifida (yields oleanolic acid and glucose), japonica (lvs, yielding oleanolic acid and heØagenin ?) Araliin (Aralin) is a glucoside of aralidin. Is it related to the aralosides? Arali. Aralia spinosa (bk, rt) Araloside-A yields oleanolic acid, glucuronic acid, D-glucose and Larabinose. Arali. Aralia elata, mandschurica Araloside-B yields oleanolic acid, glucuronic acid, glucose and 2 x arabinose. Arali. Aralia data, mandschurica Araloside-C yields oleanolic acid, glucuronic acid, glucose, xylose and galactose. Arali. Aralia elata, mandschurica Arjunolic acid (Tomentosic acid?; fig. 183) is a ß-amyrin derivative (2-OH; 23-CH2OH; z8-COOH). It is recorded from Bix. Bixa orellana (as tomentosic acid) ? Myrt. Tristania conferta (wd), Syzygium cordatum (bk, spwd) Combret. Terminalia arjuna (as terminaliasaponin), tomentosa (as tomentosic acid?) Rubi. Mussaenda pubescens (st.) Armillarigenins-A to -D occur in jacquinia-saponin(s). It seems that -C is primulagenin-A, and -D is probably primulagenin-B. Asiatic acid is an a-amyrin derivative (2-OH; z3-CH2OH; z8-COOH). It is the aglycone of asiaticoside.

826 CHEMOTAXONOMY OF FLOWERING PLANTS

Asiaticoside yields asiatic acid, 2 x glucose, and rhamnose. Umbell. Centella (Hydrocotyle) asiatica (from Madagascar) Aster-saponin yields hederagenin and glucose? (Hiller et al. say astersapogenin and arabinose.) Comp. Aster tataricus (rt) Astragalus-saponin yields a mixture of genins. Legum. Astragalus glycyphyllos (lvs) Atriplex-saponin yields oleanolic acid and (?). Chenopodi. Atriplex canescens Avenacin yields avenagenin, O-monomethyl-amino-benzoic acid, 2 x glucose, and a pentose. Gram. Avena sativa Avenagenin is a ß-amyrin derivative. Bacogenin-A (fig. 183) is an aglycone of monnierin and the bacosides. Bacogenins-A2, -A3 and -A4 have also been reported. Bacosides-A and -B yield bacogenins-A1 to -A4, glucose and arabinose. Scrophulari. Bacopa monniera Barrigenol-A1(3ß, 15 a,i6a,2za,28-Pentahydroxy-olean-i2-ene) has been obtained from pittosporum-saponin-A and from hydrolysates of Griselinia scandens. Barrigenol-R1 is a ß-amyrin derivative (15,16-OH; 27,28-CH2OH). Lecythid. Barringtonia racemosa (as saponin ?) Barringtogenic acid is a ß-amyrin derivative (2-OH; 23,28-COOH). Lecythid. Barringtonia racemosa (as saponin) Barringtogenol (Barrigenol-R2) is a ß-amyrin derivative (2-OH; 23,28CH2OH). Lecythid. Barringtonia racernosa (as saponin) Barringtogenol-B (3ß,2Iß,22a,z8-Tetrahydroxy-I6a-angeloyloxy-oleaniz-ene) occurs in barringtonia-saponin-B. Barringtogenol-C (Aescinidin; Escinidin) is a ß-amyrin derivative (16,21,22-OH; z8-CH2OH) which occurs in barringtonia-saponin-B, and as a salt in aescin. Barringtogenol-D is a ß-amyrin derivative (22-OH; 16 —> 21-OXo; 28-CH2OH) which occurs in barringtonia-saponin-B. Barringtonia-saponin-A yields barringtogenol and barringtogenic acid or barrigenol-R1. Lecythid. Barringtonia racemosa Barringtonia-saponin-B yields barringtogenols-B to -D, barringtonic acid and (?). Lecythid. Barringtonia acutangula Bassia-saponin(s) yield(s) bassic acid and (?). Sapot. Bassia latifolia (sd), longifolia (sd); Butyrospermum (Bassia) parkii

TRITERPENOIDS 827

Bassic acid (Mimusops-sapogenin) is a 13-amyrin derivative (z,3-OH; 23-CH2OH; z8-COOH; 0(6).12(13>) which occurs in saponins from seeds of members of the Sapotaceae. Bayogenin (C30H4805) occurs in castanopermum-saponin and sideroxylonsaponin-A. Beta-saponin yields oleanolic acid and (?). Chenopodi. Beta vulgaris (rt) Betulin is a lupeol derivative (R = 's' ; R1 = CH2OH). Betul. Betula alba (white pigment of bk) Cact. Lemaireocereus Legum. Soppora japonica (in sophora-saponin) Eben. Diospyros melanoxylon (bk), peregrina (bk) Comp. Helichrysum dendroideum Betulinic acid (fig. 183) is a lupeol derivative (R = `7' ; R1 = COOH). It is widely distributed (Stabursvik, 1953). My records include Loranth. Nuytsia floribunda (lvs, st.) Cact. Lemaireocereus spp. (in saponins ?), Machaerocereus spp. (in saponins ?) Platan. Platanus acerifolia (bk ?) Guttif. Hypericum androsaemum (rtbk), elatum (rtbk) Rhamn. Ziziphus vulgaris var. spinosa (sd) Myrt. Melaleuca (bks of 6 spp.), Syncarpia laurifolia (bk) Corn. Cornus florida (bk), sanguinea? Apocyn. Alyxia buxifolia (lys of plants from dry inland areas; not in coastal forms) Eben. Diospyros melanoxylon (bk), peregrina (bk) Scrophulari. Gratiola officinalis (?gratiolone) Menyanth. Menyanthes trifoliata (rhiz.; accompanied by saponins) Blighia-saponin: where does this belong? It is said to yield a sapogenin (C16H2602), arabinose and rhamnose. Sapind. Blighia unijugata Boquila-saponin yields oleanolic acid and glucose. Lardizabal. Boquila trifoliata Brahmic acid (6-Hydroxy-asiatic acid) is an a-amyrin derivative. It is the aglycone of brahminoside and brahmoside. Umbell. Centella asiatica (free ?) Brahminoside yields brahmic acid, z x glucose, arabinose and rhamnose. Umbell. Centella asiatica (Indian var.) Brahmoside yields brahmic acid, glucose, arabinose and rhamnose. Umbell. Centella asiatica (Indian var.) Bredemeyera-saponin yields bredemolic acid, tenuifolic acid and glucose. Polygal. Bredemeyera floribunda Bredemolic acid is the genin of bredemeyera-saponin.

828 CHEMOTAXONOMY OF FLOWERING PLANTS

Bryogenin is tetracyclic, like the cucurbitacins. It is the aglycone of bryonin. Bryonin yields bryogenin and (?). Cucurbit. Bryonia cretica (dioica) Bupleurum-saponin yields saikogenins-A to -G. Umbell. Bupleurum falcatum Caccinia-saponin: belongs here ? Boragin. Caccinia glauca Calendula-saponins: at least 3 are said to yield oleanolic acid, glucuronic acid, glucose and a methyl-pentose. Comp. Calendula officinalis Camellia-sapogenol (C30H2004) is derived from camellia-saponin-A. Camellia-saponin-A yields camellia-sapogenol, arabinose, galactose, a uronic acid and tiglic acid (another report says 3 x glucose and 2 x arabinose). The. Camellia japonica (frt) Camellia-saponin-B yields theasapogenin, galactose, glucose and a pentose. The. Camellia sasanqua (frt) Caryocar-sapogenin (C22H44O4)—see caryocar-saponin. Caryocar-saponin yields caryocar-sapogenin and (?). Caryocar. Caryocar glabrum Castanogenin has been obtained from castanospermum-saponin. Castanospermum-saponin yields castanogenin, bayogenin and (?). Legum. Castanospermum australe (wd) Centellic acid, an isomer of centoic acid, is the aglycone of centelloside. Centelloside yields centellic acid, 10 x glucose (!), and 2 X fructose. Umbell. Centella asiatica (Ceylonese var.) Centoic acid is an a-amyrin derivative (5,6-OH; 23-CH2OH; 28-COOH). Cestrum-saponin: belongs here? Solan. Cestrum diurnum Chichipegenin is a ß-amyrin derivative (16,22-OH; 28-CH2OH). Cact. Lemaireocereus chichipe (in saponin ?), Myrtillocactus spp. (in saponins ?) Cimigenol is a sapogenin which occurs as a xyloside. Cimigenol-xyloside Ranuncul. Cimicifuga racemosa Cincholic acid, a ß-amyrin derivative (27,28-COOH), is the aglycone of cinchona calisaya-glycoside-C. Cinchona calisaya-glycoside-C yields cincholic acid and 2 x glucuronic acid. Rubi. Cinchona calisaya ß-Citraurin (C30H40O2) is often classed as a carotenoid. Rut. Citrus aurantium (frt)

TRITERPENOIDS 829

Clematis-saponin(s) yield(s) hederagenin, oleanolic acid, and (?). Ranuncul. Clematis paniculata, vitalba (yields hederagenin) Clematosides-A, -B and -C yield oleanolic acid, hederagenin, and (from -C) 5 x glucose, arabinose, 3 x rhamnose and xylose. Ranuncul. Clematis mandschurica (rt) Cochalic acid (i6ß-Hydroxy-oleanolic acid), isomeric with queretaroic acid, is a ß-amyrin derivative (i6-OH; z8-COOH). Cact. Myrtillocactus spp. (in saponins) Coronilla-saponins: include saponinic acid? Legum. Coronilla emerus Cryptoaescins-A and -B are said to be a mixture of aescin, aescinmethyl ester and cholesterol. Cucurbitacins are bitter principles of the Cucurbitaceae. According to Basu and Rastogi (1967) they are derivatives of the parent substance shown in fig. 183. Cucurbitacin-A (Ri-OH; R2-O; R3-CH2OH; R4-Ac; 6,21(24)) occurs free. Cucurbit. Cucumis Cucurbitacin-B (R1-0H; R2-O; R3-CH3; R4-Ac; A23(24)) occurs as glycoside. Cucurbit. Acanthosicyos, Bryonia, Citrullus, Coccinia, Corallocarpus, Cucumis, Cucurbita, Ecballium, Echinocystis, Gerrardanthus, Kedrostis, Lagenaria, Luffa, Melothria, Sicyos, Telfairia, Toxanthera?, Trochomeria Cucurbitacin-C (R1-OH; R2-OH; R3-CH2OH; R4-Ac; 6.23(24)) occurs free. Cucurbit. Cucumis sativus var. ` Hanzil' Cucurbitacin-D (Elatericin-A) (R1-OH; R2-O; R3-CH3; R4-H; A23(24)) occurs as glycoside. Cucurbit. Acanthosicyos, Bryonia, Citrullus, Coccinia, Corallocarpus, Cucumis, Cucurbita, Ecballium, Gerrardanthus, Kedrostis, Lagenaria, Luffa, Melothria, Telfairia, Toxanthera, Trochomeria Cucurbitacin-E (a-Elaterin) (R1-OH; R2-O; R3-CH3; R4-Ac; 6.1(2),23(20) occurs as glycoside. Cucurbit. Bryonia, Citrullus, Cucurbita, Ecballium, Echinocystis, Kedrostis, Lagenaria, Luffa, Peponium, Telfairia Cucurbitacin-F (R1-OH; R2-OH; R3-CH3; R4-H; A23(24)) occurs free. Cucurbit. Cucumis Cucurbitacin-G (C30H5209) occurs as glycoside. Cucurbit. Acanthosicyos, Citrullus, Corallocarpus, Cucumis, Ecballium, Gerrardanthus, Kedrostis, Lagenaria, Luffa, Melothria, Telfairia, Toxanthera, Trochomeria

830 CHEMOTAXONOMY OF FLOWERING PLANTS

Cucurbitacin-H Cucurbit. Acanthosicyos, Citrullus, Corallocarpus, Cucumis, Cucurbita, Ecballium, Gerrardanthus, Kedrostis, Lagenaria, Luffa, Melothria, Telfairia, Toxanthera, Trochomeria Cucurbitacin-I (R1-OH; R2-O; R3-CH3; R4-H; Wu2).23(24)) occurs as glycoside. Cucurbit. Bryonia, Citrullus, Cucurbita, Ecballium, Echinocystis, Kedrostis, Lagenaria Cucurbitacin-J (R1-OH; R2-0; R3-CH3; R4-H; & (2); C24-OH) occurs as glycoside. Cucurbit. Citrullus, Cucurbita, Kedrostis Cucurbitacin-K, a C24-OH isomer of cucurbitacin-J, occurs as glycoside. Cucurbit. Citrullus, Cucurbita, Kedrostis Cucurbitacin-L (R1-OH; R2-O; R3-CH3; R4-H; 01(2)) occurs as glycoside. Cucurbit. Bryonia, Citrullus Cyclamen-saponin yields cyclamigenins-A, -B, -C, -D and (?). Primul. Cyclamen europaeum (corm) Cyclamigenins-A, -B, -C, and -D from cyclamen-saponin. -B is 13ß,28epoxy-16, 3 o-dioxo-oleanan-3ß-ol. Cyclamin (1) yields cyclamiretins-A, -B, -C, -D, 3 x glucose, D-xylose, and L-arabinose. Primul. Cyclamen europaeum (corms), and other spp. ? Cyclamiretin-A is an aglycone of cyclamin (1). Cyclamiretins-B, -C and -D are said (1968) to be artefacts. Diospyros-saponin yields oleanolic acid and glucose. Eben. Diospyros peregrina Doryanthes-sapogenins: belong here ? Agay. Doryanthes palmeri (as saponins?) Dumoria-saponin yields bassic acid and (?). Sapot. Dumoria heckelii (sd) Dumortierigenin (fig. 183) is a ß-amyrin derivative. Cact. Lemaireocereus dumortieri (as saponin) Echinocystic acid (?Helianthic acid) is a ß-amyrin derivative (16-OH; 28-COOH). It occurs in saponins. Echinocystis-saponin yields echinocystic acid and (?). Cucurbit. Echinocystis fabacea Eglantol (C30H4804) is the aglycone of eglantoside. Eglantoside yields eglantol, glucose and rhamnose. Ros. Rosa canina (it) Elvira-saponin yields echino cystic acid, galactose and xylose. Comp. Elvira biflora

TRITERPENOIDS 831

Entada-saponins-A and -B yield entagenic acid, glucose, galactose, xylose and arabinose. Legum. Entada scandens Entagenic acid (3ß, 2 Ia,22a-Trihydroxy-olean-Iz-en-28-oic acid) occurs in saponins of Entada scandens and pursaetha. Legum. Entada phaseoloides (sd, as saponin ?) 3-Epi-oleanolic acid Hamamelid. Liquidambar orientalis Eryngium-saponin ? yields oleanolic acid. Umbell. Eryngium incognita Erythrodiol is a ß-amyrin derivative (28-CH2OH). Cact. Lemaireocereus spp. (as saponins?) Escontria-saponin yields longispinogenin and maniladiol? Cad. Escontria chiotilla Ethyl machaerinate is an aglycone of proceranin. Eupteleogenin occurs in eupteleosides-A and -B. Eupteleoside-A yields eupteleogenin and (?). Euptele. Euptelea polyandra (rt) Eupteleoside-A-acetate (Eupteleoside-B) Euptele. Euptelea polyandra (rt) Fouquieria-saponin yields echinocystic acid and (?). Fouquieri. Fouquieria peninsularis (bk) Ginsenosides-a to -f, -g', -g2, -ga, and -h yield panaxadiol, panaxatriol, and protopanaxadiol. Arali. Panax schinseng. Githagenin may be gypsogenin. Githagin yields githagenin and (?). Caryophyll. Agrostemma githago (sd) Githagoside Caryophyll. Agrostemma githago (sd) Glycyrrhetic acid is a ß-amyrin derivative (i i-O; 29-COOH). It is the aglycone of glycyrrhizin and monesin. Glycyrrhizin (Glycyrrhizic acid) yields glycyrrhetic acid and 2 x glucuronic acid. Some of the following are old records and may not be reliable. [Ferns] Legum. Abrus precatorius; Astragalus ammodytes, glycyphyllos?; Glycyrrhiza echinata, glabra, uralensis, Trifolium alpense Sapot. Pradosia (is the saponin also called monesin?) Gratiogenin: belongs here ? It is the aglycone of gratioside. Gratioside yields gratiogenin and 2 x glucose. Scrophulari. Gratiola officinalis (Ns ?) Guaiac-saponin yields oleanolic acid (guaiagenin) and (?). Zygophyll. Guaiacum officinale

832 CHEMOTAXONOMY OF FLOWERING PLANTS

Gummosogenin is a ß-amyrin derivative (i 6-OH ; 28-CHO). Cact. Machaerocereus gummosus (as saponin) Gypsogenin is a ß-amyrin derivative (23-CHO; 28-COOH). It is the aglycone of gypsoside and luffa-saponin-D. I have records of it (as saponins ?) from Caryophyll. Gypsophila, Saponaria vaccaria (as vaccaroside) Cucurbit. Luffa operculata (as luffa-saponin-D) Sapot. Sideroxylon (as saponin) Gypsoside is said to yield gypsogenin, n glucose, n galactose, D-arabinose, L-rhamnose, n fucose, D-glucuronic acid, and 3 x n-xylose! Is it in all the following ? Caryophyll. Gypsophila elegans, oldhamiana, pacifica, paniculata, struthium Hederacoside-A yields hederagenin, D-glucose and L-arabinose. Arali. Hedera helix Hederacosides-B and -C: belong here ? Arali. Hedera helix Hederagenin (Melanthigenin, Caulosapogenin), a f3-amyrin derivative (23-CH2OH; 29-COOH), has been obtained from saponins (in all cases ?) of Ranuncul. Clematis, Nigella sativa (sd, from melanthic acid) Berberid. Leontice Lardizabal. Holboellia Sapind. Sapindus Arali. Acanthopanax, Fatsia?, Hedera Comp. Aster Heliabravoa-saponin yields oleanolic acid, oleanolic aldehyde and (?)• Cact. Heliabravoa chende Helianthus-saponin yields echinocystic acid, a hexose, a pentose and a methyl pentose. Comp. Helianthus annuus (petals) Hepatigenin occurs in hepatisaponin. Hepatisaponin yields prosapogenin and arabinose, then hepatigenin and glucose? Ranuncul. Hepatica triloba Herniaria-saponin(s) yield(s) two sapogenins and (?). Caryophyll. Herniaria glabra, hirsuta Holboellia-saponin(s) yield(s) hederagenin and (?). Lardizabal. Holboellia angustifolia, latifolia Hydrocotyle-saponins -A, -A2, -B, and -S4: belong here ? Umbell. Hydrocotyle vulgaris Hydroxy-gratiogenin : belongs here ?

TRITERPENOIDS 833

Illipe-saponin (Mowrin) yields bassic acid and glucose. Sapot. Bassia (Illipe) butyracea Indocentelloside yields indocentoic acid and (?). Umbeil. Centella asiatica (Indian var.) Indocentoic acid is of unknown structure (1967) ?. It is the aglycone of indocentelloside. Isobrahmic acid Umbell. Centella asiatica Jacquinia-saponin(s) yield(s) armillarigenins-A and -B. Theophrast. Jacquinia armillaris Jacquinic acid (3ß,i6oc,28-Trihydroxy-ß-amyrin-3oß-oic acid): belongs here ? Theophrast. Jacquinia pungens (frt) Japoaescigenin (Hydroxy-aescigenin) is the aglycone of japoaescin. Japoaescin yields japoaescigenin, 2 x glucuronic acid, xylose and tiglic acid. Hippocastan. Aesculus turbinata Jegosapogenol ß-amyradiene with axial OH at C19 ?—is derived from jegosaponin. Jegosaponin, originally described as a steroidal saponin, yields jegosapogenol, tiglic acid and (?). Styrac. Styrax japonica (frt) Kalopanax-saponin yields oleanolic acid, 2 x glucose and 2 x arabinose. Arali. Kalopanax septemlobus (rtbk) Kalopanax-saponin-A yields oleanolic acid (Hiller et al. 1966 say hederagenin), L-arabinose and L-rhamnose. Arali. Kalopanax septemlobus (rtbk) Kalopanax-saponin-B yields oleanolic acid (Hiller et al. say hederagenin), D-arabinose and D-rhamnose. Arali. Kalopanax septemlobus Kalosaponin (Kalotoxin) yields hederagenin (kalosapogenin) and (?). Arali. Kalopanax ricinifolius Kujalgin (C30H52O3) is a neutral sapogenin. Myrsin. Aegiceras majus (bk, sd, as saponin?) Lardizabala-saponin yields oleanolic acid and (?). Lardizabal. Lardizabala biternata (lvs) Lemaireocereus-saponins yield queretaroic acid, chichepegenin, oleanolic acid, longispinogenin, dumortierigenin, erythrodiol, betulinic acid, stellatogenin and thurberogenin. Cact. Lemaireocereus spp. Leontice-saponin (Leontosaponin) yields hederagenin, glucose and arabinose. Berberid. Leontice leontopetalum 6

aco II

834 CHEMOTAXONOMY OF FLOWERING PLANTS

Leontin (Caulosaponin): what is this? Ranuncul. Clematis vitalba (plt) Berberid. Caulophyllum thalictroides (rt, rhiz.) Leonurus-saponin: belongs here ? Lab. Leonurus quinquelobatus Lippia-saponin-A ? yields oleanolic acid, icterogenin, and (?). Verben. Lippia rehmanni (lvs) Lippia-saponin-B ? yields icterogenin, rehmannic acid (lantadene-A), 22ß-angeloyloxy-oleanolic acid, and 2213-angeloyloxy-24-hydroxyoleanolic acid. Verben. Lippia rehmanni (rtbk) Longispinogenin, a ß-amyrin derivative (i6-OH; 28-CH2OH), has been recorded (as saponins?) from Cact. Escontria chiotilla; Lemaireocereua chichipe, griseus, hystrix, longispinus, quevedonis; Myrtillocactus spp. Umbell. Bupleurum falcatum Lotus-saponin yields soyasapogenol-B and (?). Legum. Lotus corniculatus Luffa-saponin-A yields oleanolic acid, glucose and rhamnose. Cucurbit. Luffa echinata Luffa-saponin-B yields oleanolic acid, glucose, arabinose and rhamnose. Cucurbit. Luffa graveolens Luffa-saponin-C yields oleanolic acid, a neutral genin and (?). Cucurbit. Luffa aegyptica Luffa-saponin-D yields gypsogenin and (?). Cucurbit. Luffa operculata (frt) Lupeol (Cautchicol; ß-Viscol; Xanthosterin; Lup-zo(3o)-en-3ß-ol; fig. 183) is the `parent' of a few sapogenins—betulin, betulinic acid, thurberogenin, stellatogenin. It is recorded (free or as saponins) from Loranth. Viscum Mor. Ficus, Maclura Betul. Alnus Cact. Lophocereus Capparid. Crataeva Legum. Lupinus luteos (hence the name), Spartium Lin. Roucheria Euphorbi. Euphorbia (2), Ricinus communis (sd-coat) Celastr. Celastrus, Lophopetalum Rut. Aegle, Citrus, Zanthoxylum Eben. Diospyros melanoxylon (bk) Sapot. Achras, Butyrospermum, Palaquium Apocyn. Alstonia, Dyera, Ervatamia, Holarrhena, Tabernaemontana Asclepiad. Daemia, Decalepis, Gymnema, Hemidesmus

TRITERPENOIDS 835

Logani. Fagraea Verben. Clerodendron infortunatum Acanth. Asteracantha Comp. Calendula officinalis (fl.) Gram. ? Lupeol-acetate Lardizabal. Stauntonia hexaphylla (sd) Apocyn. Alstonia, Ervatamia, Leuconotis Asclepiad. Daemia Machaeric acid (2I-Oxo-oleanolic acid) Cact. Machaerocereus spp. (as saponin) Machaerinic acid, a ß-amyrin derivative (2I-OH; z8-COOH), is the aglycone of proceranin. Cact. Machaerocereus spp. (as saponins) Legum. Albizia odoratissima (as saponin) Machaerocereus-saponins yield stellatogenin, oleanolic acid, gummosogenin, machaeric acid, machaerinic acid, quillaic acid and gysogenin. Cact. Machaerocereus spp. Mahonia-saponin: belongs here? Berberid. Mahonia pubescens Maniladiol is a ß-amyrin derivative (16-OH). Cact. Escontria chiotilla (as saponin ?), Myrtillocactus eichlamii (as saponin?) Medicagenic acid is a ß-amyrin derivative (2-OH; z3,z8-COOH). Medicago-saponin yields medicagenic acid and D-glucose. Legum. Medicago sativa Melanthic acid yields hederagenin (melanthigenin). Ranuncul. Nigella sativa (sd) Micromeria-saponin ? yields micromeritol and (?). Lab. Micromeria chamissonis (plt) Micromeritol: the genin of micromeria-saponin? Mimusops-saponin(s) yield(s) bassic acid and (from one or more) glucose, L-rhamnose and D-xylose. Sapot. Mimusops djave, globosa, heckelii? Mollugo-saponin-A yields a sapogenin (C30H5005), glucose, rhamnose and galactose. Mollugin. Mollugo nudicaulis (plt) Mollugo-saponin-B yields spergulagenin and (?). Mollugin. Mollugo spergula Momordin yields oleanolic acid (momorgenin) and (?). Cucurbit. Momordica cochinchinensis (rt) Monesin may be identical with glycyrrhizin. It yields glycyrrhetic acid and (?). 6-2

836 CHEMOTAXONOMY OF FLOWERING PLANTS

Sapot. Chrysophyllum glyciphloeum (Lucumaglyciphloeum, Pradosia lactescens) Monnierin is bacogenin-A-ß-n glucose-[L-arabinose] 3. Scrophulari. Bacopa monnieri Monninin: belongs here ? Polygal. Monnina polystachya (rt) Mora-saponin yields morolic acid, glucose, arabinose (and oleanolic acid?). Legum. Mora excelsa, gongrijpii (htwd) Morolic acid (Agauriolic acid) is a ß-amyrin derivative. Legum. Mora excelsa (as mora-saponin) Myrt. Eucalyptus papuana (bk) Eric. Agauria salicifolia Mukurosin yields hederagenin (mukurosigenin). Sapind. Sapindus mukorossa, rarak, saponaria, utilis (frts in all) Musennin yields echinocystic acid, D-glucose and 3 x L-arabinose. Legum. Albizia anthelmintica Myrtillocactus-saponins yield chichepegenin, myrtillogenic acid, cochalic acid, oleanolic acid, longispinogenin and stellatogenin. Cact. Myrtillocactus spp. Myrtillogenic acid is a ß-amyrin derivative (i6-OH; 28-CH2OH; 3o-COOH). Cact. Myrtillocactus spp. (in saponins) Odoratissimin yields echinocystic acid, glucose, arabinose, rhamnose and xylose. Legum. Albizia odoratissima Oleanolic acid (Araligenin; Caryophyllin; Guagenin; Momorgenin; Oleanol; Panax-sapogenin; Swertia acid; Taraligenin, Viscum acid), a ß-amyrin derivative (28-COOH), has been reported free and as the genin of many saponins. Is it significant that my list includes no monocotyledons ? Santal. Exocarpus cupressiformis (st., sd) Loranth. Viscum (in saponin) Amaranth. Achyranthes (2, as saponin) Chenopodi. Atriplex (as saponin), Beta, Chenopodium Mollugin. Glimu (as saponin) Cad. Heliabravoa, Lemaireocereus spp. Myrtillocactus spp. (all as saponins?) Hamamelid. Liquidambar orientalis Ros. Crataegus Legum. Albizia, Mora, Sesbania (all as saponins?) Cochlosperm. Cochlospermum Euphorbi. Petalostigma Rhamn. Zizyphus (as saponin)

TRITERPENOIDS 837

Vit. Vitis labrusca Myrt. Eugenia Cucurbit. Luffa (as saponins), Momordica Corn. Griselinia (as saponin?) Arali. Aralia spp. (as saponins) Eric. Vaccinium Eben. Diospyros (as saponin) Ole. Ligustrum, Olea (lys) Apocyn. Alyxia, Nerium (lys) Gentian. Centaurium, Swertia Valerian. Patrinia (as saponins) Plantagin. Plantago Rubi. Randia (frt, as saponin) Solan. Anthocercis (z) Lab. Prunella (2, as saponins), Salvia, Thymus Comp. Calendula (fl., as saponin) Oleanolic acid-3(galactosyl-(glucosyl))-glucuronide Comp. Calendula officinalis (fl.) Oleanolic acid-3( (galactosyl)-(glucosyl)-glucuronide)-17-glucoside Comp. Calendula officinalis (fl.) Oleanolic acid-3-(galactosyl-glucuronide) Comp. Calendula officinalis (fl.) Oleanolic acid-i7-glucoside Comp. Calendula officinalis (fl.) Oleanolic acid-3-glucuronide Comp. Calendula officinalis (fl.) Oleanolic aldehyde has been obtained from Heliabravoa-saponin and from Anacardi. Mangifera indica (resin, free ?) Comp. Calendula officinalis (fl.) Ononis-saponins yield glycyrrhetic acid and (?). Legum. Ononis repens (rt), spinosa (rt) Oxy-allo-betulin Cact. Lemaireocereus spp. (as saponins?) Pachyrhizus-saponin-A and -B yield pachysapogenin-A and -B and (?). Legum. Pachyrhizus erosus Pachysapogenin-A (C30H38O6) from pachyrhizus-saponin. Pachysapogenin-B: belongs here? It has been obtained from a pachyrhizus-saponin. Palaquium-saponin(s) yield(s) bassic acid and (?). Sapot. Palaquium gutta (sd), and other spp. ? Panaquilon yields oleanolic acid and (?). Arali. Aralia (Panax) quinquefolia

838 CHEMOTAXONOMY OF FLOWERING PLANTS

Panaxadiol is said to arise from protopanaxadiol. Panaxatriol (fig. 183) occurs in some ginsenosides. Panaxosides-A to -F are ginsenosides? Arali. Panax schinseng (ginseng) (rt) Panax-saponin yields oleanolic acid and (?). Arali. Panax repens (rt) Panax-toxin Arali. Panax repens (rt) Patrinia-saponin(s) yield(s) oleanolic acid and (?). Valerian. Patrinia scabiosifolia (rt, rtstk), villosa Patrinin yields a sapogenin, fructose, and a pentose. Valerian. Patrinia intermedia Patrinosides-A to -D yield oleanolic acid, glucose and xylose. Are they distinct entities ? Valerian. Patrinia intermedia (rt, rtstk) Patrizid-A yields oleanolic acid, glucose and xylose. Is it one of the patrinosides? Valerian. Patrinia intermedia Payena-saponin yields bassic acid and (?). Sapot. Payena lucida (bk, sd) Periandra-saponin yields glycyrrhetic acid and (?). Legum. Periandra Phaseolus-saponin yields soyasapogenol-C, glucose, rhamnose, arabinose and glucuronic acid. Legum. Phaseolus radiatus Phillyrigenin (C30H4804) has been obtained from pittosporum-saponin-B. Phytolaccagenin is a ß-amyrin derivative (2-OH; 23-CH2OH; 28COOH; 29-COOCH3). It is the aglycone of phytolaccatoxin. Phytolaccatoxin yields phytolaccagenin, glucose and xylose. Phytolacc. Phytolacca americana Picene: when triterpenoid sapogenins are dehydrogenated they yield 1,8-dimethyl picene which is not given by steroidal sapogenins. Pithecellobium-saponin yields pithecogenin and (?). Legum. Pithecellobium dulce Pithecogenin (C28H44O4): belongs here? Pittosapogenin (C30H5006) has been obtained from pittosporum-saponinsA and -B. Pittosporum-saponin-A yields pittosapogenin, barrigenol-A1 and (?). Pittospor. Pittosporum undulatum Pittosporum-saponin-B yields pittosapogenin, phillyrigenin and (?). Pittospor. Pittosporum phillyraeoides Platycodigenin (C30H4807) Campanul. Platycodon grandiflorum (rt, as saponin)

TRITERPENOIDS

839

Podalyria-saponin yields glycyrrhetic acid and (?). Legum. Podalyria tinctoria (it) Polygalacic acid is a ß-amyrin derivative (2,16-OH; 23-CH2OH; 28-COOH). It is the genin of polygala-saponin-A. Polygala-prosapogenin is a ß-amyrin derivative. Polygal. Polygala senega, tenuifolia (as saponin) Polygala-saponin-A yields polygalacic acid and (?). Polygal. Polygala `paenea' (what is this ?) Polygala-saponin-B yields a sapogenin (C27H4608), D-glucose, L-arabinose and L-rhamnose. Polygal. Polygala major Polygalic acid (Senegenic acid) is a ß-amyrin derivative. Polygal. Polygala senega Polyscias-sapogenin resembles hederagenin? Polyscias-saponin-A yields oleanolic acid and (?). Arali. Polyscias elegans (lvs) Polyscias-saponin-B yields polyscias-sapogenin and (?). Arali. Polyscias nodosa (Ns) Primula-genins-A to -G are neutral. They are said to come from primulasaponin-A. Primula-genin-A and armillarigenin-C are said to be identical; and probably primula-genin-B and armillarigenin-D are identical. Primula-genins-SC, -SD, -SF, and -SG are acidic. They are said to come from primula-saponin-A. Primula-saponin-A must be an extraordinary substance if it yields all the genins mentioned above! In addition it is said to give D-glucose, D-galactose, D-galacturonic acid and L-rhamnose. Primul. Primula elatior Primula-saponin-B yields 2 sapogenins, 3 x glucose, rhamnose and galactose. Primul. Primula vulgaris Priverogenin-A (3ß,i6a,22oc-Trihydroxyolean-12-en-28-al) Primul. Primula veris (rt, rhiz.) Priverogenin-A-16-acetate Primul. Primula veris Priverogenin-B( i 3,28-Epoxy-oleanane-3ß,16«,22a-triol) Primul. Primula veris (rt, rhiz.) Proceranin yields machaerinic acid, ethyl machaerinate, D-glucose, D-xylose and D-arabinose. Legum. Albizia procera Proceric acid: what is this? Legum. Albizia procera a-Profatsin yields hederagenin and 2 x glucose. Arali. Fatsia japonica (rt)

840 CHEMOTAXONOMY OF FLOWERING PLANTS

ß-Profatsin yields oleanolic acid and sugars. Arali. Fatsia japonica (rt) Protoaescigenin is a ß-amyrin derivative (16,z1,zz-OH; z3,z9-CH2011). It occurs as an angelic or tiglic salt in aescin. Protopanaxadiol Arali. Panax schinseng (from ginsenosides) Prunella-saponin(s) yield(s) oleanolic acid and (?). Lab. Prunella grandifolia, vulgaris Queretaroic acid (3o-Hydroxy-oleanolic acid) Cact. Lemaireocereus queretaroensis, etc. (in saponin ?) Quillaia-saponin yields quillaic acid, galactose, and glucuronic or galacturonic acid. Ros. Quillaia saponaria (bk) Quillaic acid (Quillic acid; Quillaia-sapogenin) is a ß-amyrin derivative. It may occur in herniaria-saponin-A. Quinovic acid, an a-amyrin derivative (z7,z8-COOH), is the aglycone of quinovin and of quinovic acid-glycoside-B. Rubi. Cinchona (as saponin?); Mitragyna (3 spp.) Quinovic acid-glycoside-B yields quinovic acid and D-glucose. Rubi. Cinchona calisaya Quinovin (Quinovic acid-glycoside-A) yields quinovic acid and quinovose. Rubi. Cinchona calisaya Randia-saponin(s) yield(s) oleanolic acid, glucose, fructose, xylose and glucuronic acid? Rubi. Randia brandis (frt), dumetorum (frt) Saikogenins-A to -G are obtained from bupleurum-saponin. SaikogeninsA, -B and -C are artefacts; -E, -F and -G are said to be true sapogenins; -E is 13ß,z8-epoxyolean-11-ene-3ß,16ß-diol; -F and -G are said to be very similar. Sanguisorbigenin (Tomentosolic acid) is an a-amyrin derivative, the aglycone of sanguisorbin, and a constituent of vangueria-saponin. Sanguisorbin yields sanguisorbigenin, 2 x glucose, and a pentose. Ros. Poterium sanguisorba (rt), Sanguisorba officinalis Sanicula-saponins Umbell. Sanicula europaea (lvs, rts) Sapindus-saponin yields hederagenin and (?). Sapind. Sapindus laurifolius Saponigellin Caryophyll. Agrostemma githago Saponinic acid: belongs here ? It yields a resinous genin and galacturonic acid. Legum. Coronilla emerus

V TRITERPENOIDS 84I

Saporubin yields gypsogenin and (?). Caryophyll. Saponaria officinalis Sapteroxyloside: belongs here ? Meli. Ptaeroxylon Schima-saponin yields barrigenol-A1(K-schimagenol) and (?). The. Schima kankoensis (bk) Scrophularia-saponin yields triterpene-A (smithiandienol, a ß-amyrin derivative), triterpene-B (also a ß-amyrin derivative), and (?). Scrophulari. Scrophularia smithii Senegenin is a ß-amyrin derivative, occurring in senegin. Senegin yields senegenin and (?). Polygal. Polygala senega Sesbania-saponin(s) yield(s) oleanolic acid, a neutral genin and ( ?)• Legum. Sesbania aculeata (frt), aegyptica (sd) Sideroxylon-saponin-A yields bayogenin and (?). Sapot. Sideroxylon pohlmanianum (all pts ?) Sideroxylon-saponin-B yields gypsogenin and (?). Sapot. Sideroxylon tomentosum (frt) Silene-saponins-A and -B Caryophyll. Silene brahuica (one in the st., one in the rt) Solidago-saponin(s) yield(s) oleanolic acid, glucose and arabinose. Comp. Solidago canadensis Sophoradiol (C3,H50O2) from sophora-saponin. Sophora-saponin yields betulin, sophoradiol, glucose, glucuronic acid and glucurono-lactone. Legum. Sophora japonica Soyasapogenol-A is a ß-amyrin derivative (21,22-OH; 23-CH2OH) from soyasaponin and trifolium-saponin. Soyasapogenol-B is a ß-anayrin derivative (2i-OH; 23-CH2OH) from saponins of Glycine (Soya), Lotus, and Trifolium. Soyasapogenol-C is a ß-amyrin derivative (z3-CH2OH; A21(22)) from saponins of Glycine, Phaseolus and Trifolium. Soyasapogenol-D is of unknown structure (1967) ? It occurs in a soyasaponin. Soyasapogenol-E Soya-saponins yield soyasapogenols-A to -D and (?). Legum. Glycine (Soya) max Spergulagenic acid (3ß-Hydroxy-olean-12-ene-z8,29-dioic acid) is a sapogenin from mollugo-saponin(s). Spergulagenin (3ß-Hydroxy-olean-I2-ene-28,30-dioic acid) occurs in mollugo-saponin-B.

842 CHEMOTAXONOMY OF FLOWERING PLANTS

Spergulariasaponin yields spergulariagenin, glucose, 4 x arabinose, 2 x xylose and rhamnose. Caryophyll. Spergularia marginata (media?) OH Stellatogenin is a lupeol derivative (17,19-lactone; R `j') Cact. Lemaireocereus stellatus, etc.; Machaerocereus spp.; Myrtillocactus schenckii (as saponins in all ?) Stryphnodendron-genin-B is a ß-amyrin derivative (zi - 28 lactone). Stryphnodendron-genin-F is a ß-amyrin derivative (2-OH; 20 28 lactone). Stryphnodendron-saponin yields stryphnodendron-genins-B, -F, and (?). Legum. Stryphnodendron coriaceum Styrax-saponin: belongs here ? (Its sapogenin (C27H4405) is said not to be steroidal.) It yields also benzoic acid, glucose, galactose, rhamnose, and glucuronic acid. Styrac. Styrax officinalis Swartziagenin (C30H4804) occurs in swartzia-saponins. Swartzia-saponins-A and -B yield swartzia-genin, glucose, xylose, rhamnose, and glucuronic acid. Legum. Swartzia madagascariensis (frt) a-Taralin yields oleanolic acid, 2 x glucose and glucuronic acid. Arali. Aralia chinensis (rtstk) Tenuifolic acid from bredemeyera-saponin. What is it ? Terminalia-saponin yields arjunolic acid and glucose. Combret. Terminalia arjuna Thankunic acid: of unknown structure (1967) ? Thankuniside yields thankunic acid, 2 x glucose, and rhamnose. Umbell. Centella asiatica (Indian var.) Thea-sapogenin occurs in camellia-saponin-B. Thurberogenin is a lupeol derivative (17,19-lactone; R`?') Cact. Lemaireocereus thurberi, etc. (in saponins?) Thymunic acid is an acidic saponin which yields thymuninic acid and sugars. Lab. Thymus vulgaris Thymuninic acid from thymunic acid. Thymusapogenin from thymusaponin. Thymusaponin is a neutral saponin yielding thymusapogenin and sugars. Lab. Thymus vulgaris Tormentol (C30H4806) is the aglycone of tormentoside. Tormentoside yields tormentol and z x glucose. Ros. Potentilla tormentilla (rt); Poterium sanguisorba (rt) Treleasegenic acid (21-Hydroxy-queretaroic acid) Cact. Lemaireocereus treleasei (as saponin?)

TRITERPENOIDS

843

29 21 22 28

28

16 HO HO 23

27 HO

ß - Amyrin

oC-Amyrin

Arjunolic acid

HO

Bacogenin-A

Lupeol

(R=

Betulinic acid

R1:CH3)

R1 R2

OH

"Parent usubstance

Dumortierigenin

Panaxatriol

of Cucurbitacins Fig. 183.

Some triterpenoid sapogenins.

Trifolium-saponins are said to yield soyasapogenols-A, -B and -C, glucose, galactose, xylose and rhamnose. Legum. Trifolium alpinum?, repen, fragiferum (has a saponin yielding at least 2 soyasapogenols) Vaccaroside yields gypsogenin and glucose. Caryophyll Saponaria vaccaria Vangueria-saponin(s) (`Vanguerin') yield(s) a mixture (`vanguerigenin') of vanguerolic acid, sanguisorbigenin (tomentosolic acid), and (?). Rubi. Vangueria spinosa (rt), tomentosa (rt)

844. CHEMOTAXONOMY OF FLOWERING PLANTS

Vanguerolic acid is an a-amyrin derivative. Xanthocephalum-saponins: belong here ? Comp. Xanthocephalum spp. Xanthophyllum-saponin yields oleanolic acid and (?). Polygal. Xanthophyllum octandrum Ziziphus-saponin yields oleanolic acid and (?). Rhamn. Ziziphus xylopyrus

V.2 Triterpenoids other than Saponins and Sapogenins GENERAL These terpenoids are less numerous than are the triterpenoid saponins and sapogenins, but they still form a large group. They show different degrees of oxidation. Thus Alves et al. (1966) have found in the sapwood of Machaerium incorruptibile (a legume) four pentacyclic triterpenes ß-amyrin acetate, erythrodiol-3-acetate, 0-acetyloleanolic aldehyde, and 0-acetyl-oleanolic acid which have the oxidation sequence R—CH3, R—CH2OH, R—CHO and R—COOH. Djerassi had previously noted the occurrence in the Cactaceae (but in different members) of f3-amyrin, erythrodiol, oleanolic aldehyde and oleanolic acid. There are many tetracyclic triterpenes. Several occur in the Euphorbiaceae, and Ponsinet and Ourisson have started work on them, using thin-layer chromatography and RMN spectroscopy. The cucurbitacins of the Cucurbitaceae (p. 829) are thought to be related to the tetracyclic triterpenes; so, too, are the limonoids and simaroubolides. Dreyer (1964) has suggested that simaroubolides arise by a process in which a 5-carbon unit is split from a limonoid precursor, followed by loss of a —CH3 group from C4. It is known that limonoids are split hydrolytically by alkali and that the C21 compound formed has the basic skeleton of the simaroubolides. Chemotaxonomically there is much of interest in the triterpenoids. Djerassi (1957) says that to out of 16 triterpenes known (at that time) from the Cactaceae are known only from the family. It is obvious from the following list that a few families are particularly rich in triterpenoids. Note the Meliaceae, Simaroubaceae and Rutaceae in this connection (p. 168o).

TRITERPENOIDS 845

List and Occurrence I Iß-Acetoxy-gedunin is a tetranortriterpenoid. Meli. Carapa guianensis (htwd) 3ß-Acetyl-oleanolic acid (O-Acetyl-oleanolic acid) Saxifrag. Philadelphus coronarius Legum. Drepanocarpus lunatus (wd), Machaerium incorruptibile (spwd), Pterocarpus angolensis Myrt. Eugenia jambolana Eric. Leucothoe grayana Ole. Ligustrum japonicus 3ß-Acetyl-oleanolic aldehyde Legum. Machaerium incorruptibile (spwd) Adianenediol Eric. Rhododendron linearifolium Agaurilol (C30H4502 .OH) Eric. Agauria salicifolia (wax of bk ?) Aglaiol Meli. Aglaia odorata (lvs) Ailantholide (C20H2607) is a simaroubolide. Simaroub. Ailanthus Ailanthone (fig. 185) is a simaroubolide. Simaroub. Ailanthus (2) Amarolide is a simaroubolide. Simaroub. Ailanthus glandulosa (bk) Amarolide-l2-acetate Simaroub. Ailanthus glandulosa a-Amyrin acetate Sapot. Madhuca butyracea (bk, frt) Apocyn. Alstonia, Ervatamia, Plumeria Asclepiad. Daemia fl-Amyrin acetate Mor. Artocarpus Lardizabal. Stauntonia hexaphylla (sd) Legum. Machaerium incorruptibile (spwd) Burser. Canarium strictum (resin) Sapot. Madhuca butyracea (bk, frt) Apocyn. Plumeria Amyrin isovalerate: is this a- or ß- ? Rhamn. Ceanothus a-Amyrin-methyl ether Gram. Cortaderia toeto

846 CHEMOTAXONOMY OF FLOWERING PLANTS

ß-Amyrin-methyl ether (Isosawamilletin) Gram. Cortaderia toetoe Andirobin is a tetranortriterpenoid closely related to the hypothetical precursor of swietenine. Meli. Carapa guianensis (sd) Angolensic acid (C28H3207): a limonoid? Meli. Cedrela odorata, Entandrophragma angolense, Guarea thompsonii Anthocleistin: belongs here? Logani. Anthocleista procera Anthothecol is an I Ia-acetoxy derivative of cedrelone. Meli. Khaya anthotheca (htwd) Arborinol is pentacyclic. Rut. Glycosmis arborea Arnidiol (fig. 185) is pentacyclic. It seems to be rather widely distributed in the composites. Comp. Arnica, Calendula officinalis (fl.), Helianthus, Taraxacum, Tussilago Artostenone (C 30H500) Mor. Artocarpus integrifolia (frt) Arundoin (Fernenol-methyl ether; 3ß-Methoxy-E:C-friedo-isohop9(I I)-ene) Gram. Cortaderia toetoe (wrongly identified as Arundo), Imperata cylindrica (rhiz.), Saccharum officinarum (1f-wax) Azadiradione Meli. Melia azedarach (sd-oil) Azadirone Meli. Melia azedarach (sd-oil) Bauerenol is a pentacyclic triterpene. Euphorbi. Gelonium multiflorum (bk) Rut. Acronychia baueri Apocyn. Haplophyton cimicidum (plt) Bauerenyl-acetate Apocyn. Ervatamia wallichiana (lvs, bk), Tabernaemontana laurifolia (bk) Betulinic acid-palmitate Sapot. Madhuca butyracea (bk) a-Boswellic acid is a pentacyclic triterpene which occurs as acetate ? Burser. Boswellia carteri, frereana ß-Boswellic acid (3a-Hydroxy-urs-I2-en-24-oic acid) occurs as acetate with a-boswellic acid? Bourjotone: belongs here ? Rut. Flindersia bourjotiana

TRITERPENOIDS 847

Brein is pentacyclic. Burser. Canarium commune (resin) Bruceine-A, -13, and -C are simaroubolides (bitter principles). Simaroub. Brucea amarissima (sumatrana) Bussein: is very like entandrophragmin (a limonoid) ? Meli. Entandrophragma bussei (htwd), caudatum (htwd, little), ekebergioides (htwd ?), spicatum (htwd) Calenduladiol is very like arnidiol. Comp. Calendula officinalis (fl.) Campanulin Eric. Rhododendron campanulatum Canaric acid: belongs here ? Burser. Canarium muelleri (resin) Candollein: is very near entandrophragmin? Meli. Entandrophragma candollei (htwd) Carapin is a bicyclononanolide. Meli. Carapa procera (htwd), Cedrela glaziovii (htwd) Cedrelone is a limonoid. Meli. Cedrela toona Cedronine (7-Dihydro-samaderine-B) is a simaroubolide. Simaroub. Simaba cedron Cedronyline (7-Dihydro-samaderine-C) Simaroub. Simaba cedron Chaparrin is a simaroubolide whose `close structural relationship to quassin is striking'. Simaroub. Castela nicholsoni Chaparrinone: a simaroubolide? Simaroub. Ailanthus altissima (sd) Cyclobuxine Bux. Buxus sempervirens Cylindrin (3ß-Methoxy-arbor-9(i i)-ene) Gram. Imperata cylindrica var. koenigii (rhiz.) Dammaradienone (fig. 185) is tetracyclic. Dipterocarp. Dipterocarpus (42 spp. ?) Dammaradienol-I Dipterocarp. Doona (in all spp. ?) Dammaradienol-II Dipterocarp. Anisoptera (2?), Cotylelobium (2 ?), Dipterocarpus, Upuna (1 ?) 7-Deacetoxy-3-deacetyl-7-oxo-khivorin is a limonoid. Meli. Khaya senegalensis (sd) 7-Deacetoxy-7-oxo-dihydro-a-gedunin is a limonoid Meli. Guarea thomsonii (wd)

848 CHEMOTAXONOMY OF FLOWERING PLANTS

7-Deacetoxy-7-oxo-gedunin is a tetranortriterpenoid (limonoid?) Meli. Carapa guianensis (sd); Cedrela glaziovii (htwd), odorata (htwd); Pseudocedrela kotschyii (wd) 7-Deacetoxy-7-oxo-khivorin Meli. Khaya senegalensis (htwd, but only in some specimens) 7-Deacetyl-gedunin: a limonoid (meliacin) ? Meli. Pseudocedrela kotschyii (wd) 3-Deacetyl-khivorin is a limonoid. Meli. Khaya anthotheca (sd), senegalensis (sd) Deacetyl-nomilin (Iso-limonin ?) is a limonoid. Rut. Citrus (11 spp. and some hybrids), Microcitrus australasica var. sanguinea (prob. in sd), Poncirus trifoliata (sd) 3-Dehydro-mexicanol Meli. Cedrela glaziovii (htwd) Deoxy-andirobin: a limonoid? Deoxy-limonin: a limonoid. Rut. Citrus paradisi (sd) 6-Deoxy-swietenolide: a bicyclononanolide? Meli. Khaya ivorensis (sd) 6;i iß-Diacetoxy-gedunin Meli. Carapa guianensis (htwd) Dihydro-gedunin Meli. Gaurea thomsonii (htwd), but absent from G. cedrata? ß,ß-27-Dihydroxy-24(28)-methylen-(25e)-cycloartane Anacardi. Mangifera indica (resin) Diospyric acid: belongs here ? Eben. Diospyros melanoxylon (bk) Dipterocarpol (Hydroxy-dammarenone-II) Dipterocarp. Anisoptera (2), Dipterocarpus (42 ?) Dryobalanone (20,21-Dihydroxy-dammar-24-en-3-one) Dipterocarp. Dryobalanops aromatica (resin) Emmolic acid Rhamn. Alphitonia Entandrophragmin (fig. 185) is a limonoid. Meli. Entandrophragma bussei (wd), caudatum (wd), cylindricum Epialnusenol: belongs here ? Lab. Salvia glutinosa (gummy secretion) Epifriedelinol (Friedelan-3ß-ol) seems to be very widely distributed. It has been reported from lichens and from Balanop. Balanops Salic. Salix Ros. Photinia Cunoni. Ceratopetalum

TRITERPENOIDS 849

Euphorbi. Aporusa chinensis (lvs, st.), Baccaurea sapida, Mallotus paniculatus (lys, st.) Myrt. Syxygium cordatum (bk, spwd) Eric. Rhododendron Verben. Clerodendron Comp. Mikania cordata (rt) Epi-glutinane: belongs here? Eric. Rhododendron westlandii Epi-lupeol: belongs here ? Euphorbi. Glochidion hohenackeri (latex ?) Burser. Bursera spp. (latex) Epoxy-malabaricol is of malabaricane type. Simaroub. Ailanthus malabarica (resin) Erythrodiol-3-acetate Legum. Machaerium incorruptibile (spwd) Erythrodiol-stearate Erythroxyl. Erythroxylum novogranatense (frt) Eurycoma-lactone is a simaroubolide. Simaroub. Eurycoma longifolia (bk) Faradiol is very like arnidiol. Comp. Calendula officinalis (fl.) Fernenol (3ß-Hydroxy-fern-9(xr)-ene) Comp. Artemisia vulgaris Gram. Imperata cylindrica var. koenigii (rhiz.) Ferreol Legum. Ferreirea spectabilis Fissinolide (Grandifoliolin) is a bicyclononanolide. Meli. Cedrela fissilis (frt), Guarea trichilioides, Khaya grandifoliola (wd) Flindissol is a limonoid. Rut. Flindersia dissosperma (lvs, bk) Friedelane-3,7-dione (Putranjivadione) Euphorbi. Putranjiva roxburghii (plt) Friedelanol: is this friedelan-3ß-ol (epifriedelinol) ? Euphorbi. Euphorbia antiquorum (plt) Friedel-3-ene Eric. Vaccinium membranaceum (underground pts) Friedelin, a pentacyclic triterpene ketone, is widely distributed Balanop. Balanops Fag. Shiia Salk. Salix Ulm. Zelkova Menisperm. Hypserpa

850 CHEMOTAXONOMY OF FLOWERING PLANTS

Cunoni. Ceratopetalum Euphorbi. Aporusa chinensis (lvs, st.), Baccaurea sapida, Bridelia micrantha (bk), Mallotus paniculatus (lvs, st.) Hippocastan. Aesculus Myrt. Syzygium cordatum (bk, spwd) Eric. Rhododendron Sapot. Madhuca butyracea (bk) Apocyn. Acokanthera spectabilis Verben. Clerodendron Lab. Salvia glutinosa (gummy secretion) Comp. Inula, Mikania cordata (rt) Friederin Gram. ? Gedunin (fig. 185) is a limonoid. Meli. Cedrela glaziovii (htwd), odorata (wd); Entandrophragma angolense (wd), delevoyi; Xylocarpus granatum Germanicol (Isolupeol) is pentacyclic. Euphorbi. Euphorbia balsamifera (latex), pulcherrima (plt) Comp. Lactuca Germanicol-3-methyl ether (3ß-Methoxy-olean-I8-ene; Miliacin) Gram. Panicum miliaceum, Syntherisma sanguinalis var. ciliaris Glaucarubin is a simaroubolide, the a-methyl-a-hydroxy-butyryl ester of glaucarubol. Simaroub. Perriera madagascariensis, Simarouba glauca Glaucarubinone is a simaroubolide. Simaroub. Perriera madagascariensis, Simarouba glauca Glaucarubol is a simaroubolide. Simaroub. Castela nicholsoni, Holacantha emoryi Glaucarubolone is a simaroubolide. Simaroub. Castela nicholsoni, Hannoa klaineana (sd), Simarouba glauca Glut-5(6)-en-3a-ol Euphorbi. Euphorbia cyparissias Glut-5(6)-en-313-ol (D:B-Friedo-olean-5-en-313-ol) Euphorbi. Euphorbia cyparissias (plt), royleana (plt) Lab. Salvia glutinosa Glut-5(6)-en-3-one (Glutenone ?) Euphorbi. Euphorbia cyparissias Gossypol (C30H9008; fig. 185) is really a sesquiterpene-dimer? It is related to gossyverdurin. Maly. Gossypium (in sds of all spp. ?) Gossyverdurin is related to gossypol. Maly. Gossypium

TRITERPENOIDS

851

Grandifoliolenone Meli. Khaya grandifoliola (htwd) Havanensin Meli. Trichilia havanensis (as I,7-diacetate, 3,7-diacetate, and as a triacetate) Heudelottin is related to havanensin. Meli. Trichilia heudelottii (wd) Hirtin is related to havanensin. Meli. Trichilia hirta (lvs, sd) I 1a-Hydroxy-ß-amyrin Lab. Salvia glutinosa (gummy secretion) 6-Hydroxy-angolensic acid-methyl ester: a limonoid? Meli. Khaya grandifoliola (also as acetate), senegalensis Hydroxy-dammarenone-I Dipterocarp. Doona (all spp. ?) Trans-3ß-Hydroxy-24(28)-methyl-cycloart-24-en-27-al Anacardi. Mangifera indica (resin) 2u-Hydroxy-ursolic acid is isomeric with maslinic acid. Onagr. Chamaenerion angustifolium (lvs) 19-Hydroxy-ursolic acid (Benthamic acid; Pomolic acid) Ros. Malus (frt) Labi. Micromeria benthami (above-ground pts) Hystrix-lactone: belongs here ? It may well be a sapogenin. Cact. Lemaireocereus spp. Ichangin is a limonoid. Rut. Citrus ichangensis and some of its hybrids Icterogenin is a ß-amyrin derivative, related to rehmannic acid. Verben. Lippia rehmanni (lvs, rts) Iso-arborinol (3ß-Hydroxy-arbor-9(II)-ene) is an epimer of arborinol. Rut. Glycosmis arborea Gram. Imperata cylindrica var. koenigii (rhiz.) I I-Keto-a-amyrin Burser. Canarium strictum (resin) Khayanthone: a limonoid? Meli. Khaya anthotheca (sd) Khivorin is a limonoid related to gedunin. Meli. Khaya grandifoliola (htwd), ivorensis; Trichilia splendida? Lactucerin: acetyl derivative(s) of taraxasterol. Comp. latices of many ß-Lactucerol (ß-Anthesterin): belongs here ? It occurs as acetyl derivatives in the latices of composites. Lactucon: acetyl derivative(s) of taraxasterol. Comp. Iatices of many

852 CHEMOTAXONOMY OF FLOWERING PLANTS

Lansic acid is a variant of the onocerin group. It is bicyclic. Meli. Lansium domesticum (frt, peel of var.) Limonin (fig. 185) is a limonoid. Rut. Citrus (all spp. ?), Calodendrum, Dictamnus, Evodia (3), Fortunella, Luvunga, Microcitrus, Phellodendron, Poncirus Limonin-diosphenol (Evodol) is a limonoid. Rut. Calodendrum capensis (sd), Evodia rutaecarpa (sd) Lurenol is isomeric with lupeol. Mor. Madura Malabaricanediol: similar to malabaricol? Simaroub. Ailanthus malabarica (resin) Malabaricol (fig. 185) is described as of malabaricane type—a new group of 8 similar compounds in Simaroub. Ailanthus malabarica (resin) Mangiferolic acid: belongs here? It is 3ß-hydroxy-cycloart-24-en-26 (or 27)-oic acid. Anacardi. Mangifera indica Maslinic acid is isomeric with 2x-hydroxy-ursolic acid. Onagr. Chamaenerion angustifolium (lvs) Meliacin (fig. 185) is the hypothetical `parent' of the meliacins (limonoids). Melianodiol Meli. Melia azedarach Melianol Meli. Melia azedarach Melianone (24,25-Epoxy-flindissone) Meli. Melia azedarach (frt) Melianotriol is a locust phago-repellent. Meli. Melia azedarach Methyl-6-acetoxy-angolensate is a limonoid or tetranortriterpenoid. Meli. Khaya grandifoliola (htwd) Methyl-angolensate is a limonoid. Meli. Cedrela glaziovii (htwd), odorata (wd); Entandrophragma (3 ?); Guarea thompsonii (wd); Khaya grandifoliola (htwd) Methyl-6-hydroxy-angolensate Meli. Khaya grandifoliola Mexicanol Meli. Cedrela glaziovii (htwd), mexicana (htwd) Mexicanolide is a bicyclononanolide. Meli. Cedrela glaziovii (htwd), odorata (htwd); Khaya grandifoliola? Micromeric acid: an a-amyrin derivative ? Lab. Micromeria benthami (above-ground pts)

TRITERPENOIDS 853

Multiflorenol (D : C-Friedo-olean-7-en-3ß-ol) Euphorbi. Gelonium multiflorum Neoandrographolide: belongs here? Acanth. Andrographis Neohavanensin: a limonoid? Meli. Trichilia havanensis (as an ester) Neoquassin is a simaroubolide, nearly related to quassin. Simaroub. Quassia amara Nimbin is a limonoid (see salannin). Meli. Melia azedarach (sd) Nimbinin: a limonoid? Meli. Melia azedarach, indica Nimbolide: a limonoid? Meli. Melia indica (lvs) Nomilin is a limonoid. Rut. Casimiroa edulis (sd), tetrameria (sd) ; Citrus; Poncirus trifoliata 3o-Norlupan-3ß-ol-zo-one Euphorbi. Ricinus commonly (sd-coat) Nyasin is a limonoid. Meli. Khaya nyasica Obacunone is a limonoid. Rut. Casimiroa, Citrus (q, and some hybrids), Dictamnus, Fortunella, Poncirus, Phellodendron Ocotillol: belongs here ? Cact. Neolloydia texensis (plt) Fouquieri. Fouquieria splendens (` ocotillo', bk) zog-i-Ocotillone is pentacyclic. Dipterocarp. Dipterocarpus (42?) 2O -2-OcotillOne (fig. 185) is pentacyclic. Dipterocarp. Dipterocarpus (42?) Olean-13(18)-en-3ß-ol is pentacyclic. Oleanolic acid-palmitate Sapot. Madhuca butyracea (frt) oc-Onocerin (Onocol) Legum. Ononis spinosa (rt) Pachysandiol-A (2a,3ß-Dihydroxy-friedelane) Bux. Pachysandra terminalis Pachysandiol-B Bux. Pachysandra terminalis Phyllanthol (C30H5500) is pentacyclic. Euphorbi. Phyllanthus acidus (bk), engleri (rtbk) Picrasmin (Isoquassin) is a simaroubolide. Simaroub. Aeschrion excelsa (wd)

854 CHEMOTAXONOMY OF FLOWERING PLANTS

Pseudo-epitaraxastane-diol Burser. Canarium strictum (resin) Pseudo-taraxasterol is pentacyclic. Dipterocarp. Doona Burser. Canarium strictum (resin) Comp. Calendula officinalis (fl.), Cynara, Taraxacum Pseudrelone-A is a meliacin or limonoid in the same class as bussein. Meli. Pseudocedrela kotschyii (wd) Pseudocedrelone-B Meli. Pseudocedrela kotschyii (wd) Psidiolic acid Myrt. Psidium guajava (lvs) Quassin (C22H3008; fig. 185) is a simaroubolide. Simaroub. Quassia amara Rehmannic acid (Lantadene-A; fig. 184) is a photosensitizes (pp. 2307-8) Verben. Lantana camara, Lippia rehmanni (rt) Rutaevin (Dictamnolide ?) is a limonoid. Rut. Calodendrum capensis (sd); Dictammus (dictamnolide); Evodia hupehensis (sd), rutaecarpa (sd) Salannin is a tetranortriterpenoid (limonoid?). Henderson et al. (1968) say: `Salannin and nimbin, both isolated from the same plant, are at present unique, being the only tetranortriterpenoids in which ring C of apoeuphol is cleaved.' Meli. Meli azadarach (sd), dubia (frt) Samaderines -A, -B (fig. 184), and -C are all simaroubolides? Simaroub. Samadera indica (bk) Shionone: belongs here? Comp. Aster tataricus (rt) Siaresinolic acid (Siaresinol) is pentacyclic. Styrac. Styrax tonkinensis (resin) Simarolide is a simaroubolide. Simaroub. Simarouba amara Simiarenol (Adian-5-en-3ß-ol) Eric. Rhododendron simiarum Gram. Imperata cylindrica var. koenigii (rhiz.) Squalene (Spinacene; C30H50; fig. 184) is a `straight-chain' hydrocarbon of very wide distribution. It occurs in yeasts and in Papaver. Papaver Crucif. Brassica Legum. Arachis hypogaea (sd-oil), Glycine max (sd-oil) The. Camellia Lin. Linum usitatissimum (sd-oil) Euphorbi. Aleurites

TRITERPENOIDS 855

Maly. Gossypium Tili. Tilia vulgaris (wd) Vit. Vitis Anacardi. Anacardium Ole. Olea europaea (frt) Comp. Hypochoeris Palmae. Cocos, Elaeis, Oenocarpus Gram. Oryza, Zea Swietenine (fig. 184) is described by Connolly, Henderson et al. (1965) as the first bicyclononanolide. Others are carapin, mexicanolide, swietenolide, and fissinolide. Meli. Swietenia macrophylla (sd ?) Swietenolide is a bicyclononanolide. Meli. Swietenia macrophylla (sd) Taraxasterol (a-Anthesterin; a-Lactucerol; Taraxasterin) occurs as acetyl derivatives (lactucerin, lactucon) in the latices of many composites. It has been obtained (free in some cases ?) from Euphorbi. Euphorbia tirucalli (latex), watanabei (plt) Asclepiad. Calotropis (as esters)

Comp. Calendula officinalis (fl.), Eupatorium cannabinum, Taraxacum Taraxerol (Alnulin; Skimmiol; Tiliadin) is pentacyclic. It seems to be widely distributed.

Myric. Myrica Betul. Alnus Laur. Litsea Euphorbi. Bridelia micrantha (bk), Euphorbia (at least 9 spp.) Rut. Skimmia Tili. Tilia (`Tiliadin') Eric. Pieris, Ledum, Vaccinium (2) Sapot. Mimusops Comp. Taraxacum (2) Taraxerol-methyl ether (Crusgallin; Sawamilletin) Gram. Echinochloa crus-galli (sd, oil), Saccharum officinarum (1f-wax) Taraxerone (Protalnulin; Skimmione)

Betul. Alnus (3) Euphorbi. Bridelia micrantha (bk) Rut. Skimmia Simaroub. Samadera indica (bk) Eric. Vaccinium (2) Trichilenone: a limonoid? Meli. Trichilia havanensis (as acetate)

856 CHEMOTAXONOMY OF FLOWERING PLANTS

COOH

Rehmannic acid

Samaderine-B

O. Tigloyl

Squalene

Swietenine

HO

Ursolic acid

Fig. 184. Some triterpenoids and derivatives. Turraeanthin: belongs here? Meli. Turraeanthus afrkanus (htwd) Ursolic acid (Malol; Prunol; Matesterine; Masterin; Urson(e); fig. 184) is pentacyclic, is widely distributed in the wax-like coating of leaves and fruits, and was first isolated as 'ursone' more than a century ago from leaves of Arctostaphylos uva-ursi. It has the C-structure of picene. Ros. many Dipterocarp. Doona Aquifoli. Ilex (g)

TRITERPENOIDS 857 O

HO HO

Arnidiol

Dam marad ien one

RCO O O

CH3

Dammarened iol-II

OCOR OCOR OH

OH

Entandrophragmin ?

Gedunin

Ailanthone

Gossypol

Qua ssin

Malabaricol

Meliacin

Limonin

20c 2-Ocotillone

Fig. as. Some triterpenoids and derivatives. Myrt. Metrosideros Onagr. Chamaenerion Pyrol. Pyrola (3, as `urson') Eric. Arbutus, Arctostaphylos, Cassandra, Erica (3), Ledum, Rhododendron, Vaccinium (z) Empetr. Empetrum (i) Ole. Osmanthus Apocyn. Alyxia, Strophanthus, Vinca Solan. Anthocercis

858 CHEMOTAXONOMY OF FLOWERING PLANTS

Lab. many Verben. Duranta Utilin: a limonoid? Meli. Entandrophragma utile (htwd) Uvaol is the alcohol corresponding to ursolic acid. Ros. Crataegus cuneata (lys) Eric. Arctostaphylos uva-ursi (lvs), Cassandra calyculata, Ledum palustre, Leucothoe keiskei (lvs) Veprisone Rut. Vepris

VI TETRATERPENOIDS (CAROTENOIDS, etc.) GENERAL A recent review of the carotenoids is that of Goodwin (in Swain, 1966), and the following notes are based largely on his paper. In the chloroplasts of higher plants, he says: The major pigment components are always ß-carotene..., lutein..., violaxanthin. .. and neoxanthin... [fig. 186]. In this apparent immutability the carotenoids in the photosynthetic tissues of higher plants resemble the chlorophylls which exist together as chlorophylls a and b with no variants. Taxonomically this can mean only that all higher plants have evolved from the same common ancestor... It is in their flowers and fruits that higher plants exert their individuality in regard to carotenoid synthesis and accumulation. The fruits, Goodwin says, may be divided into seven main groups: 1. With almost no carotenoids (e.g. Pyracantha rogeriana) 2. With the usual chloroplast carotenoids (e.g. Sambucus nigra) 3. With much lycopene and its precursors (phytoene, phytofluene, ~-carotene, neurosporene) (e.g. Citrullus vulgaris—red-fleshed watermelon) 4. With much ß-carotene and/or cryptoxanthin and zeaxanthin (Physalis alkakengi) 5. With large amounts of epoxides (e.g. Citrus aurantium) 6. With large amounts of allegedly unique pigments (capsanthin, rubixanthin, rhodoxanthin) (e.g. Taxus baccata) 7. With large amounts of poly-cis-carotenes (pro-y-carotene, prolycopene) (e.g. Arum maculatum)

TETRATERPENOIDS 859

Biogenesis Isopentenyl pyrophosphate (C-5)

1 Geranylgeranyl pyrophosphate (C-zo) 4, (dimerization) Phytoene (C-4o) y (oxidation) Phytofluene 4, (oxidation) ~-Carotene 4, (oxidation) Neurosporene /

ß-Zeacarotene

1

Lycopene

4,

y-Carotene 4,

ß-Carotene Some carotenoids, at least, occur in petals as mono- and di-esters with fatty-acids (Kleinig and Nietsche, 1968). The fatty-acids involved are myristic, lauric, etc.

List and Occurrence Adonirubin (4,4'-Diketo-3-hydroxy-ß-carotene) Ranuncul. Adonis annua (fl.) Adonixanthin (4-Keto-3,3'-dihydroxy-ß-carotene) Ranuncul. Adonis annua (fl.) Antheraxanthin (5,6-Epoxy-zeaxanthin) may occur in the chloroplasts of higher plants. Celastr. Euonymus europaeus (frt) Solan. Capsicum annuum (lvs, frt) Lili. Lilium tigrinum (anthers) (and other spp. ?) Antheraxanthin esters Ole. Forsythia intermedia (fl., mono- and di-esters) Astaxanthin occurs in animals, in lower plants and in Ranuncul. Adonis annua (fl., main xanthophyll present) Aurochome: what is this ? Ros. Cotoneaster bullata (frt)—absent from frts of frigida, hebephylla. Auroxanthin (5,8 : 5',8'-Diepoxy-zeaxanthin) Viol. Viola tricolor (fl.)

86o

CHEMOTAXONOMY OF FLOWERING PLANTS

Caprifoli. Lonicera japonica (frt), periclymenum, but absent from Sambucus nigra, Viburnum opulus. Buxine (1): a carotenoid ? Bux. Buxus Capsanthin (fig. 187) has a quite unusual structure. It has been found in cycads, and in Solan. Capsicum annuum (frt, red var.), frutescens var. japonicum; but absent from some members of the family. Bignoni. Tecoma radicans (fl., chief carotenoid?) Lili. Asparagus officinalis (frt); Lilium amabile (fl.), tigrinum (stamen) Capsorubin has been found in cycads and in Solan. Capsicum annuum (frt, red var.), but absent from yellow var. and from several other members of the family. cc-Carotene is widely spread. It sometimes occurs in small amounts in chloroplasts. fl-Carotene (fig. 186) is universal in leaf-chloroplasts of higher plants, amounting to about 25% of the total carotenoids. It occurs also in other organs. Elaeagn. Hippophae rhamnoides (frt), Shepherdia canadensis (frt) ? Umbell. Daucus carota (rt) Eben. Diospyros kaki (frt) Convolvul. Cuscuta australis Solan. Cyphomandra betacea (frt), Solanum lancifolium (frt) Amaryllid. Narcissus (fl.) y-Carotene seems to be widely distributed. Ros. Prunus armeniaca (frt) Icacin. Gonocaryum obovatum (frt), pyriforme (frt) Elaeagn. Elaeagnus longipes (frt), Hippophae rhamnoides (frt), Shepherdia canadensis (frt) ? Cucurbit. Citrullus vulgaris (frt) Eben. Diospyros kaki (frt) Convolvul. Cuscuta australis Comp. Gazania rigens (fl.) 8-Carotene Rut. Citrus aurantium (frt) Cucurbit. Citrullus vulgaris (frt, red-fleshed) ~-Carotene Crucif. Brassica rutabaga (rt) Rut. Citrus Eben. Diospyros kaki (frt) Solan. Lycopersicum esculentum, Physalis alkekengi (frt), Solanum tuberosum Caprifoli. Lonicera japonica (frt)

TETRAPERTENOIDS

861

Comp. Calendula officinalis (fl.) Palmae. Elaei: guineensis (palm-oil)

ß-Carotenone Rut. Murraya exotica (frt), Triphasia trifolia (frt)

Celaxanthin Celastr. Celastrus flagellaris (sd), scandens (frt, as ester) Chrysanthemaxanthin (fig. 187) or the isomer (flavoxanthin), occurs in Ranuncul. Ranunculus acer (fl.) Ros. Cotoneaster frigida (frt), hebephylla (fit) Legum. Sarothamnus scoparius (fl.) Comp. Calendula officinalis var. (fl.)

Cryptoxanthin (Caricaxanthin; 3-Hydroxy-ß-carotene) may occur in small amounts in chloroplasts. Karrer (1958) gives a long list of records from non-leaf sources. Ros. Eriobotrya japonica (fit), Rubus chamaemorus (unripe fit), Sorbus aucuparia (fit) Prote. Grevillea robusta (fl.) Elaeagn. Hippophae rhamnoides (fit) Celastr. Euonymus europaeus (fit) Caric. Carica papaya (frt) Rut. Citrus poonensis and other spp. Cucurbit. Cucurbita pepo (fl.) Eric. Arbutus unedo (fit) Eben. Diospyros costata (fit), kaki (fit) Caprifoli. Lonicera japonica (fit) Solan. Cyphomandra betacea (frt), Physalis spp. (calyx, frt—as ester), Solanum lancifolium (fit) Comp. Gazania rigens (fl.) Mus. Strelitzia reginae (fl.)

Cryptoxanthin-epoxide esters Balsamin. Impatiens noli-tangere (fl., monoester) Ole. Forsythia intermedia (fl., monoester) Comp. Taraxacum officinale (fl., diester)

Cryptoxanthin esters Ballamin. Impatiens noli-tangere (fl., monoester) Ole. Forsythia intermedia (fl., monoester) Comp. Taraxacum offrcinale (fl., monoester), Tussilago farfara (fl.,

monoester) 5,6-Epoxy-a-carotene Ranuncul. Ranunculus acer (fl.) Legum. Acacia dealbata var. (pollen) Convolvul. Cuscuta australis Comp. Tragopogon pratensis (fl.)

862 CHEMOTAXONOMY OF FLOWERING PLANTS

5,6-Epoxy-ß-carotene Ros. Sorbus aucuparia (frt) Solan. Capsicum annuum (lvs, young frt) Eschscholtzxanthin is said to be a 3,3'-Dihydroxy-dehydro-ß-carotene. Papaver. Eschscholtzia californica (fl., as ester) Flavochrome (5,8-Epoxy-a-carotene) Ranuncul. Ranunculus acer (fl.) Umbell. Daucus carota (rt) Comp. Calendula oficinalis (fl.) Flavoxanthin: an isomer of chrysanthemaxanthin? Some of the following may have one or the other. Ranuncul. Ranunculus acer (fl.) Ros. Cotoneaster frigida (frt), hebephylla (frt) Legum. Acacia dealbata var. (pollen); Sarothamnus scoparius (fl.); Ulex europaeus (fl.), gallii (fl.) ? Viol. Viola tricolor (fl.) Ole. Forsythia intermedia (?fl.) Comp. Calendula officinalis (fl.), Senecio vernalis, Taraxacum officinale (fl.) Lili. Asphodelus albus (pollen) Mus. Strelitzia reginae (fl.) Gazaniaxanthin (?Dihydro-rubixanthin) Comp. Gazania rigens (fl.) 3-Hydroxy-echinenone (4-Keto-3-hydroxy-ß-carotene) is in Euglena and Ranuncul. Adonis annua (fl.) Lutein (Xanthophyll; fig. 186) is universal in the leaf-chloroplasts of higher plants, where it may be about 4o% of the total carotenoids. It is also present in many flowers and fruits. Lutein-dipalmitate (Helenien) Crucif. Cheiranthus Ros. Kerria japonica (fl.) Comp. many 5,6-Lutein-epoxide (Eloxanthin; Xanthophyll-epoxide) Ranuncul. Caltha palustris (fl.), Ranunculus acer (fl.), Trollius europaeus (fl.) Ros. Kerria japonica (fl.), Pyracantha coccinea (frt) Legum. Acacia dealbata var., Laburnum anagyroides (fl.), Lotus corniculatus (fl.), Sarothamnus scoparius (fl.) Solan. Capsicum (red frt) Comp. Arnica montana (fl.), Tragopogon pratensis (fl.) Hydrocharit. Elodea canadensis (lvs) Lili. Colchicum autumnale (stamen)

TETRATERPENOIDS 863

Amaryllid. Clivia miniata (stamen) Mus. Strelitzia reginae (fl.) 5,6-Lutein-epoxide esters Balsamin. Impatiens noli-tangere (fl., mono- and di-esters) Comp. Taraxacum officinale (fl., mono- and di-esters), Tussilago farfara (fl., mono- and di-esters) Lutein esters Balsamin. Impatiens noli-tangere (fl., mono- and di-esters) Ole. Forsythia intermedia (fl., mono- and di-esters) Comp. Taraxacum officinale (mono- and di-esters), Tussilago farfara (fl., mono- and di-esters) Luteochrome (5,6; 5',8'-Diepoxy-ß-carotene) Solan. Physalis alkekengi (frt, 18% of total carotenoids) Lycopene (Dicarotene; Solanorubin; fig. 187) is widely distributed, particularly in many fruits, but also in other organs. Crucif. Brassica napus (rt), rutabaga (rt) Elaeagn. Elaeagnus longipes (frt), Hippophae rhamnoides (frt), Shepherdia canadensis (frt) Passiflor. Passiflora coerulea (sd) Umbell. Daucus carota (rt) Eric. Arbutus unedo (frt) Primul. Cyclamen persicum (pollen) Eben. Diospyros kaki (frt) Solan. Lycopersicum esculentum (frt), Solanum spp. (frts) Comp. Calendula officinalis, Gazania rigens (fl.) Lycophyll (Lycopen-i 6,16'-diol) Solan. Solanum dulcamara (frt) Lycoxanthin (Lycopen-i6-ol) Elaeagn. Elaeagnus longipes (frt), Shepherdia canadensis (frt) Solan. Lycopersicum esculentum (frt), Solanum dulcamara (frt) Dioscore. Tamus communis (frt) Lycoxanthin-acetate Elaeagn. Shepherdia canadensis (prob. present in frt) Mutatochrome (Citroxanthin; 5,8-Epoxy-fl-carotene) Legum. Phaseolus vulgaris (lvs) Rut. Citrus (frt) Umbell. Daucus carota (rt) Solan. Capsicum annuum (lvs, frt), Physalis alkekengi (frt), Solanum tuberosum (lvs) Comp. Calendula officinalis var. (fl.) Gram. Zea mays (lvs) Neo-a-carotene-W, a di-cis-cc-carotene, is reported from a few plants.

864 CHEMOTAXONOMY OF FLOWERING PLANTS

Neo-ß-carotene-B (Pseudo-a-carotene) is a di-cis-ß-carotene. Chenopodi. Spinacia oleracea Ros. Eriobotrya japonica (frt) Legum. Medicago sativa Solan. Capsicum annuum (lvs, frt), Lycopersicum esculentum, Solanum tuberosum Neo-ß-carotene-U (Carotenoid-X) is a mono-cis-ß-carotene. Ros. Eriobotrya japonica (frt) Legum. Medicago saliva Solan. Lycopersicum esculentum Neo-y-carotene Ros. Pyracantha angustifolia (frt) Palmae Elaeis guineensis (palm-oil) Neo-cryptoxanthin-A is a di-cis-cryptoxanthin. Gram. Zea mays (yell. frt) Neolycopene-A is a mono-cis-lycopene. Ros. Pyracantha angustifolia (frt) Solan. Lycopersicum Comp. Calendula officinalis var. (fl.) Palmae Elaeis guineensis (palm-oil) Neoxanthin (fig. 186) is universal in the chloroplasts of higher plants, amounting to about 15% of the total carotenoids. Neoxanthin esters Ballamin. Impatiens noli-tangere (fl., di-ester) Ole. Forsythia intermedia (fl., di-ester) Neurosporene is said to be an intermediate in the biogenesis of carotenoids (fig. 859). Does it occur naturally in any quantity in any higher plant ? Physalien (Physalin; Zeaxanthin-dipalmitate ?) Elaeagn. Hippophae rhamnoides (frt) Solan. Lycium barbarum (fit), carolinianum (frt), halimifolium (frt); Physalis alkekengi (frt), francheti (frt); Solanum hendersonii (fit), pseudo-capsicum Lili. Asparagus officinalis (frt) Phytoene is a colourless polyene; an intermediate in the biogenesis of carotenoids (fig. 859). Euphorbi. Hevea brasiliensis (lvs, etc.) Cucurbit. Citrullus vulgaris (frt, red-fleshed) Umbell. Daucus carota (rt) Eben. Diospyros kaki (frt) Solan. Lycopersicum esculentum (frt) Phytofluene is a colourless polyene; an intermediate in the biogenesis of

VI TETRATERPENOIDS 865

carotenoids. It was found in very small amounts in all the plants (21 spp. belonging to 18 families) examined by Zechmeister and Karmakar (1953). It is also present (in larger amounts ?) in Legum. Acacia acuminata (wd) Euphorbi. Hevea brasiliensis (lvs, etc.) Elaeagn. Shepherdia canadensis (fit) Cucurbit. Citrullus vulgaris (frt, red-fleshed) Umbell. Daucus carota (it) Eric. Arbutus undo (fit) Eben. Diospyros kaki (fit) Convolvul. Cuscuta californica (st.) Solan. Lycopersicum Pro-y-carotene is a penta-cis-y-carotene. Ros. Pyracantha angustifolia (fit) Celastr. Euonymus fortunei (sds) Scrophulari. Mimulus longiflorus (fl.) Palmae Butia capitata (fit), eriospatha (fit) Prolycopene is a hexa-cis-lycopene. Ros. Pyracantha angustifolia (frt) Celastr. Euonymus fortunei (sd) Solan. Lycopersicum Scrophulari. Mimulus longiflorus var. (fl.) Palmae Butia capitata (fit) Arac. Arum maculatum (fit, 40% of carotenoids)

Rhodoxanthin (Thujorhodin; 3,3'-Dioxo-retro-ß-carotene) has been found in some gymnosperms, and in Resed. Reseda lutea (lvs) Potamogeton. Potamogeton crispus (lvs), natans (lvs) Rubixanthin Ros. Rosa canina (fit), moyesii (fit), rubrifolia (fit); Rubus chamaemorus (unripe fit) Convolvul. Cuscuta salina, subinclusa Comp. Gazania rigens (fl.), Tagetes patula (fl.) Palmae Butia capitata (fit)

Semi-ß-carotene Rut. Murraya exotica (fit), Triphasia trifolia (fit) Taraxanthin: of unknown structure? Convolvul. Cuscuta australis? Scrophulari. Mimulus tigrinus (fl.)

Trollixanthin Ranuncul. Trollius europaeus (fl.) Violaxanthin (5,6:5',6'-Diepoxy-zeaxanthin; fig. 186) is universal in the chloroplasts of higher plants, amounting to about 15% 7

Gco II

866

CHEMOTAXONOMY OF FLOWERING PLANTS

ß-Carotene

Lutein (Xanthophyll)

Violaxanthin

Neoxanthin ?

HO

HO

OH

HO HO H

Fig. 186. Carotenoids of chloroplasts.

Capsanthin

HO

Chrysanthemaxanthin (and Flavoxanthin )

1-10

Lycopene

Fig. 187. Some carotenoids.

TETRATERPENOIDS 867

of the carotenoids present. It also occurs widely in flowers and fruits. Papaver. Eschscholtzia californica (fl.) Crucif. Sinapis officinalis (fl.) Ros. Cotoneaster occidentalis (frt) Legum. Cytisus laburnum (fl.); Lotus corniculatus (fl.); Ulex europaeus (fl.), gallii (fl.) Cucurbit. Cucurbita maxima (frt) Viol. Viola tricolor (fl.) Caric. Carica papaya (frt) Eric. Arbutus unedo (frt) Eben. Diospyros costata (frt), kaki (frt) Ole. Forsythia intermedia (fl.) Solan. Capsicum annuum (lys, frt) Comp. Calendula officinalis (fl.), Crepis aurea (fl.), Tagetes grandiflora (fl.), Tragopogon pratensis (fl., as esters) hid. Iris pseudacorus (fl.) Violaxanthin esters Balsamin. Impatiens noli-tangere (fl., mono- and di-esters) Ole. Forsythia intermedia (fl., mono- and di-esters) Comp. Taraxacum officinale (fl., mono- and di-esters), Tussilago farfara (fl., mono- and di-esters) ß-Zeacarotene is on the biogenetic line leading to ß-carotene p. 859. Zeaxanthin (3,3'-Dihydroxy-ß-carotene) occurs in chloroplasts, and in many fruits and flowers. Papaver. Eschscholtzia californica (fl.) Ros. Cotoneaster frigida; Rosa canna (frt), moyesii (frt), rubrifolia (frt) Rut. Citrus aurantium (frt) Viol. Viola tricolor (fl.) Celastr. Euonymus europaeus (aril) Elaeagn. Hippophae rhamnoides (frt) Eben. Diospyros costata (frt), kaki (frt) Solan. Capsicum annuum (frt); Cyphomandra betacea (frt); Physalis alkekengi (frt-5o% of carotenoids); Solanum landfolium (frt). Not in Atropa belladonna; Solanum dulcamara Comp. Arnica montana (fl.) Zeaxanthin esters Ole. Forsythia intermedia (fl., mono- and di-esters)

7-2

868

CHEMOTAXONOMY OF FLOWERING PLANTS

VII PENTATERPENOIDS GENERAL These must be very rare in plants. I know of but one, solanesol, an unsaturated alcohol isolated by Rowland, Latimer and Giles (1956). It is said to be formed from mevalonate. It has been suggested that solanesyl pyrophosphate plus a quinone may form ubiquinone-45 or vitamin-

K2-45. List and Occurrence Solanesol ((CH3)2C=CH. CH2 . (CH2 . C(CH3). CH: CH2)8CH2 . C(CH3)= CH . CH2OH) Solan. Nicotiana tabacum (lvs)

VIII POLYTERPENOIDS GENERAL We have here another example of the difficulty one has in classifying chemical compounds. It is nearly as difficult as classifying plants! We should, perhaps, use the term `polyisoprene' or even `polyhemiterpene' instead of polyterpene. And what does one mean by `poly-' ? In this section on the terpenoids we have recognized hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, triterpenes, tetraterpenes and pentaterpenes with 1, 2, 3, 4, 6, 8 and 10 C5H8 units respectively. The isoprenoid alcohols listed in the present sub-section have from 6 to 13 or more C5H8 units and so overlap the tri-, tetra- and penta-terpenes. Nothing in this world seems to be perfect and our classification does not claim to be so. Incidentally, one wonders why there are so many sesqui- (` one-and-ahalf') terpenes and no, or almost no, `two-and-a-half —(C5H8)5

terpenes. Williams (1962), in a series of papers on `laticiferous plants of economic importance', says that Schultes has estimated that there are about 35,000 plants that have latex. Most latices have polyterpenoids—often rubber—present, though there are some latices, such as that of Carica papaya, that are said to be devoid of them. Williams says further: `Of the gymnosperms, only a few are known to yield latex or to form rubber or gutta. [Few monocotyledons have rubber, but] Polhamus [a footnote says "personal communication"] reports that he has been able to

POLYTERPENOIDS 869

extract rubber-containing latex from the peel of Musa sapientum L. Rubber has been extracted also, according to him, from a fungus attacking the roots of a certain tree in the Far East.' Rubber (and other polyterpenoids ?) may occur in non-latex form. Thus guayule (Parthenium argentatum), which may well be the best rubber-plant in the world, has the rubber in colloidal form in almost every living cell (Lloyd, 1911, 1932). Plants almost always contain only cis- or trans polyterpenoids. Rubber has the cis- structure, while balata, gutta, jelutong, etc. have the transstructure. These may be distinguished by differences in light-absorption near 12 p, and Hendricks, Wildman and Jones (1946) have looked into this. They say: Hydrocarbons of the rubber (r) or gutta (g) types isolated from Hevea brasiliensis (r), Mimusops balata (g), Asclepias erosa (milkweed (r) ), A. syriaca (milkweed (r) ), Oenothera biennis (evening primrose (r) ), Solidago leavenworthii (golden-rod (r) ), Eucommia ulmoides (g), Euonymus japonicus (g), and Jatropha sp. (chiltre (r)) were positively identified by their light-absorptions near 12 µ. Mixed cis- and transisomers were absent in all cases even though the plants examined were selected as giving hydrocarbons of questionable types. To my knowledge only one relatively recent claim to the occurrence of cis- and trans- forms in the same latex has been made. Schlesinger and Leeper (1951) say: `Chicle has been shown to contain two polyisoprenes ... one of these ... has been shown to correspond to the polymer of gutta-percha, and is presumed to be the trans- modification. The other.. . corresponds to Hevea rubber and is presumed to be the cis- modification.' Unfortunately the literature is full of records of occurrences of `rubber', `balata', `jelutong', etc., without further details. It is often impossible to decide whether the cis- or trans- form is meant. We shall not attempt in the following list to give all occurrences. More detailed records will be given for each family known to have polyterpenoids when the families are discussed in turn. List and Occurrence Balata has the trans- structure. Sapot. Mimusops spp. Betulaprenols—see isoprenoid alcohols (below) with n = 6, 7, 8 and 9. Betul. Betula alba (verrucosa) (wd) Caoutchouc—see rubber.

870 CHEMOTAXONOMY OF FLOWERING PLANTS

Castaprenols—see also isoprenoid alcohols (below) with n = 1o, I I, 12, and 13. According to Wellburn and Hemming (1966) these are widely distributed. They are absent from cryptogams (except for Chlorella?) and gymnosperms ? Mor. Ficus elastica (lvs) Chenopodi. Beta vulgaris (lvs) Polygon. Polygonum cuspidatum (lvs) Laur. Laurus vulgare (lvs) ? Crassul. Umbilicus rupestris (lvs) Legum. Vicia faba (lvs) ? Hippocastan. Aesculus hippocastanum (lvs) Aquifoli. Ilex aquifolium (lvs) ? Arali. Hedera helix Solan. Nicotiana virginiana (lvs) Caprifoli. Sambucus nigra (lvs) Arac. Arum maculatum (spadix) Chicle has been discussed by Egler (1947). He says that it was obtained originally from the Sapotaceae, but that other plants, particularly members of the Apocynaceae, are now used also. See also under `general' (above). Sapot. Achras spp. Apocyn. some Chilte: a cis polyterpenoid ? Euphorbi. Jatropha spp. Dolichol—see isoprenoid alcohols (below, n = zo). Arac. Arum maculatum (spadix) Gutta or Gutta-percha (fig. 188) is a trans-polyterpenoid. Sapot. Palaquium, Payena Isoprenoid alcohols (fig. 188) have been discussed in a recent paper by Wellburn and Hemming (1966). They have the basic structure H—[CH2 C(CH3)—CH—CH2]n—OH. Lower members in the series have been dealt with elsewhere, as indicated. n = I 3-Methyl-but-2-en-I-ol is a hemiterpenoid. Does it occur in plants ? n = 2 Nerol, Geraniol—see monoterpenoids n = 3 Farnesol—see sesquiterpenoids n = 4 Geranyl-geraniol—see diterpenoids n= $ ? n = 6 Betula-hexaprenol (a triterpenoid) n = 7 Betula-heptaprenol n = 8 Betula-octaprenol (a tetraterpenoid) n = 9 Betula-nonaprenol—see under betulaprenols for these four alcohols.

POLYTERPENOIDS 871

OH Isoprene

Rubber (cis-) Gutta (trans-)

Isoprenoid alcohols

Fig. 188 Isoprene and some polymers. n = io Solanesol See also Castaprenols (n = to, It, iz, i3) n = Ii and Pistaciaprenols (n = II, 12, 13). n = iz n = 13 An all-trans- C50 alcohol occurs in the Spadix of Arum maculatum. n = 14 to n = 19 Do any of these occur in plants ? n = 20 Dolichol, which has one double bond less than it `should', has been found in plant and animal materials by Burgos, Hemming, Pennock and Morton (1963). It may be esterified (in part?) with fatty-acids. Jelutong: a trans polyterpenoid ? Apocyn. Dyera spp. Massaranduba: a gutta ? Sapot. Manilkara huberii, Mimusops elata (latex, used like milk) Pendare: a gutta? Sapot. Mimusops Pistaciaprenols are Isoprenoid alcohols (n = 11, 12, 13). Anacardi. Pistacia terebinthus (lvs, st.) Rubber (fig. 188) has the cis-configuration. It is extremely common in Nature. The great economic importance of rubber has led to the investigation of thousands of plants—Moyle (1942) for example, lists about 1800 rubber-yielding species—and some hundreds have been exploited commercially at one time or another. We shall mention only a few of the most important or interesting ones here: others will be found in the discussions of the families to which they belong. Mor. Castilla elastica, which yields rubber called caucho, ule, or Panama rubber, Ficus elastica, is the familiar Indiarubber tree', Manihot glaziovii—ceara rubber. Euphorbi. many members have rubber in appreciable amounts. Euphorbia intisy is said to yield rubber of very high quality. Hevea brasiliensis, in cultivation, is the world's great rubber producer. Apocyn. Funtumia elastica is the source of Lagos silk rubber or Ire.; Landolphia heudelotii, owariensis.

872 CHEMOTAXONOMY OF FLOWERING PLANTS

Comp. Parthenium argentatum is the ' guayule', probably the highest yielder of rubber. Lloyd, for years the present writer's colleague and friend, published a monograph on this plant (191i). I worked on it during 1927-8 and first made an ultimate analysis of the rubber, finding it to be (C5H8),,; Scorzonera tau-saghyz and other spp.; Taraxacum kok-saghyz Solanesol is an isoprenoid alcohol (above) with n = 1o. See VII, Pentaterpenoids. Sorva: a chicle or gutta? Apocyn. Couma spp.

WAXES The term wax is used rather loosely for substances with physical rather than chemical properties, as Eglinton and Hamilton (1963) point out: ' Chemically speaking, the term wax refers to an ester of a higher fattyacid and a higher aliphatic alcohol, but in the present context it applies to all substances of "waxy" character isolated from the plant. Plant waxes may constitute anything from a fraction of a per cent to several per cent of the dry weight of a plant.' They give a table of the major constituents of such ' waxes' which shows what a wide variety of chemical substances may be included. Our list follows theirs closely. Alkanes (p. 648) Normal, with odd numbers of C-atoms from C21 to C37—common, particularly C29 and C31. Normal, with even numbers of C-atoms from C20 to C3, common, but in small amount. Branched, C27 to C33—infrequent. Alcohols (p. 1o6), usually as esters in true waxes. Primary, with odd numbers of C-atoms from C25 to C31 infrequent. Primary, with even numbers of C-atoms from C22 to C32—common. Secondary, with odd numbers of C-atoms from C21 to C33—common. Diols and Ketols—rare. Terpene alcohols—infrequent. Aldehydes (p. 128), occurring as polymers. Normal, with even numbers of C-atoms from C22 to C34--rare. Ketones (p. 66o) Di-normal-alkyl ketones—rare. Carboxylic acids (p. 421), usually as esters in true waxes.

WAXES 873

Normal, with odd numbers of C-atoms from C15 to C33—of doubtful occurrence ? Normal, with even numbers of C-atoms from C14 to C34—common. Keto-acids—rare. Dicarboxylic acids—rare. Esters between normal acids and primary and secondary alcohols, common as true waxes. Estolides of hydroxy-acids: infrequent ? Triterpenoids—minor constituents. Diterpenoids—minor constituents. Glycerides (fats)—minor constituents. Phenolic compounds—minor constituents. Waxes occur chiefly on the surfaces of leaves and stems, and modern methods of microscopy, including electron microscopy, have yielded much interesting information about the origin and disposition of such surface waxes. They seem to arise as oily droplets within the cells of the epidermis and travel through plasmodesmata to the outside. There they (or some of them) would appear to crystallize, as judged from X-ray diffraction photography. Not much is known of chemotaxonomic interest about the true waxes. Certain families, the Palmae, for example, produce large amounts of wax on their leaves, and these may be of considerable economic interest. The wax from the Carnauba palm (Copernicia cerifera) is collected and marketed in great quantity. It is very hard (for a wax) and is used for a variety of purposes. Another palm, Ceroxylon andicola, produces a somewhat similar wax on its trunk. Other palms, too, have waxes, but only a very few of these substances have been studied in detail. Although some fruits have waxy substances on their skins not all of these are true waxes. The so-called waxes of the bayberry (Myrica pensylvanica) and of the wax myrtle (M. cerifera) are actually fats. The reserve-materials of many seeds, too, are fats, but the seeds of Simmondsia have a liquid wax.

FAMILIES AND ORDERS OF FLOWERING PLANTS V/

FAMILIES AND ORDERS OF FLOWERING PLANTS INTRODUCTION Following this small section we deal with the families and orders of flowering plants in alphabetical order. It would have been relatively easy to do this if we had restricted ourselves to a few modern treatments, but we have gone back to Linnaeus, and even further, in our search for opinions on relationships. This has made the job difficult, for the early workers used terms differing from those of today, and had different ideas as to classification. Let us examine the problems briefly, and explain how we have attempted to deal with them. Linnaeus, in his Philosophia botanica of 1751, had gropings towards `natural' groups in his 68 `fragments'. Do we treat these as families, or as orders, or do we deal with each fragment on its merits ? After some dithering I decided to list them as orders, since many of them include genera belonging to several of our modern families. We received some support for this from Copeland (1957), who revived many of L.'s names for his orders—Scabridae, for example, as more or less equivalent to our Urticales. Copeland was not consistent, however, for his Preciae and Luridae each included Linnaean fragments in addition to the `type' ones. Necker, in his Enumeratio stirpium Palatinarum, etc. of 177o, had 46 units, not defined as categories, which I have treated as families, though some include genera from more than one of `our' families—e.g. Labiaceae; Sedaceae; Anagallideae with Lisimachia, Anagallis, and Centunculus (all of our Primulaceae); but Rhaeades with Monotropa, Chelidonium, Papaver, Nymphaea, Fumaria, and Impatiens. In compiling my list of families I have met this problem. Can one say that a man names a family when he says that if one makes a family then it would be such-and-such ? For example, A. L. de Jussieu (1804) says: `Si on se decide å former une nouvelle familie qu'il faudroit nommer Loasees (loaseae)...on la caracteriseroit aisement de la maniere suivante...' Jules de Tristan (181 1) says that Reseda is suspended between three families, `les cistes, les passiflorees et les capparidees'. On p. 402 he has: `Apres les cruciferes viendroients les capparidees...puis les passiflorces. Le reseda, soit qu'on le laisse seul ou qu'on le reunisse a la famille suivante. Les cistes, composes de l'helianthemum et du cistus.' Do we credit him, for our purposes, with the Resedaceae ? Ad. Brongniart (1824) dithers on p. 32: ` ... on pourra regarder ce groupe (Cytinus, Rafesia, Nepenthes) tres-voisin des Aristolochiees, soit comme une simple section de cette familie, soit comme une familie particuliere'. On p. 39 8-2 1 8771

878 CHEMOTAXONOMY OF FLOWERING PLANTS

he seems to have decided, for he lists Cytineae, with a diagnosis and the 3 genera mentioned. And what do we do with the categories of men like Reichenbach and Horaninow who, though groping towards a natural system, are obsessed with groupings into set numbers ? Reichenbach, in his Conspectus regni vegetabilis, etc. of 1828, has Classes IV-VIII, each divided into ordi. Each ordo has z formatii, and there are 3o of these, so that a formatio is more or less equivalent in size to our modern order. Each formatio has 3 families. Here are examples: Form. Glumaceae with families Gramineae, Cyperoideae, and Commellinaceae (sic). Form. Campanaceae with families Compositae, Cucurbitaceae, and Campanulaceae. I have listed each formatio as an order. Horaninow (1843) is obsessed with groupings of 4. He has, for example: Class 9. Calycanthae Ordo 1. Araliastra with 4 `series' Ordo z. Portulacastra Ser. 1. Turneraceae with Samydeae, Homalieae, Loaseae (with 4 smaller groups), and Passijloreae. Ser. 2. Opuntiaceae Ser. 3. Ribesiaceae with 4 groups Ser. 4. Sesuviaceae with 4 groups Ordo 3. Combretastra with 4 `series' Ordo 4. Cassiastra with 4 `series' We must credit him with some attempt to regularize the endings of names. He uses -astra for orders (at least towards the end of his classification), the first part of the name being derived from a (type ?) family: Rutastra (from Rutaceae), and Meliastra (from Meliaceae). He uses -aceae endings fairly consistently for his `series' (see the examples above), but his series are sometimes almost our orders—for example: Malvaceae with Sterculieae, Buttnerieae, Malveae and Bombaceae. Lindley (1836) antedates him with the use of consistent endings. We may note: Class i. Exogens or Dicotyledons Subclass. Polypetalae Alliances (our orders) with -ales endings—e.g. Ranales, Ericales (with Pyrolaceae, Monotropaceae, Ericaceae, Vaccinaceae, and Epacridaceae—how modern!). Orders (our families) with -aceae endings—see examples above.

FAMILIES AND ORDERS OF FLOWERING PLANTS 879

Lindley (1833) had used the name nixus' much as he later used `alliance', and Grisebach (1854) has the spelling ` nexus '—a difference which confused my typist! Ecklon (1827)—we seem to be working backwards—is even more confusing. He uses 'familia' much as we would use order', and ordo' as we would use `family'! e.g. Familia Coronariae Ordo I. Liliaceae; Ordo 2. Haemodoreen R. Br.; Ordo 3. Spathaceen. Familia Ensatae Ordo I. Irideae; Ordo 2. Ixiaceae; Ordo 3. Gladioli. Dumortier, as early as 1822 or 1823, was using 'ordo' much as we should use `order', and in 1827 he was using the name `family'. It is hardly worth while to pursue further the matter of early names for taxonomic groups, but one must emphasize once more the difficulty of reconciling the many different systems with one using modern names. In an effort to standardize names three modern taxonomists, Cronquist, Takhtajan and Zimmermann, have got together (1966) and produced a scheme for the major units, while Takhtajan, in his Flowering plants (1969), has the following scheme (part): Division: Magnoliophyta (Angiospermae) Class: Magnoliatae (Dicotyledons) Subclass A. Magnoliidae Superorder 1. Magnolianae Order 1. Magnoliales (with 8 fams) Order 2. Laurales (with II fams) +4 other orders Subclass B. Ranunculidae Superorder 2. Ranunculanae Order 7. Illiciales (with 2 fams) +4 other orders Such a standardization certainly would be a useful thing.

Lumpers and Splitters By and large Engler and his school, as seen in the several editions of the Syllabus, have been lumpers, recognizing relatively few orders and families: EPI (1889-1898) had 216 families of dicots.

88o

CHEMOTAXONOMY OF FLOWERING PLANTS

Syll. 5 (1907) had 234 families of dicots. Syll. 11 (1936) had 44 orders and 258 families of dicots. Syll. 12 (1964) has 48 orders and 291 families of dicots. Thorne (1968) is even more of a lumper, with 43 orders and 269 families of dicots. Cronquist (1968) closely parallels the nth syllabus, having 56 orders and 292 families of dicots. Hutchinson (1969), on the other hand, has 82 orders and 348 families of dicots. Takhtajan (1969), is also a splitter, with 74 orders and 369 families of dicots. These all, lumpers and splitters alike, reflect a tendency towards a slow increase in the numbers of orders and families. This is, of course, due to two factors. Firstly we have the discovery of new plants so different from those already known that they do not fit into existing taxa. Secondly we find that new facts of morphology, anatomy, cytology and chemistry bring out the differences between taxa. One is tempted to add that vanity sometimes urges men to make new families and orders! I have not mentioned Nakai as a splitter in the notes above, but anyone leafing over my lists of families and orders will find his name as author of many of them: Abrophyllaceae, Adenogrammataceae, Agdestidaceae, Aldrovandaceae, Barbeuiaceae, Berzeliaceae, Bifariaceae and so on; Apiales, Bruniales, Byblidales and so on. He seems to have made a family for every genus he studied, and an order for many single families! I have not mentioned here the lumping and splitting of certain outstanding families—the Cornaceae and Saxifragaceae, for example— because I deal with them elsewhere in this book.

FAMILIES OF FLOWERING PLANTS Introduction In the previous section we have dealt briefly with some problems met with in compiling the lists of families and orders which follow. Here we must add but a note or two about the list of families. Some readers may say that sufficient lists have already been compiled. I would have agreed with them a few years ago, but I found that the lists available to me were out of date, inaccurate, incomplete, or insufficiently detailed—and sometimes all of these. That of Barnhart (1895), for example, listed all names ending in -aceae as family names. When I checked some of these I found that they had been applied to minor

FAMILIES OF FLOWERING PLANTS 881

divisions of the families as recognized by the writers. Some had such abbreviated references that I wasted many hours in trying to track down the names of interest to me. Others dealt with questions of legitimacy and, though useful, did not meet my needs. The lists of Bullock (1958) are examples. For let us be clear, we are not concerned with legitimacy in my compilation—we want to know who first put forward a `new' family. We want to know also (if that was indicated) what genera the author included and what relationships he saw with other groups. My list is incomplete, I know, for I have been unable to check, for the features mentioned above, a small proportion of the names that I have included. It will displease some of my critics because I have included as family names some that they would exclude. I can only plead that I have spent an enormous amount of time, perhaps too much for the results, and that I felt the labour was necessary for the purposes of this book. Finally I should like to add that corrections and additions will be welcomed, and that I hope that my list will prove useful, even though imperfect, to others.

FAMILIES OF DICOTYLEDONS Abrophyllaceae: T. Nakai, Ord., Fam., etc., App. p. 243. 1943. `A. Nakai 1940' with Abrophyllum Hook. f. only, in Hydrangeales. Barkley (1948) and Hutchinson (1969) incl. Abrophyllum in Escalloniaceae. Airy Shaw (in W., 1966) says = Escalloniaceae—Cuttsieae Engl. See Saxifragaceae Acalyphaceae: J. G. Agardh, Theoria, 1858, p. 258. (`Acalypheae'). Fam. 313, between Urticeae, and Crotoneae and Trigoniaceae. Fr. Klotzsch (1859 or 186o) had `Acalyphaceae' in Tricoccae. Klotzsch and Garcke (1862), and Kerner (1891) maintained the family. Barkley (1948) has a large family A. (Ricinaceae) with about 25o genera listed, leaving the Euphorbiaceae as a small family (19 genera listed). Others, including Hutchinson (1969), consider A. to be a part of the Euphorbiaceae (q.v.). Acanthaceae n.c.: B. de Jussieu, 1759, in A. L. de Jussieu, Gen. pl., 1789 (`Acanthi'). A. with Acanthus, Ruellia, Justicia, and other genera which we place elsewhere. A. L. de J., whose name is conserved as Acanthaceae, had genera which we include in A. today. Almost all taxonomists have recognized the family and have placed it in Tubiflorae or in segregate orders. Although most authors agree on most of the genera to be included, there are some points of difference. Burnett (1835) included Sesamidae (Pedalidae). Lindau (in EP 1, 1895) had 4 sub-families: Nelsonioideae (5), Mendoncioideae (3), Thunbergioideae (3) and Acanthoideae (162). Van Tieghem (1908) segregated the first 3 sub-families as Thunbergi-

aceae. Bremecamp (1953) would put the Nelsonioideae in Scrophulariaceae; would elevate the Mendoncioideae and Thunbergioideae to family rank and would put them near to Bignoniaceae. Melchior (in Syll. 12, 1964), who recognizes a family of 250/2600, follows Lindau closely. See Mendonciaceae, Thunbergiaceae; Tubiflorae for discussion. Acarnaceae: H. F. Link, Enum. pl. Berol. 2, 1822. On p. 295 Link had 17 genera including Acarna (= Atractylus) most of which would be placed in Compositae—Cardueae (Cynareae). On p. 355 he had 4 further genera, which also would be placed in Cardueae. [ 88z ]

FAMILIES OF DICOTYLEDONS 883 Dostål (1958) has Acornaceae (a misprint ?). See Compositae Aceraceae n.c.: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 491, 177o (`Aceratae'). Necker included Acer and Aesculus. The conserved name is that of A. L. de Jussieu (1789-2 Acera'). Most modern authors place A. in the Sapindales (Bessey, 1915; Rendle, 1938; Skottsberg, 1940; Barkley, 1940; Gates, 1940; Gundersen, 1950; Pulle, 195o; Boivin, 1956; Benson, 1957; Crete, 1959; Scholz, in Syll. 12, 1964; Cronquist, 1968; Takhtajan, 1969; Hutchinson, 1969); in the Terebinthales, an order with many of the same families (Wettstein, 1935; Sod, 1953) ; or in the Rutales (Thorne, 1968). Most authors recognize but 2 genera: Acer (Tourn.) L. with about 200 spp., and Dipteronia Oliv. with 2 spp. Some believe that a third genus—Negundo Boehmer ex Ludwig (ING), carved from Acershould be retained. We shall discuss the chemistry of the family when dealing with the order Sapindales (q.v.). Achariaceae n.c.: H. Harms, in EP1, Nachtr. zu ni, 6a: p. 256, 1897. Harms included Acharia, Ceratiosicyos and Guthriea. His name is conserved. This little family, with 3/3-4 in S. Africa, is almost always associated with the Passifloraceae, and included in Parietales (Wettstein, 1935; Skottsberg, 1940; Pulle, 1950; Soo, 1953); Passiflorales (Boivin, 1956; Crete, '959; Takhtajan, 1969; Hutchinson, 1969) ; Guttiferales (Bessey, 1915); Cistales (Thorne, 1968); or Violales (Syll. 12, 1964; Cronquist, I968)—orders in which the authors named have included Passifloraceae. Some taxonomists (B. & H.; Gundersen, 1950) have even included the Achariaceae in the Passifloraceae. Van Tieghem and Constantin (1918) are almost alone in placing Achariaceae away from the Passifloraceae, in their order Plumbagales with Caricaceae, Plumbaginaceae and Salvadoraceae. See Violales for discussion Achatocarpaceae n.c.: A. Heimerl, in EP2, 16C: 174-8. 1934. As established by Heimerl, whose name is conserved, this is a little family with Achatocarpus (ca. io) and Phaulothamnus (1). It has been included in the Phytolaccaceae (by Gundersen, 1950; M. & C., 1950; Sod, 1953; Dostål, 1957; Thorne, 1968; and Takhtajan, 1969); placed as a family near the Phytolaccaceae in the Centrospermae (by Skottsberg, 1940; and Eckardt, in Syll. 12, 1964); in the Caryo-

884 CHEMOTAXONOMY OF FLOWERING PLANTS

phyllales (by Pulle, 1952); or in the Chenopodiales (by Barkley, 1948). Hutchinson (1969), on the other hand, puts this little family in his Bixales! See Centrospermae for discussion Achraceae: G. Roberty, Bull. Inst. franc. Afrique noire, 15: 1414. 1953 (`Achracees'). Roberty proposed this name in place of Sapotaceae. Dostål (1958) would retain it. See Sapotaceae Achradaceae: J. Dostål, Botan. Nomenkl. 1957, p. 197. ` Achradaceae n.n. typ Achras L. 1753, syn. Sapota Gaertn. 1791; syn. Sapotaceae.' A misprint for Achrasaceae? See Sapotaceae Achrasaceae: Sir E. ff. Bromhead, Edinb. New Phil. Y. 25: 134. 1838. Bromhead had A. as fam.' 2 of Myrsinales. See Sapotaceae Actinidiaceae n.c.: Ph. van Tieghem, Your. de bot. 13: 173. 1899 (`Actinidiacees'). V.T. says (pp. 172-3): `Les genres Actinidie et Sauravie...doivent eire separes desormais des Dilleniacees et des Theackes, et reunis dans une meme familie, qu'on nommera les Actinidiacees.' The conserved name is that of Hutchinson (1926). Almost all modern authors associate the Actinidiaceae with suen families as Dilleniaceae, Marcgraviaceae, and Theaceae (s.l.) in orders variously named Guttiferales (Wettstein, 1935; Skottsberg, 1940; Pulle, 1950; Benson, 1957; Crete, 1959; Melchior, in Syll. 12, 1964); Guttiferae (Copeland, 1957); or Theales (Barkley, 1948; Gundersen, 1950; Boivin, 1956; Thorne, 1968; Cronquist, 1968; Hutchinson, 1969). A few have other placings. Van Tieghem and Constantin (1918) put the family in their Pittosporales; Takhtajan (1969) has it in Ericales. See Clethraceae, Dilleniaceae, Saurauiaceae; Guttiferales for discussion. Adenaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 174. A. as a synonym for Droseraceae (q.v.). Adenogrammataceae: T. Nakai, Your. Yap. Bot. 18: 101. 1942. `A. (Fenzl) Nakai... anno 1939 et seq.' with Adenogramma.

FAMILIES OF DICOTYLEDONS 885

Eckardt (in Syll. 12, 1964) says that A. is one of a group of genera linking Molluginaceae with Phytolaccaceae. The former family is said to have anthocyanins and to lack betalains: the latter to lack anthocyanins and to have betalains. It would be of great interest to know the chemistry of the group of genera referred to by Eckardt (Gisekia, Limeum, Polpoda, and Adenogramma). Unfortunately we know nothing of it. See Aizoaceae, Molluginaceae, Phytolaccaceae. Adoxaceae n.c.: J. G. Agardh, Theoria, 1858, p. 77. Few plants are so difficult to place as the little moschatel (Adoxa moschatellina), the sole member of the Adoxaceae. Early taxonomists (Lindley, 1836; Endlicher, 1836-40; and Camel, 1881) put it into or near the Araliaceae. Some (Bentham, 1885; Hallier, 1912) have included it in the Caprifoliaceae. Many (Bessey, 19,5 ; v.T. & C., 1918 ; Wettstein, 1935 ; Rendle, 1938 ; Skottsberg, 194o; Pulle, 1950; Sod, 1953; Benson, 1957; Crete, 1959) have it as a family in the Rubiales near Caprifoliaceae. Some modern taxonomists (Wagenitz, in Syll. 12, 1964; Thorne, 1968; Cronquist, 1968; and Takhtajan, 1969) place it in the Dipsacales, next to the Caprifoliaceae. A few see a relationship to the Saxzfragaceae (Gundersen, 1950, in the S.; Hutchinson, 1959, 1969, as a fam. of the Saxifragales). Barkley (1948) had it in Asterales! Boivin (1956) has it in a small order Valerianales. In all probability, then, the relationships of Adoxa are with Araliaceae, Caprifoliaceae or Saxzfragaceae. Sprague (1925-7) studied 19 (non-chemical) characters and concluded that Adoxa is nearest to Saxifragaceae, less close to Caprifoliaceae, and even less to Araliaceae. Its pollen, says Copeland (1957), is like that of Caprifoliaceae and Rubiaceae. In serodiagnostic tests, however, Adoxa is said to react strongly with representatives of Caprifoliaceae, Rubiaceae and Dipsacaceae, but not with Saxifragaceae. See Dipsacales for further discussion Aegicer(at)aceae: C. L. Blume, Ann. des Sd. Nat. Bot., Ser. 2, 2: 97. 1834 (`Aegicereae'). B. had Aegiceras Gaertn. (only) in his family. Some taxonomists have a little family, Aegiceraceae, and have recognized an affinity with Myrsinaceae, by putting it in the Myrsinales (Hutchinson, 1969). Others have actually put Aegiceras in the Myrsinaceae itself (Lindley, 1853 ; Melchior, in Syll. 12, 1964). See also Ardisiaceae, Lysimachiaceae; Myrsinaceae for discussion.

886 CHEMOTAXONOMY OF FLOWERING PLANTS Aeginetiaceae: E. J. Livera, Ann. Roy. Bot. Gard. Peradeniya, ro(z): 153. 1927. 'A. Liv., fam. nov. Ord. Personales...' with Aeginetia L. and 5 other genera. All but one of these are referred today to the Orobanchaceae, the sixth, Hyobanche L., to the nearly related Scrophulariaceae. See Orobanchaceae, Scrophulariaceae. Aesculaceae: G. T. Burnett, Outlines of Bot. 1835. pp. 887, 891, 1126. B. had A.—with Aesculus, Pavia, and Caryocar (Rhizobolus)—in his Acerinae. Lindley (1836) put it in Acerales; Bromhead (1838) in Aesculales; v.T. & C. (1918) in Geraniales, near Sapindaceae; Gates (1940) in Sapindales. Most authors regard A. as a synonym of Hippocastanaceae (q.v.). Aextoxicaceae n.c.: F. Pax, Jahresb. Schles. Ges. f. vaterl. Cultur, 94, Abt. 2: 21. 1917. A. of Engler and Gilg (1919) is conserved. Aextoxicon Ruiz and Pay. has been placed in Euphorbiaceae (Hooker, 1837; M. & C., 1950); near Villaresia (Icacinaceae) (Miers, 186o-9); in Aquzfoliaceae; in Elaeagnaceae (Baillon, 1872); in Monimiaceae (Lemaout, Decaisne, Hooker, 1873); and as a family, Aextoxicaceae, in Terebinthales (Wettstein, 1935; Soo, 1953); in Sapindales (Skottsberg, 194o; Gundersen, 195o; Pulle, 195o; Scholz, in Syll. 12, 1964); in Euphorbiales (Barkley, 1948; Thorne, 1968; Cronquist, 1968); or in Celastrales (Takhtajan, 1969, doubtfully; Hutchinson, 1969). A careful study of its chemistry might well help us to decide its ' proper' placing. Unfortunately we know little beyond that its fruits are poisonous, that it is rich in tannins, and that it probably lacks raphides! See Sapindales Agdestidaceae: T. Nakai, your. Jap. Bot. 18: 104. 1942. 'Agdestidaceae (Heimerl) Nakai. .. anno 1838' with Agdestis A. P. DC only. Hutchinson (1959, 1969) puts this little family in his Chenopodiales and believes it to be related to Basellaceae. Eckardt (in Syll. 12, 1964) puts Agdestis in his Phytolaccaceae, as do Barkley (1948) and Takhtajan (1969). Heimerl (in EP2, 1934) says that A. has raphides, and some of the Phytolaccaceae are said to have them, but I have seen no true raphides in material of Agdestis available to me. See Phytolaccaceae

FAMILIES OF DICOTYLEDONS 887

Aggregat(ace)ae: A. J. G. K. Batsch, Tab. affin., etc., 1802, p. 228 (`Aggregatae'). Fam. 3 of Marcidae, with Dipsacus, Scabiosa and Knautia of our Dipsacaceae (q.v.), and Globularia. Agialidaceae: Ph. van Tieghem, Ann. des Sd. nat., Ser. 9, 4: 225. 1906 (`Agialidacees'). Van Tieghem included Agialida (Agialid, Balanites), Agiella (Balanites) and Balanites. See Balanidaceae, Balanitaceae, Zygophyllaceae Agrimoniaceae: J. B. DelaMarck and A. P. De Candolle, Flore Franc., 3rd ed., Iv: 448. 1805 (1815 ?). The genera included were Agrimonia, Alchemilla, Poterium, Sanguisorba and Sibbaldia. S. F. Gray (1821) had all but the last in his Agrimoniaceae, and all but the last have been grouped as Sanguisorbeae of the Rosaceae. It would be interesting to know if they are set aside chemically from the rest of that family. See Rosaceae Ailanth(ac)eae: J. G. Agardh, Theoria, 1858, p. 223 (`Ailantheae'). Ailanthus Desf. is placed in Simaroubaceae by most taxonomists, and Airy Shaw (in W., 1966) says that Agardh's family is equivalent to Simaroubaceae–Ailanthinae Engler. Eckey (1934) points out that fat from seeds of Ailanthus differs from the fats of other members of the Simaroubaceae that have been investigated. See Simaroubaceae Aitoniaceae: ?Harvey, 1859. Hutchinson (1969) includes `A. Harvey (1859)' in Sapindaceae. Takhtajan (1969) includes A. (with Nymania) doubtfully in Rutales. Aizoaceae n.c.: K. Sprengel, Anl. Kenntn. Gew., 2nd ed., II (2): 842, 1818 (`Aizoiden'). I have not been able to check this. A. of Rudolphi (1830—`Aizoideae') is conserved. There seems to be almost complete agreement as to the placing of Aizoaceae. It is grouped with such families as Caryophyllaceae, Portulacaceae, Phytolaccaceae, etc. in orders variously named : CaryophyØe (Hallier, 1912); Caryophyllales (Bessey, 1915; Gates, 1940; Barkley, 1948; Gundersen, 1950; Boivin, 1956; Benson, 1957; Cronquist, 1968; Takhtajan, 1969; Hutchinson, 1969); Centrospermae (Wettstein,

888 CHEMOTAXONOMY OF FLOWERING PLANTS 1935; Rendle, 1938; Skottsberg, 1940; Pulle, 1950; Soo, 1953; Eckardt, in Syll. 12, 1964); and Chenopodiales (Thorne, 1968). There is less agreement as to the content of the family. The Molluginaceae are made a separate family by some, and we recognize it in this book. Single genera have also been made types of families. See (add -aceae): Adenogrammat., Ficoid., Giseki., Glin., Mesembry (anthem)., Mollugin., Polpod., Sesuvi., Telephi., and Tetragon. ; Centrospermae for discussion. Akaniaceae n.c.: O. Stapf, Kew Bull. for 1912, p. 378, 1912. Stapf's name is conserved. This tiny family—with Akania hillii Hook. f. only—was put by early workers (Radlkofer, 1890; Solereder, 1908) in the Staphyleaceae, but since the time of Stapf it has been associated as a distinct family with the Sapindaceae in Sapindales (Stapf, 1912; Barkley, 1948; Gundersen, 1950; Pulle, 1950; Boivin, 1956; Takhtajan, 1966; Cronquist, 1968), or with the Meliaceae in Terebinthales (Wettstein, 1935; Skottsberg, 1940; Soo, 1953), or Rutales (Scholz, in Syll. 12, 1964; Thorne, 1968— with Meliaceae and Sapindaceae). See Rutales for discussion Alangiaceae n.c.: A. P. and A. de Candolle, Prodr., III, 203. 1828 (`Alangieae'). The De Candolles had Alangium Lam. only in their family. It is apparently a very difficult genus to place by the traditional criteria of taxonomy. Jussieu (1789) included it in his Myrti, and many later workers have a family Alangiaceae in Myrtales or Myrtiflorae (Lindley, 1836; Caruel, 1881; Wettstein, 1935; Skottsberg, 1940; Gundersen, 1950; Pulle, 1950; Soo, 1953). On the other hand, several taxonomists would put Alangium in the Cornaceae (Harms, in EP,, 1897; ING), or as a family in the supposedly related Umbelliflorae (Umbellales) (Gopinath, 1945; Barkley, 1948; Melchior, in Syll. 12, 1964), or Araliales (Boivin, 1956; Hutchinson, 1969), or CorØes (Benson, 1957; Cronquist, 1968; Thorne, 1968; Takhtajan, 1969). Airy Shaw (in W. 1966), who includes Metteniusa, says that there is perhaps some connection with Oleaceae and Ehretiaceae! See Cornaceae, Metteniusaceae; Umbellales (Umbelliflorae) for discussion. Alchemill(ac)eae: J. G. Agardh, Theoria, 1858, p. 167 (`Alchemilleae'). Airy Shaw (in W. 1966) says that Agardh's family is equivalent to Rosaceae–Sanguisorbeae Juss.

FAMILIES OF DICOTYLEDONS 889

Aldrovandaceae: T. Nakai, your. yap. Bot. 24: 1o. 1949. `Aldrovandaceae Nakai, fam. nova. Aldrovanda Montalban ex L.' Most botanists, including Hutchinson (1969), put A. in Droseraceae. See Dionaeaceae, Droseraceae Allioniaceae: P. Horaninow, Prinz. lin. etc., 1834, p. 68. Horaninow had `Allioniaceae (Nyctagineae) Nyctago, Oxybaphus, Allionia, Boerhaavia'.

Barnhart (1895) and Dostål (1957) list `Allioniaceae Reichenbach, 1828', but he had the name for a tribe of his (mixed) family Nyctagineae. The name appears to be a synonym for Nyctaginaceae Juss. and is used as such by Barkley (1948), Bullock (1958), and Airy Shaw (in W. 1966). Standley (1909, 1918) is one of the few to use the name in recent times. See Nyctaginaceae Alseuosmiaceae: H. K. Airy Shaw, Kew Bull. 18: 249. 1965. Airy Shaw includes Alseuosmia, Memecylanthus and Periomphale (Pachydiscus) here. He says the new family is in some respects intermediate between Escalloniaceae and Loganiaceae (s.l.). The genera were formerly included in the Caprifoliaceae and are kept there by Hutchinson (1969) and Takhtajan (1969); but Cronquist (1968) says they are out of place in the Caprifoliaceae. He puts them, as Alseuosmiaceae, in the Rosales. Unfortunately we know virtually nothing of the chemistry of these 3 genera. See Caprifoliaceae Alsinaceae n.c.: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 484. 177o (`Alsine'). Necker included Alsine, Arenaria, Cucubalus and Gypsophila in his family. A. Bartling (in Bartling and H. L. Wendland, 1825—`Alsineae') is conserved. Barkley (1948) has Alsinaceae with 38 genera, mostly from the subfam. Alsinoideae of `our' Caryophyllaceae; while Eckardt (in Syll. 12, 1964) uses the name as a synonym of Alsinoideae. Nakai (1942), on the other hand, applies it to the whole of `our' Caryophyllaceae. Airy Shaw (in W. 1966) has Alsinaceae Lam. and DC Caryophyllaceae Juss. Hutchinson (1969) agrees. See Caryophyllaceae Alsodeiaceae: J. G. Agardh, Theoria, 1858, p. 197. The type of this `family' would be Alsodeia Thou (Rinorea Aubl.).

890 CHEMOTAXONOMY OF FLOWERING PLANTS

Agardh had the family immediately before Violaceae, and Airy Shaw says it is equivalent to Violaceae—Rinoreeae Reiche and Taub. See Violaceae Altingiaceae n.c.: Hayne (?) in Flora, 13 (I): 172. 183o. The writer in Flora (unnamed) says that Hayne (where and when ?) concluded that: `dass beide genannten genera (Liquidambar, Altingia) ...eine kleine Familie bilden, die man Altingiaceae nennen konnte '. A. Lindley (1846) is conserved. Lindley (1846) put Altingiaceae in his Amentales; Agardh (1858) has it between Platanaceae and Bucklandieae; Nakai (1943) and Takhtajan (1966) place it in the Hamamelidales; while Schulze-Menz (in Syll. 12, 1964) and Hutchinson (1969) include Altingia and Liquidambar in the Hamamelidaceae. Chzhan (1959) says that the pollens of A. and L. differ from those of the Hamamelidaceae; while Skvortsova (196o) argues on anatomical grounds for a separate family. See Hamamelidaceae Alyp(ace)ae: J. C. Graf von Hoffmannsegg and H. F. Link, Fl. port. I: 451. 1809 (`Alypinae'). H. and L. had Globularia (Alypum) only in their family. See Globulariaceae Amamelidaceae: Pfeiffer (1873) has Amamelidaceae Lemaire 1849 in Orb. Dict. Iv, p. 745 sub Dicoryphe: corr. pro Hamamelidaceae' . See Hamamelidaceae Amaraceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 447. A. as a synonym of Gentianaceae (s.l.) (q.v.). Amarantaceae: Lawrence (1951) says that Sprague (Kew Bull., 1928, pp. 287-8) established the correct spelling as Amaranthaceae (q.v.). Amaranthaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 87 (`Amaranthi'). Jussieu had Amaranthus, Celosia, Aerua, Digera, Achyranthes and Gomphrena here, all of which are put in Amaranthaceae by the moderns; but he also included Illecebrum, Paronychia and Herniaria (see Caryophyllaceae s.l.). It has been agreed since the writings of R. Brown (181o) and Lindley (183o) that the family is closely related to the Chenopodiaceae. It has been placed, with that family, in Chenopodiales (Lindley, 1853; Standley, 1916-17; Barkley, 1948; Boivin, 1956; Thorne, 1968; Hutchinson,

FAMILIES OF DICOTYLEDONS 891

1969); Caryophyllinae or Caryophyllales (Hallier, 1912; Gundersen, 1950; Benson, 1957; Takhtajan, 1969); or Centrospermae (Wettstein, 1935; Rendle, 1938; Skottsberg, 1940; Soo, 1953; Eckardt, in Syll. 12, 1964).

We shall see, when discussing the Centrospermae, that the chemistry of the Amaranthaceae is in line with this placing. See also Deeringaceae, Subscariosaceae; Centrospermae for discussion. Amborellaceae n.c.: P. Pichon, Bull. Mus. d'Hist. Nat. (Paris), Ser. 2, 20: 384. 1948. In dealing with the Monimiaceae Pichon `makes' 3 familiesMonimiaceae (s.s.), Atherospermataceae and Amborellaceae (with Amborella only). Most modern authors associate Amborella with the Magnoliales (s.l.) and particularly with the Monimiaceae. Thus Barkley (1948) and Hutchinson (1969) have it in the Monimiaceae; Thorne (1968) as a family in Annonales; Takhtajan (1966) and Cronquist (1968) as a family in Laurales; Buchheim (in Syll. 12, 1964) as a family in Magnoliales. The chemistry of Amborella, then, should be close to that of the Monimiaceae. Unfortunately we know almost nothing of it. See Monimiaceae, Magnoliales Ambraceae: Barnhart (1895) lists Ambraceae Reichb., 1828', but H. G. L. Reichenbach, Consp. reg. veg. 1828, p. 113, treats A. as a part of the Compositae, not as a family. See Compositae Ambrosiaceae n.c.: B. C. Dumortier, Anal. 1829, p. 15; H. F. Link, Handb. I: 816. 1829. Dumortier has A. with Xanthium, Franseria and Ambrosia—which we would put in Compositae–Heliantheae–Ambrosiinae. Dostål (1957) lists Cassini, 1815' as the author of the family, but he had it as a tribe of the Compositae. Barnhart (1895) lists Reichb., 1828', but he, too, has this group as part of the Compositae. Gates (1940) and Barkley (1948) maintain the family, the latter including at least 8 genera. See Compositae Amentaceae. It is difficult to decide what to do about this name. It goes back at least to Gmelin (1747) as a class (?) name. B. de Jussieu (1759), in A. L. de Jussieu (1789), had it as a family (ordo) name, but his group included members of several of today's families. Agardh

892 CHEMOTAXONOMY OF FLOWERING PLANTS (1825) had Amentaceae, but a very mixed bunch it was! So was that of Dumortier (1827). Grisebach (1854) had Amentaceae as family 4 of his Terebinthinae. Dulac (1867) used A. as a synonym of Salicaceae. See also A. as an order and as a class, and see Øentiferae. Ammanniaceae: P. Horaninow, Prim. lin. etc., 1834, p. 86. A. (Lythrariae) with 10 genera, all now in Lythraceae (q.v.). Ammiaceae: J. K. Small, Flora S.E. United States, 1903, p. 856. Small had Ammiaceae Presl', and Barnhart (1895) listed `A. Presl, 1822'; but Presl (1822) treated A. as a tribe of Umbelliferae. The name is sometimes used in place of Umbelliferae (q.v.). Ampelidaceae: C. S. Kunth, in HBK, Nov. gen., etc., v: 222. 1821

(` Ampelideae').

K. included Cissus and Vitis. Although the name Ampelidaceae has been used by M. & C. (1950), Kerner (1891), Crete (1959), etc., we usually use the name Vitaceae (q.v.). Amygdalaceae n.c.: D. Don, Prodr. Fl. Nepal, 1825, p. 239 (`Amygda-

linae'). A family A., distinct from Rosaceae (s.s.), was recognized by many authors, and as recently as 1943 by Nakai and 1954 by Takhtajan. See Rosaceae, Chrysobalanaceae Amyridaceae: R. Brown in Tuckey, Narr. Exped. Congo, 1818, p. 431

(`Amyrideae'). The name has been maintained by several authors. Airy Shaw (in W. 1966) says that A. R.Br. = Rutaceae–Amyridinae Engl. See Rutaceae Anacardiaceae n.c.: R. Brown in Tuckey, Narr. Exped. Congo, 1818, p. 431 (`Anacardeae'). J. Lindley's name (in Introd. Nat. Syst. 1830, p. 127) is conserved. All taxonomists are agreed that the Anacardiaceae belong in the first set of what Good (1956) calls `the core of the dicotyledons '—a set which includes Aceraceae, Aquifoliaceae, Burseraceae, Celastraceae, Connaraceae,

Erythroxylaceae, Hippocrateaceae, Myrsinaceae, Olacaceae, Rhamnaceae, Sabiaceae, Sapotaceae, Simaroubaceae, and some smaller families or parts of families. It is difficult, indeed, to define the limits of orders in this area—the so-called `natural' orders being largely a matter of opinion. Thus we find Anacardiaceae placed as follows: Terebinthales (or the equivalent)—Burnett, 1835; Endlicher, 1836–

FAMILIES OF DICOTYLEDONS 893

4o; Drude, 1887; Wettstein, 1935 ; Soö, 1953 ; Hallier, 1912 (in Terebinthaceae). Sapindales—Bessey, 1915; Rendle, 1938; Skottsberg, 1940; Gates, 1940; Pulle, 195o; Boivin, 1956; Benson, 1957; Scholz, in Syll. 12, 1964; Cronquist, 1968; Hutchinson, 1969. Rutales (or the equivalent)—Lindley, 1853 ; Caruel, 1881; Gundersen, 1950; Takhtajan, 1966; Thorne, 1968. Geraniales—van Tieghem and Constantin, 1918. A few genera which we, following Syll. 12, 1964, would include in the family, have been segregated. See Blepharocaryaceae, Pistaceae or Pistaciaceae, Podoönaceae, Spondiaceae; Sapindales for discussion. Anagallid(aceae): M. Adanson, Fam. Pl. II: 227. 1763 (`Anagallides'). A.'s family is essentially our Primulaceae, but he included Montia (Portulac.) and Theophrasta (Theophrast., a family considered to be near Primulaceae). See Primulaceae Ancistrocladaceae n.c.: J. E. Planchon, Ann. des Sd. nat. Bot., Ser. 3, 13 : 316. 1849 ( `Ancistrocladees' ). A. of Walpers (1851—`Ancistrocladeae' with Ancistrocladus only) is conserved. Nearly all systematists, from Planchon to Hutchinson, have associated this family with those of the old `Parietales' (Guttiferales, Theales, Violales, Ochnales). Thus Melchior (in Syll. 12, 1964) has A. in his Guttiferales, but says it is of doubtful position; Airy Shaw (in W. 1966) says that it is possibly related to Dioncophyllaceae (which Melchior includes in Guttiferales); and Erdtman (1958) finds its pollen to be like that of the Dioncophyllaceae. Boivin (1956), and Takhtajan (1966) put A. in Theales; Cronquist (1968) in Violales; Thorne (1968) in Geraniales; and Hutchinson (1969) in Ochnales! See Guttiferales for further discussion Andromed(ac)eae: Sir E. ff. Bromhead, Edinb. New Phil. Your. 25: 134• 1838 (`Andromedeae'). Bromhead had Andromedeae' as fam. 4 of Ericales. See Ericaceae Androsaceae: Barnhart (1895) lists `A. Reichb., 1828', but H. G. L. Reichenbach, Consp. reg. veg. 1828, p. 128, has Androsaceae as part of the Primulaceae (q.v.).

894 CHEMOTAXONOMY OF FLOWERING PLANTS

Androstachydaceae: H. K. Airy Shaw, Kew Bull, 18: 25o. 1965. A. with Androstachys Prain (1) only; affinities perhaps with Euphorbiaceae (q.v.). Anemonaceae: J. E. Guettard, Observ. sur les plantes, I : z66. 1747 (`Anemonees'). Hutchinson (1969) includes `Anemonaceae Bartling, 1830' in Ranunculaceae. Bartling did not have a family A., but a group Anemonea in Ranunculaceae. See Ranunculaceae Angelicaceae: G. T. Burnett, Outlines of Bot. 1835, pp. 772, 773. A. (Orthospermae), with Saniculidae, Angelicidae and Daucidae, in Angelicinae (Umbellatae). See Umbelliferae Anisophylleaceae: L. Pierre, Bull. Mens. Soc. Linn. Paris, I (no. 158, 1896 (7)), p. 1251 (` Anisophyllees'). The copy in the library of the Linnean Society, London, has the pencilled date II 1 1897. Ridley (1922) has `Anisophylleae' with Anisophyllea only; Burkill (1935) has Anisophylleaceae with A. and Combretocarpus; Airy Shaw (in W. 1966) adds Polygonanthus. See Rhizophoraceae, Polygonanthaceae Annonaceae n.c.: Bernard de Jussieu, 1759 in A. L. de Jussieu, Gen. pl. 1789 (`Anonae'). B. de Jussieu's family was a mixed one. The conserved name is that of A. L. de Jussieu (1789—`Anonae', as Annonaceae). Virtually all botanists have included Annonaceae in Polycarpicae, Ranales (or the equivalent), Magnoliales or Annonales. Thus we have: Polycarpicae—Endlicher, 1836-40; Grisebach, 1854; Drude, in Schenk, 1887; van Tieghem and Constantin, 1918; Wettstein, 1935; Emberger, in Chadefaud and E., 1960. Ranales (or its equivalent)Dumortier, 1829; Burnett, 1835; Caruel, 1881; Bessey, 1915; Rendle, 1938; Gates, 1940; Pulle, 1950; Benson, 1957; Crete, 1959. Magnoliales (part of Polycarpicae or Ranales)—Gundersen, 195o; Soo, 1953 Fries, in EP2, 1959; Buchheim, in Syll. 12, 1964; Cronquist, 1968; Takhtajan, 1969. Annonales (part of Magnoliales)—Lindley, 1836; Hallier, 1912; Thorne, 1968; Hutchinson, 1969. Some taxonomists have included Eupomatia—but see Eupomatiaceae. See Monodoraceae, Hornschuchiaceae; Magnoliales for discussion.

FAMILIES OF DICOTYLEDONS 895

Annulaceae: J. Dulac, FL Dept. Hautes-Pyren. 1867, p. 301. A. as a synonym of Rosaceae (q.v.). Anreder(ac)eae: J. G. Agardh, Theoria, 1858, p. 357 (`Andredereae'). See Basellaceae Anthemidaceae: H. F. Link, Handb. I, 752. 1829 (`Anthemideae'). Link includes Cotula, Bellis, Anthemis, etc. in his family. Bessey (1915) and Gates (1940) have a family Anthemidaceae in Asterales. See Compositae Anthobol(ac)eae: B. C. Dumortier, Anal. 1829, p. 15 (' Anthoboleae'). Dumortier's family included Exocarpos(sic) and Anthobolus. Lindley (1836) placed these genera in Thymelaceae (sic). Others have recognized affinity with Santalaceae (q.v.). Antidesm(at)(ac)eae: R. Sweet, Hort. Brit., 2nd ed., 1830, p. 460 (`Antidesmeae'). Sweet included Antidesma and Stilago. Horaninow (1843, 1847) had a mixed family Antidesmaceae. Airy Shaw (in W. 1966) says Antidesm(atac)eae Sweet ex Endl. = Stilaginaceae C. A. Agardh. Hutchinson (1969) includes Antidesmataceae Endl. 1837' in Euphorbiaceae. See Stilaginaceae, Euphorbiaceae Antirrhinaceae: DC. and Duby, 1828 ? Airy Shaw (in W. 1966) has Antirrhin(ac)eae DC. and Duby = Scrophulariaceae. Hutchinson (1969) includes it in Scrophulariaceae. Antitypaceae: J. Dulac, Fl. Dept. Hautes-Pyren., 1867, p. 228. A. as a synonym of Oxalideae DC. Antoniaceae: J. G. Agardh, Theoria, 1858, p. 307 (`Antonieae'). Hutchinson (1959) has Antoniaceae with Antonia, Bonyunia, Norrisia and Usteria of our Loganiaceae, and Peltanthera (Buddlejaceae). Airy Shaw (in W. 1966) has the same loganiaceous genera in Antoniaceae (Endl.) J. G. Agardh. Hutchinson (1969) has A. as fam. 4 of Loganiales. See Loganiaceae, Buddlejaceae Apamaceae: A. Kerner von Marilaun, Pflanzenl. II: 700. 1891. Apama Lam. (12, Indomalaya, S. China) is usually placed in Aristolochiaceae (q.v.).

896 CHEMOTAXONOMY OF FLOWERING PLANTS

Aparin(ac)eae: J. C. Graf von Hoffmannsegg and H. F. Link, Fl. port. II: 38. 18zo (`Aparineae'); C. S. Rafinesque, Ann. Gen. Sci. Phys. 6: 84. 1820 (`Aparinia', `Aparinees'). Airy Shaw (in W. 1966) says Aparin[ac]eae Hoffragg and Link = Rubiaceae Juss. Actually H. & L. included Asperula, Crucianella, Galium, Rubia, Sherardia and Vaillanta (sic)—all members of the RubioideaeRubieae. Rafinesque included as sub-families Chimarhidees, Astrophylla (with Asperula, etc.), Coffeacees, and Antirhidees. See Rubiaceae Apiaceae n.c.: J. Lindley, Nat. Syst., 2nd ed., 1836, p. 21. The name Apiaceae is an alternate for Umbelliferae (q.v.). It has been used by many authors. Apocynaceae n.c.: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 478. 1770 (`Apocinatae'). Necker included Asclepias and Vinca. We put the former nowadays in Asclepiadaceae. Apocynaceae Juss. 1789 (`Apocyneae') is conserved. Almost all taxonomists have recognized a family Apocynaceae and have associated it with Asclepiadaceae, Gentianaceae, etc. in orders variously named. Thus we have: Contortae—Endlicher, 1836-40; Drude, 1886-7; Wettstein, 1935; Rendle, 1938; Skottsberg, 1940; Pulle, 1950; Tournay and Lawalree, 1952; Soo, 1953. Gentianales—Lindley, 1853; Bessey, 1915; Gates, 1940; Crete, 1959; Wagenitz, in Syll. 12, 1964; Takhtajan, 1966; Cronquist, 1968; Thorne, 1968. Loganiales—Gundersen, 1950. Apocynales—Boivin, 1956; Benson, 1957; Hutchinson, 1969. Hallier (1912) put A. in Tubiflorae. We must expect the chemistry of this large family (zoo/z000) to resemble that of the Asclepiadaceae more particularly and we shall see that it does. There has been some segregation, and there are other names. See Emeticaceae, Plumeriaceae, Vincaceae, Willughbeiaceae; Gentianales for discussion. Apodanthaceae: A. Kerner von Marilaun, Pflanzenl. II: 700. 1891. Kerner included his family in Rafflesiales; van Tieghem and Constantin (1918) put A. in Castaneales (which included Rafflesiaceae); Melchior (in Syll. 12, 1964) includes Apodantheae in Raiesiaceae; while Hutchinson (1969) includes Apodanthaceae v.T. in Rafflesiaceae. See Rafflesiaceae

FAMILIES OF DICOTYLEDONS 897

Aptandraceae: J. Miers, Ann. and Mag. Nat. Hist. 7 (ser. z): zoo, zo6. 1851. Aptandraceae (with Aptandra) near Berberidaceae, Menispermaceae and Annonaceae. Later workers see a relationship to Olacaceae, etc. Thus we have the family in: Olacales—van Tieghem and Constantin (1918); Hutchinson (1969) —with Aptandra, Ongokea, and Harmandia (but see Opiliaceae!). Santalales—Takhtajan (1966). Schultze-Motel (in Syll. 12, 1964), and Airy Shaw (in W. 1966) include Aptandreae in Olacaceae (q.v.). Aquifoliaceae n.c.: A. P. De Candolle, Thdorie diem. bot., Ist ed., 1813, p. 217 ( `Aquifoliacees' ). Aquifoliaceae Bartling (183o) is conserved. Almost all taxonomists have recognized a family, as Aquifoliaceae or Ilicineae, and almost all have placed it near Celastraceae. Thus we have: Celastrales (or its equivalent)—Burnett, 1835; Camel, 1881; Bessey, 1915; Wettstein, 1935; Rendle, 1938; Skottsberg, 1940; Gundersen, 195o; Pulle, 195o; Soo, 1953; Boivin, 1956; Scholz, in Syll. 12, 1964; Takhtajan, 1966—but see Phellineaceae; Cronquist, 1968; Hutchinson, 1969. Sapindales—Benson, 1957 (next to Celastraceae). FrangulaeDrude, 1886-7 (as Ilicineae, his order includes Celastraceae). Hallier (1912) says it may be derived from Celastraceae; Hall (1949) says that floral anatomy supports a relationship to Celastraceae; Airy Shaw (in W. 1966) says it is very close to Celastraceae. Lindley (1853) has A. in Gentianales; Thorne (1968) has it in Theales! See Ilicaceae, Phellineaceae, Sphenostemonaceae, Vasovulaceae; Celastrales for discussion. Aquilariaceae: R. Brown in Tuckey, Narr. Exped. Congo, 1818, p. 422 (`Aquilarinae'). Brown said that Aquilaria Lam. and Gyrinops Gaertn. might form a new family with or without Chailleteae. Others—such as Burnett (1835), who put it in Ulminae, and Lindley (1836)—had a family Aquilariaceae; and a few modern taxonomists retain the name, putting the family into Thymelaeales (Takhtajan, 1959, but not 1966; Hutchinson, 1969). Following Wagenitz (in Syll. 12, 1964) we include Brown's plants in the Thymelaeales—the first two as Aquilarieae in Thymelaeaceae, the Chailleteae as Dichapetalaceae. See Thymelaeaceae, Dichapetalaceae, Thymelaeales

898 CHEMOTAXONOMY OF FLOWERING PLANTS

Aragoaceae: D. Don, Edinb. New Phil. y. 19: 109, 113. 1835. Don has Aragoa Kunth (only) in his family which he would put `very near to the Polemoniaceae, especially to the genus Diapensia ...'[1]. We put Aragoa in the Scrophulariaceae (q.v.). Araliaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 217 (`Araliae'). There is almost, but not quite, complete agreement that the Araliaceae is a most natural family whose relationships are with the Umbelliferae. Thorne (1968) even has a family A. including `our' Umbelliferae, in his Cornales; while Hallier (1912) included Araliaceae in his Umbelliferae! Thus we have: Umbellales (Umbellißorae, etc.)—Lindley, 1836, 1853 ; Grisebach, 1854; Caruel, 1881; Drude, 1886-7; Bessey, 1915; v. Tieghem & Constantin, 1918; Wettstein, 1935; Rendle, 1938; Skottsberg, 1940; Gates, 1940; Gundersen, 1950; Pulle, 1950; Soo, 1953; Benson, 1957; Copeland, 1957; Crete, 1959; Melchior, in Syll. 12, 1964; Cronquist, 1968. Araliales (Araliastra, etc.)—Burnett, 1835, incl. Adoxa?; Horaninow, 1843; Boivin, 1956; Hutchinson, 1969, but not including the Umbelliferae. With the opinions of so many taxonomists lined up we must surely expect the chemistry of the Araliaceae and Umbelliferae at least, to be very similar, and we are not disappointed. The relationships with Cornaceae and some other families, as we shall see, are less clear. See Botryodendraceae, Hederaceae; Umbellales Arbutaceae: J. G. Agardh, Theoria, 1858, p. Io6 (`Arbuteae'). See Ericaceae Arceuthobiaceae: Ph. van Tieghem, Bull. Soc. Bot. France, 43: 543. 1896 (`Arceuthobiacees'). See Loranthaceae Arctostaphyl(ac)eae: J. G. Agardh, Theoria, 1858, p. 106 (`Arctostaphyleae'). See Ericaceae Arctot(id)aceae: C. E. Bessey, Ann. Missouri Bot. Gard. 2: 163. 1915. Bessey had Arctotidaceae as fam. 4 of his Asterales (q.v.). Buchheim (1963) lists Arctotaceae Gates, 1940' as legitimate. See Compositae-Arctotideae

FAMILIES OF DICOTYLEDONS 899

Ardisiaceae: A. L. de Jussieu, Ann. Mus. d'Hist. Nat. (Paris), 15: 336. 181o. See Myrsinaceae Argophyll(ac)eae: S. L. Endlicher, Gen. pl. 1839, p. 822 (`Argophylleae') Endlicher's family had Argophyllum only. See Saxifragaceae–Escallonioideae Arionaceae: Ph. van Tieghem, Bull. Soc. Bot. France, 43: 548. 1896

(`Arionacees').

Van Tieghem separated Ariona and Ouinchanaalium from the Santalaceae. Bullock (1958) would use the spelling Arjonaceae. See Santalaceae Aristolochiaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 72 (`Aristolochiae').

Jussieu included Aristolochia, Asarum and Cytinus (which last we put today in Rafflesiaceae). The family is difficult to place. Masters (1875) thought it nearest to Dioscoreaceae (Monocots!). It has been put in Myrtales (an advanced order) by Bessey (1915) and Gates (1940). Burnett (1835) had A. in his Asarinae. Most authors have an order Aristolochiales to include A. and often Rafflesiaceae and Hydnoraceae—among these are Lindley (1836) ; Hallier (1912); Rendle (1938); Skottsberg (1940); Gundersen (195o); Pulle (1950); Sod (1953); Boivin (1956); Benson (1957); Crete (1959); Emberger (in Chadefaud and Emberger, 1960); Melchior (in Syll. 12, 1964); Cronquist (1968); Hutchinson (1969); and Takhtajan (1969). Most of these authors, and a few others, believe the family to be related to the Magnolialean or Ranunculalian complex, and probably the former. We shall see that the chemistry is in line with this view. See Apamaceae, Asaraceae, Pistolochiaceae, Sarum(at)aceae; Aristolochiales for discussion. Aristoteliaceae: B. C. Dumortier, Anal. 1829, pp. 37, 41. Dumortier had Aristotelia (only?) in his family. Lindley (1836) placed A. in Philadelphaceae. Endlicher (1836-4o) had a family Aristoteliaceae in Guttiferae. The moderns include Aristotelia in Elaeocarpaceae (Schultze-Motel, in Syll. 12, 1964) or Tiliaceae (Hutchinson, 1969). See Elaeocarpaceae, Tiliaceae Arjonaceae: see Arionaceae

900 CHEMOTAXONOMY OF FLOWERING PLANTS

Armeriaceae: B. C. Dumortier, Comm. bot. (1822) 1823, p. 61. Dumortier separated Armeriaceae and Plumbaginaceae, as did Horaninow (1843). Burnett (1835) used the name for our Plumbaginaceae. We shall see that there are chemical differences between the subfamilies which contain Armeria and Plumbago respectively. See Plumbaginaceae Artocarpaceae: R. Brown in Tuckey, Narr. Exped. Congo, 1815, p. 454 (`Artocarpeae'). Many authors have a family Artocarpaceae to include what we would call Moraceae or, in some cases, Moraceae-Artocarpoideae. Many, from Lindley (1853) on, recognize a relationship to Urticaceae and the Urticales. See Moraceae Asaraceae: E. P. Ventenat, Tabl. reg. veg. 1799, II: 226 (`Asaroideae'). Ventenat included Aristolochia, Asarum and Cytinus. Most later authors have treated the family, excluding Cytinus, as synonymous with Aristolochiaceae, but Nakai (1936)—a splitter—has Asaraceae, Aristolochiaceae and Sarumataceae forming his Aristolochiales. See Aristolochiaceae Asclepiadaceae n.c.: N. J. von Jacquin, Misc. austriaca ad bot., etc. I: 35. 1778 (`" Genitalia Asclepiadarum" Asclepiadeis'); R. Brown, Mem. Wernerian Nat. Hist. Soc. 1: 12-78. 1811 (read 4 November 1809) (`Asclepiadeae'). Brown seems first clearly to have distinguished between Apocynaceae and Asclepiadaceae. The International Code lists Asclepiadaceae R.Br. as conserved. Brown listed 38 genera with about 150 species. The modern estimate is 130/20001 Most authors recognize close relationship to Apocynaceae, Gentianaceae, Loganiaceae, etc. Thus we have: Contortae (Contortales)—Grisebach (1854), Drude (1886-7), Wernham(1911-12), Wettstein(1935), Rendle (1938), Skottsberg (1940), Pulle (1950), Tournay and Lawalree (1952), Sob (1953) and Emberger (in Chadefaud and E., 1960). Gentianales—Lindley (1836), Bessey (1910, Gates (1940), Crete (1959), Wagenitz (in Syll. 12, 1964), Cronquist (1968) and Takhtajan (1969). Loganiales—Gundersen (1950). Apocynales—Boivin (1956) and Hutchinson (1969). Solanales —Lindley (1853), and van Tieghem and Constantin (1918). Hallier (1912) included Asclepiadaceae in Apocynaceae, as did Thorne (1968).

FAMILIES OF DICOTYLEDONS 90I

There have been efforts to dismember the family, the Periplocaceae being a popular segregate (see Airy Shaw, in W. 1966). We shall see that the chemistry of the Asclepiadaceae—about which we know a great deal—is in line with a close relationship to the

Apocynaceae. See Periplocaceae, Stapeliaceae; Gentianales for discussion Ascyr(ac)eae: N. J. de Necker, Acta Acad. Theodoro-Palat. z: 483. 177o (`Ascyroideae'). Necker included Cistus (Cistaceae) and Hypericum (= Ascyrum Mill.; Guttiferae) here. Asperifoliaceae: A. J. G. K. Batsch, Tab. affin., etc. 18oz, p. 188

(`Asperifoliae'). Fam. 1 of Tetraspermae, with Tournefortia, Ehretia, Borago, etc. Reichenbach (1828) had Asperifoliaceae to include our Boraginaceae plus Hydrophyllaceae. Later authors have the name as an alternative to Boraginaceae (q.v.). Asteraceae n.c.: B. C. Dumortier, Comm. bot. t8zz (3), p. 55 (`Astereae'). Dumortier included Aster and Senecio. His name has been conserved as Asteraceae. Burnett (1835) had Asteraceae (Corymbiferae) for part of `our' Compositae. It may be used as an alternative name for Compositae (q.v.). Asteranthaceae n.c.: R. Knuth, Notizbl. Bot. Gart. u. Mus. BerlinDahlem, 11: 1036. 1934. Reichenbach (1828) has been credited with this family but his A. was a part of his Sapotaceae. Knuth's name is conserved. Hutchinson (1969) recognizes the family and puts it in the Myrtales. Others include Asteranthos in Lecythidaceae (also in the Myrtales). See Lecythidaceae Asterocarpaceae: A. Kerner von Marilaun, Pflanzenl. II: 688. 1891. Kerner had Resedales with Resedaceae and Asterocarpaceae. See Resedaceae Asteropeiaceae: `Takhtajan, 1952' is quoted by some for this family. Takhtajan himself says `1954'. Is this in A. A. Yatsenko-Khmelevsky, Woods (Timbers) of the Caucasus, t, Erivan, 1954, or Proiskh. Pokruitosem. Rast, 1954, p. 89 ? Takhtajan (1969) places the family in Theales. Melchior (in Syll. 12, 1964) and Hutchinson (1969) put Asteropeia in Theaceae. Airy

902 CHEMOTAXONOMY OF FLOWERING PLANTS

Shaw (in W. 1966) maintains the family and says that it may have affinities with Linaceae, Tetrameristaceae or Flacourtiaceae. See Theaceae Astrantiaceae: see Eryngiaceae Atherosperm(at)aceae: R. Brown in Flinders, Voy. Terra Austr. II: 553. 1814 (`Atherospermeae'). Brown says he differs from Jussieu in separating Pavonia R. & P. (Laurelia Juss.) and Atherosperma Labilt. from Monimieae (Monimiaceae).

Others, including Lindley (1836), Grisebach (1854), Pichon (1948— who says the spelling should be Atherospermataceae), and Airy Shaw (in W. 1966), have maintained the family. The last has 7/100. They recognize relationship to Monimiaceae. Yet others, including Buchheim (in Syll. 12, 1964), Takhtajan (1969) and Hutchinson (1969), include Atherosperma and its relatives in Monimiaceae (q.v.). Atriplic(ac)eae: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 486. 1770 (`Atripliceae'). Jussieu (1789), who included Chenopodium and many non-chenopodiaceous plants, is usually credited with this family. Agardh (1858) had Atriplicieae as a family separated from Chenopodiaceae. The moderns include Atriplicaceae in Chenopodiaceae (q.v.). Atropaceae: J. Miers, Ann. and Mag. Nat. Hist. 3 (Ser. 2): 163. 1849. Miers would have A. either as a family or as a sub-family of Solanaceae. On p. 166 he says: `The Solanaceae, Atropaceae, and Scrophulariaceae, as here defined, evidently constitute an alliance...but ... they form too large an assemblage to constitute one single family.' See Solanaceae Aucubaceae: J. G. Agardh, Theoria, 1858, p. 303. A. separated A. from Cornaceae. Virtually all botanists include Aucuba in Cornaceae (q.v.). Aurantiaceae: A. L. de Jussieu, Gen. pl. 1789, p. 259 (`Aurantia'). J's family was a mixed one with Citrus, Limonia and Murraya (Rutaceae); Ximenia and Heisteria (Olacaceae); and Camellia, Thea, Ternstroemia (Theaceae). Burnett (1835) used the name Aurantiaceae for part of `our' Rutaceae and placed his family in Rutinae. See Rutaceae

FAMILIES OF DICOTYLEDONS 903

Austrobaileyaceae n.c.: L. Croizat, Your. Cactus and Succ. Soc. Amer. 15: 64. 1943 (I have not checked this). Almost all seem agreed that the relationships of Austrobaileya are with families of the Polyearpicae (Magnoliales, Annonales, Laurales). It has been included in Magnoliaceae, Monimiaceae, Dilleniaceae and Schisandraceae. See Magnoliales Averrhoaceae: J. Hutchinson, Fam. Fl. Pl., and ed., I : 356. 1959. Averrhoa is separated from the Oxalidaceae, where it is usually placed, and put as a family in the Rutales on H.'s `woody' side. If he is right the chemistry of Averrhoa should be quite different from that of the Oxalidaceae. See Oxalidaceae for discussion Avicenniaceae n.c.: S. L. Endlicher, Enchirid. 1841, p. 314 (`Avicennieae') (I have not checked this). Endlicher (1836-40) had Avicennieae among ` Genera Verbenaceis affinia'; later he had a family which has been conserved. Takhtajan (1959) had Avicenniaceae in Lamiales. Later (1966, 1969) he includes it in Verbenaceae, as does Melchior (in Syll. 12, 1964), and Hutchinson (1969). See Verbenaceae and Tubiflorae Azimaceae: R. Wight and G. Gardner, Calcutta Your. Nat. Hist. 6: 52. 1845 (1846 on title page). W. and G. had Azima as a natural order (family) between Oleaceae and Yasminaceae. See Salvadoraceae Baccataceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 460. B. as a synonym of Caprifoliaceae (q.v.). Balanitaceae n.c.: S. L. Endlicher, Enchirid. 1841, p. 547 (`Balaniteae'). Balanites Delile (25, trop. Afr. to Burma) has been placed in Simaroubaceae, Zygophyllaceae, Rutaceae, and—by Endlicher and others—in a family of its own. Endlicher's name is conserved. The spelling Balanidaceae has been used. See Zygophyllaceae for discussion Balanop(sid)accae n.c.: G. Bentham, in Bentham and Hooker, Gen. Plant. III: 341. 188o (`Balanopseae'). The spelling Balanopaceae is conserved, but many have used the form 9

cco it

904 CHEMOTAXONOMY OF FLOWERING PLANTS

Balanopsidaceae. All include Balanops Baillon (incl. Trilocularia) only. It is isolated and of quite uncertain position as witness the following placings as a family: Malvales-Bessey (1915); Myricales-van Tieghem and Constantin (1918), Soo (1953); Urticales-Cronquist (1957); Fagales-Cronquist (1968); Balanop(sid)ales-Wettstein (1 935), Skottsberg (1940), Gundersen (195o), Pulle (195o), Boivin (1956), Benson (1957), Melchior (in Syll. 12, 1964), Thorne (1968), Hutchinson (1969), Takhtajan (1969). Hallier (1912) put Balanops in Hamamelidaceae. See Balanop(sid)ales for discussion Balanophoraceae n.c.: L. C. and A. Richard, Mem. Mus. Hist. Nat. Paris, 8: 429. 1822 (`Balanophoreae'). This family, with perhaps 18/100-120, is a puzzling one. It has been split many ways (below). It has been placed among the monocotyledons by Lindley (1830) and Salisbury (1866)! It has been placed in the Aristolochiales-Hallier (1912); Celastrales-Bessey (1915); Santalales (Viscales, or equivalent)-Grisebach (1854), van Tieghem (1896), Wettstein (1935), Rendle (1938), Gundersen (1950), Soo (1953), Boivin (1956), Benson (1957), Copeland (1957), Crete (1959), Thorne (1968), Cronquist (1968), Hutchinson (1969), and Takhtajan (1969); Balanophorales (or equivalent)-Dumortier (1829), Kerner (1891), van Tieghem and Constantin (1918), Skottsberg (1940), Pulle (1950), and Schultze-Motel (in Syll. 12, 1964). See (add -aceae): Hachette., Helosid. (Hutchinson, 1969, has Helond., in error ?), Langsdorfi., Latraeophile., Lophophyt., Sarcophyt.; Balanophorales for discussion. Balantiaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 442. B. as a synonym of Asclepiadeae R. Br. Balsamaceae: J. Lindley, Nat. Syst. Bot., 2nd ed., 1836, p. 188. Lindley placed his family in Salicales. See Altingiaceae, Hamamelidaceae Balsameaceae: B. C. Dumortier, Anal. 1829, p. 36. B. with tribe 1, Burseraceae Kunth and tribe 2, Spondiaceae Kunth. See Burseraceae, Anacardiaceae (Spondieae), Spondi(ad)aceae Balsamiflu(ace)ae: C. L. Blume, Fl. Java? Several authors credit Blume with Balsamifluae. They include Liquidambar and/or Altingia. See Hamamelidaceae

FAMILIES OF DICOTYLEDONS 905

Balsaminaceae n.c.: A. Richard, Dict. Class. d'Hist. Nat. (ed. Bory de Saint-Vincent), H: 172, 173. 1822 ('Balsamineae', 'Balsaminees'). Query A. Richard, 1810 ? Richard had Balsamina (Impatiens L. today) only in his family, which is conserved. Airy Shaw (in W. 1966) has 4/500 (Impatiens, Hydrocera, Semeiocardium, Impatientella). Most botanists recognize the family, putting it in Geraniales or in neighbouring orders: Gruinales (± Geraniales)—Martius (1835), Endlicher (1836-40), Grisebach (1854), Drude (1886-7), Hallier (1912), and Copeland (1957). Geraniales (or equivalent)—Dumortier (1829), Burnett (1835), Lindley (1853), Bessey (1915), Rendle (1938), Gates (1940), Barkley (1948), Gundersen (1950), Boivin (1956), Benson (1957), Crete (1959), Thorne (1968), Cronquist (i968—doubtfully), Hutchinson (1969), and Takhtajan (1969). Terebinthales—Wettstein (1935), and Soo (1953)• Sapindales—Skottsberg (1940), and Scholz (in Syll. 12, 1964). Balsaminales—Pulle (1950, as only family of order). See Crispaceae, Hydroceraceae, Impatientaceae; Sapindales for discussion. Barbeuiaceae: T. Nakai, Your. yap. Bot. 18: 105. 1942. 'B. Nakai in Prael. pro alum. bot. Univ. Imp. Tok. anno 1939 et seq.' with Barbeuia Thouars only. See Phytolaccaceae Barbeyaceae n.c.: A. B. Rendle in Thiselton-Dyer, Flora Trop. Africa, 1916. Rendle had Barbeya Schweinf. only in his family. Barbeya has been treated as a member of the Ulmaceae by Gundersen (1950) and Melchior (in Syll. xII, 1964); as a family of the Urticales by Boivin (1956), Cronquist (1968), and Hutchinson (1969); and as the only family of an order Barbeyales by Takhtajan (1969). Its chemistry, of which we are ignorant, should be interesting! See Ulmaceae, Urticales, Barbeyales VI (2): 14.

Barclayaceae: A. Kerner von Marilaun, Pflanzenl. II: 699. 1891. Barclaya Wall. (3-4, Indomalaya) has been placed in the Nymphaeaceae (Buchheim, in Syll. 12, 1964; Hutchinson, 1969), or has been made a family (Kerner, 1891; Li, 1955; Takhtajan, 1969). Its affinities are thought to be with Nymphaeaceae (q.v.). Barreriaceae: K(C). F. P. von Martius, Consp. regn. veg. 1835, p. 41. M.'s family included Barreria Scop. (Poraqueiba Aubl.). See Icacinaceae 9- 2

906 CHEMOTAXONOMY OF FLOWERING PLANTS

Barringtoniaceae n.c.: F. K(C). L. Rudolphi, Syst. orb. veg. 1830, p. 56 (`Barringtonieae'). R. has Barringtonieae DC. as a family, but names no genera. His name is conserved. As a family it has been placed in Myrtales by Skottsberg (1940) and Hutchinson (1969); in Grossales by Lindley (1846). It has been included in Myrtaceae by Lindley (1836), Walpers (1843) and Horaninow (1847); in Punicaceae by Horaninow (1843); and in Lecythidaceae by Gundersen (1950), Melchior (in Syll. 12, 1964), and Takhtajan (1969). The moderns seem to agree on a relationship with families of our Myrtiflorae (Myrtales) and particularly with Lecythidaceae. See Belvisiaceae, Lecythidaceae, Napoleonaceae; Myrtales for discussion. Basellaceae n.c.: A. Moquin-Tandon, Chenopod. monogr. enum. 1840, p. x. M.-T. had a family including Anredereae and Baselleae. The name is conserved. Almost all agree that a family B. finds its place in an order including Chenopodiaceae. Thus we have: Centrospermae—Wettstein (1935), Rendle (1938), Skottsberg (1940), Soo (1953), Crete (1959), and Eckardt (in Syll. 12, 1964). Chenopodiales—Standley (1916), Boivin (1956), Thorne (1968), and Hutchinson (1969). CaryophyllalesBessey (1915), Gundersen (1950), Pulle (1952), Benson (1957), Cronquist (1968), and Takhtajan (1969). Violales—v.T. and C. (1918). A few early workers—C. A. Agardh, Lindley, and Endlicher—. included B. in Chenopodiaceae. We should expect the chemistry of the Basellaceae to be that of the Centrospermae, and we shall see that it is. See Anrederaceae, Ullucaceae; Centrospermae for discussion Bat(id)aceae n.c.: K(C). F. P. von Martius, Consp. regn. veg. 1835, p. 13 (`Batideae'). Martius had Batideae with Batis only. Bataceae Mart. ex Meisn. (1842) is conserved. This little family has usually been associated with the Centrospermae or equivalent orders, or given an order of its own. Thus we have: Centrospermae—Soo (1953)• Caryophyllales—Bessey (1915), Gundersen (1950) and Takhtajan (1969). Chenopodiales—Standley (1916), Boivin (1956) and Hutchinson (1969). Bat(id)ales—Skottsberg (1940), Benson (19J7), McLaughlin (1959), Eckardt (in Syll. 12, 1964), and Thorne (1968).

FAMILIES OF DICOTYLEDONS 907

A few have seen relationships with Piperaceae—v.T. (1903), v.T. and C. (1918), and Drude (in Schenk, 1887?); with EuphorbiaceaeLindley (1853, doubtfully); or even with Verbenaceae—Clarke (1859). See Bat(id)ales for discussion Baueraceae—J. Lindley, Introd. Nat. Syst. 183o, p. 5o. L.'s family—with Bauera only—was distinguished by him from Saxifrag(ac)eae and Cunoniaceae. Others—Emberger (in C. and E., 196o), and Schulze-Menz (in Syll. 12, 1964)—have put Bauera in Saxifragaceae (s J.); or as a family in Sax(ifrag)ales—Lindley (1836), and Nakai 0943, who spells it Baueriaceae); or in Cunoniales—Hutchinson (1969). Takhtajan (1966) puts B. in Cunoniaceae. See Cunoniaceae, Saxifragaceae (for discussion), Rosales Begoniaceae n.c.: R. Brown in Tuckey, Narr. Exped. Congo, 1818, P. 464. Brown says his family is of doubtful position, and his opinion is reflected in the varied placings of it (below). Begoniaceae C. A. Agardh (1825) is conserved. It has been placed in: Cucurbitales (Peponiferae or equiv.)—Endlicher (1836-40), Grisebach (1854), Hallier (1912), Rendle (1938), Boivin (1956), and Hutchinson (1969). EuphorbinaeBurnett (1835). Parietales—Wettstein (1935), Skottsberg (1940), and Sod (1953)• Passiflorales (or equiv.)—Copeland (1957), and Crete (1959)• Cistales—Gundersen (1950), Pulle (1952) and Thorne (1968). Violales—Melchior (in Syll. 12, 1964), and Cronquist (1968). Loasales—Bessey (19,5). Begoniales—Lindley (1836), Benson (1957) and Takhtajan (1969). In analysis one finds stress on relationships to Datiscaceae, Cucurbitaceae, Passifloraceae, and Loasaceae. See Violales for discussion Belanger(ac)eae—J. G. Agardh, Theoria, 1858, p. 337 (`Belangereae'). Agardh saw a relationship to Lagerstroemieae (Lythraceae). Airy Shaw (in W. 1966), Hutchinson (1969), and Schulze-Menz (in Syll. 12, 1964) put B. in Cunoniaceae (q.v. for discussion). Belvisiaceae—R. Brown, Trans. Linn. Soc. Lond. 13: 222. 1822 (read June 20, 1820) (`Belviseae'). Brown included Napoleona Pal. (Belvisia Desv.) and Asteranthos Desf. The little family has been variously placed (Campan(ul)ales, Passiflorales, etc.). Lindley (1853) used the form Belvisiaceae, as did Burnett (1835), who put the family in Styracinae.

908 CHEMOTAXONOMY OF FLOWERING PLANTS

See Asteranthaceae, Barringtoniaceae; Lecythidaceae and Myrtales for discussion Bennettiaceae—A. Schnizlein, Iconogr. fam. nat. t. 172** in fasc. 3 (dated 1843-70) (`Bennettieae R. Brown'). Airy Shaw (in W. 1966) and Hutchinson (1969) treat this as Bennettiaceae R. Brown (where and when ?). See Pandaceae, Scepaceae, Euphorbiaceae Berberidaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 286. (`Berberides'). J.'s family (by modem standards) was a mixed one, but his name is conserved. Almost all recognize a family Berberidaceae and place it in the neighbourhood of the Menispermaceae. Thus we have Polycarpicae (or equiv.)—Endlicher (1836-40), Drude (1886-7), Wettstein (1935), Skottsberg (1940), Copeland (1957) and Emberger (in C. and E., 1960). Ranales (or equiv.)—Burnett (1835, as Berberaceae), Camel (1881), Hallier (1912), Bessey (1915), Rendle (1938), Gates (194o), Gundersen (1950), Benson (1957), and Crete (1959). Ranunculales—v.T. and C. (1918), Pulle (1952), Buchheim (in Syll. 12, 1964), Cronquist (1968) and Takhtajan (1969). Berberidales (or equiv.)—Dumortier (1829), Lindley (1836), Boivin (1956), Thorne (1968) and Hutchinson (1969). Magnoliales—Soo (1953)• Some separate from it the Podophyllaceae. Buchheim has 14/650 (incl. P.); Airy Shaw (in W. 1966) has only 4/575; and Hutchinson (1969) only Berberis and Mahonia! See (add -aceae): Coelostigmat., Diphyllei., Leontic., Nandin., Podophyll.; Ranunculales (for discussion). Bertyaceae: J. G. Agardh, Theoria, 1858, p. 190. See Euphorbiaceae Berzeliaceae: T. Nakai, Ord., Fam., etc., App., 1943, p. 241. `Berzeliaceae Nakai, I.c. Berzelia Brongn., Mniothamnea Niedenzu.' See Bruniaceae Besleriaceae: ?R. Brown (p. 586 of the Ray Society's Misc. Bot. Works of Robert Brown mentions `Besleriaceae of Richard and De Jussieu, now generally named Gesneriaceae'). See Cyrtandraceae, Gesneriaceae Betaceae: G. T. Burnett, Outlines of Bot. 1835, pp. 591, 1142. B. had B.—including our Chenopodiaceae and Amaranthaceae—in his Rumicinae.

FAMILIES OF DICOTYLEDONS 909

Betulaceae n.c.: S. F. Gray, Nat. Arr. Brit. Pl. II: 243. 1821 (`Betulideae'). Gray's family included Betula and Alnus. The name is conserved, even if Corylaceae Mirbel be included. The placing of the family is difficult but most taxonomists put it with Fagaceae. Thus we have: Fagales—Wettstein (1935), Rendle (1938), Skottsberg (1940), Gundersen (195o), Pulle (1952), Soo (1953), Boivin (1956), Benson (1957), Melchior (in Syll. 12, 1964), Thorne (1968), Cronquist (1968) and Hutchinson (1969). Quercinae—Burnett (1835). Amentales (or equiv.)—Dumortier (1827), Lindley (1853), Hallier (1912) and Crete (1959)• Juliflorae (±Amentales)—Endlicher (183640), Camel (1881) and Copeland (1957). Myricales—v.T. and C. (1918). Betulales—Bromhead (1838), Nakai (1943) and Takhtajan (1969). Sapindales—Bessey (1915), and Gates (1940). Several authors restrict B. to Betula and Alnus, having a family Corylaceae for the other genera. See Carpinaceae, Corylaceae; Fagales for discussion Bicornaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 265. B. as a synonym of Saxifrageae J. Biebersteiniaceae: S. L. Endlicher, Gen. pl. 1840, p. 1165 has Biebersteinieae among `Gen. Zygophylleis affinia'; J. G. Agardh, Theoria, 1858, p. 167 (`Biebersteinieae'). Airy Shaw (in W. 1966) has Biebersteiniaceae Endl. with Biebersteinia (5) only; Takhtajan (1969) has the family in Geraniales; Hutchinson (1969) includes B. in Geraniaceae; while Scholz (in Syll. xII, 1964) has a group Biebersteinieae, with Biebersteinia and Rhynchotheca, also in Geraniaceae. See Ledocarpaceae, Rhynchothecaceae; Geraniaceae and Geraniales for discussion Bifariaceae: T. Nakai, Bull. Nat. Sci. Mus. Tokyo, no. 31, p. 46, 1952. I have not checked this. Airy Shaw (in W. 1966) says B. Nakai = Loranthaceae. Phoradendreae Engl. See Loranthaceae Bignoniaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 137 (`Bignoniae'). J.'s family was a mixed one with genera from our Bignoniaceae, Scrophulariaceae, Pedaliaceae, and Martyniaceae—all in our Tubiflorae. Almost all botanists include the Bignoniaceae in the Tubiflorae (s.l.)

910 CHEMOTAXONOMY OF FLOWERING PLANTS

or segregates from that order. Thus we have: Tubiflorae (or equiv.)Wernham (1911-12), Hallier (1912), Wettstein (1935), Rendle (1938), Skottsberg (1940), Emberger (in C. and E., 1960), and Melchior (in Syll. 12, 1964). Scrophulariales (Personales, or equiv.)-Burnett (1835), Martius (1835), Endlicher (1836-40), Drude (1887), Bessey (1915), v.T. & C. (1918), Gates (194o), Soo (1953), Boivin (1956), Benson (1957), Crete (1959), Cronquist (1968) and Takhtajan (1969). Polemoniales-Gundersen (195o). Bignoniales-Lindley (1833, 1836, 1853), Hutchinson (1969-away from most of our Tubiflorae). A few segregates have been suggested. See: Crescentiaceae, Paulowniaceae; Tubiflorae for discussion Biligulaceae: B. C. Dumortier, Comm. bot. 1822(3), (`Biligulares'). D.'s family included Mutisia and Clarionea (=Perezia). See Mutisiaceae, Compositae Bischofiaceae: H. K. Airy Shaw, Kew Bull. 18 (2): 252. 1965. Airy Shaw has B. (Muell. Arg.) Airy Shaw and says that Bischofia, the only genus, is probably related to Staphyleaceae. Hutchinson (1969) includes B. in Euphorbiaceae. See Euphorbiaceae, Staphyleaceae Bixaceae n.c.: C(K). S. Kunth, Malv., Büttn., etc. 1822, p. 17 (`Bixinae'). K.'s family had several genera, all but one of which we now put in the Flacourtiaceae. Bixaceae Link, Handb. 1831 (`Bixinae') is conserved. All moderns are agreed that the family should have Bixa only or Bixa plus Cochlospermaceae. All agree, too, that relationships are with Parietales (s.l.) or segregated orders. Thus we have: Parietales (or equiv.)-Endlicher (1836-40), Wettstein (1935), Rendle (1938), Skottsberg (1940), Soo (1953), Copeland (1957) and Crete (1959). Cistales (or equiv.)-Burnett (1835), Martius (1835), Drude (1887), v.T. & C. (1918), Gundersen (195o), Pulle (1952) and Thorne (1968). Guttiferales-Bessey (1915), and Benson (1957). Violales (Violastra, etc.)-Horaninow (1847), Melchior (in Syll. 12, 1964), Cronquist (1968) and Takhtajan (1969). Bixales-Lindley (1836), and Boivin (1956). See Violales for discussion Blackwelliaceae: C. H. Schultz, Nat. Syst. Pflanzenr., 1832, p. 444. `Homalineae s. Blackwelliaceae' with genera we now place in Flacourtiaceae (q.v.).

FAMILIES OF DICOTYLEDONS 91I

Blakeaceae: Barnhart (1895) lists `Blakeaceae Reichb., 1828', but H. G. L. Reichenbach, Consp. reg. veg. 1828, p. 174, has B. as a part of his family Lythrariae, not as a family. Blattiaceae: F. Niedenzu in EP1, 3 (7): 16-21. 1892. N. had Blatti (Sonneratia), Duabanga (of our Sonneratiaceae) and Crypteronia (of our Crypteroniaceae) in his little family. Dostål (1957) has `Blattidaceae Niedenzu'. See Crypteroniaceae, Sonneratiaceae Blepharocaryaceae: H. K. Airy Shaw, Kew Bull. 18 (2): 2 54. 1965. Airy Shaw draws attention to a possible connection between B. (and Anacardiaceae) and Fagaceae. See Anacardiaceae Blitaceae: Dostål (1957) credits Link (1763) with this family. Is this in error for Linnaeus ? See Chenopodiaceae and Amaranthaceae Boerhaviaceae: Dostål (1957), under Mirabilaceae says `cf. Boerhaviaceae', but he doesn't list B.! Boerlagellaceae: H. J. Lam, Bull. Yard. Bot. Buitenzorg, Ser. 3, 7: 25o. 1925. Lam has B. with Boerlagella and Dubardella. Hutchinson (1969) includes B. in Sapotaceae (q.v.). Bolaceae: Barnhart (1895) lists `Bolaceae Reichb.; Moessl, 1827', but H. G. L. Reichenbach, in J. C. Moessler, Gem. Handb. Gew., and ed. I, p. xlv, 1827, has Bolaceae as a section of Umbelliferae, not as a family. Bolivariaceae: A. H. R. Grisebach, Gen. et spec. Gentian. 1839, p. 2o. G. had B. with Bolivaria Cham. & Schlecht. and Menodora Humb. Bolivaria is now included in Menodora and the genus is placed in Oleaceae-Jasminoideae (q.v.). Bombacaceae n.c.: C(K). S. Kunth, Maly., Büttn. etc., 1822, p. 5 (`Bombaceae'). K. used the spelling Bombaceae but `Bombacaceae' is conserved. Almost all agree that the family, if maintained, is to be placed near Malvaceae, Sterculiaceae, etc. Thus we have: Columniferae—Martius (1835), Grisebach (1854), Hallier (1912), Wettstein (1935), Skottsberg (194o) and Copeland (1957)• Malvales (or equiv.)—Dumortier (1829),

912 CHEMOTAXONOMY OF FLOWERING PLANTS

Bessey (1915), Rendle (1938), Gundersen (1950), Pulle (1952), Soo (1953), Benson (1957), Emberger (in C. & E., 1960), Schultze-Motel (in Syll. 12, 1964), Thorne (1968), Cronquist (1968) and Takhtajan (1969). Tiliales—Barkley (1948), Boivin (1956) and Hutchinson (1969). The group has been included in Malvaceae by a few and in Sterculiaceae by Endlicher (1836-40). See Malvales for discussion Bonnetiaceae: L. Beauvisage, Contrib. etude anat. fam. Ternstroemiaceas, 1920, pp. 256, 452 (`Bonnetiacees'). B. included Bonnetia and Archytaea in his little family, which he put near Ternstroemiaceae (Theaceae). Melchior (in Syll. 12, 1964) includes B. in Theaceae. Tahktajan (1969) and Hutchinson (1969, who includes Haploclathra from our Guttiferae) have a family B. in Theales. Airy Shaw (in W. 1966) includes Ploiarium in his B. See Theaceae for discussion Bontiaceae: P. Horaninow, Prim. lin., etc. 1834, p. 77. H.'s family included Myoporum, Pholidia, and Bontia—all of which we place in Myoporaceae (q.v.). Boopid(ac)eae: H. Cassini, Bull. des Sci. Soc. Philomat. 1816, p. 16o ('Boopideae'). C.'s family included Calycera, Acicarpha, and Boopis—which we put in Calyceraceae (n.c.), although Robert Brown considered Boopideae to have published priority over his Calycereae. See Calyceraceae Boraginaceae n.c.: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 478. 1770 (`Borragineae'). Although N.'s family had 6 genera which we place in Boraginaceae, it is Jussieu's (1789) family which is conserved. All agree that the relationships of the Boraginaceae are with the Tubiflorae (under several names) or segregates from it. Thus we have: Tubiflorae (or equiv.)—Wettstein (1935), Rendle (1938), Skottsberg (1940), Sod (1953), Emberger (in C. & E., 1960) and Melchior (in Syll. 12, 1964). Polemoniales—Bessey (1915), Gates (1940), Benson (1957), Crete (1959) and Takhtajan (1969). Solanales (or equiv.)Burnett (1835), v.T. & C. (1918) and Pulle (1952). Lamiales—Thorne (1968), and Cronquist (1968). Boraginales—Gundersen (1950), Boivin (1956) and Hutchinson (1969). Echiales—Lindley (1836).

FAMILIES OF DICOTYLEDONS 913

If there is more or less general agreement as to placing, there is little agreement as to content, many authors segregating woody and other groups in various ways. See (add -aceae): Asperifoli., Bugloss., Cordi., Ehreti., Heliotrop., Onosm., Scorpi., Tetrachondr., Wellstedi.: Tubiflorae for discussion. Boroniaceae: J. G. Agardh, Theoria, 1858, p. 229 (`Boronieae'). Kerner, 1891 uses the name Boroniaceae. See Rutaceae Botryodendr(ac)eae: J. G. Agardh, Theoria, 1858, p. 231 ('Botryodendreae'). A. had his family next to Araliaceae and we put Meryta (Botryodendrum) in Araliaceae (q.v.). B(o)ugainville(ace)ae: J. G. Agardh, Theoria, 1858, p. 364 (`Bugainvilleae'). See Nyctaginaceae Brassicaceae n.c.: G. T. Burnett, Outlines of Bot. 1835, pp. 853, 1123. Burnett had B. in his Rhaeadinae. The name, which has been used by many authors, is conserved as an alternate to Cruciferae (q.v.). Bretschneideraceae n.c.: Bullock (1958, 1959) credits Radlkofer, in EPI Nachtrage 3: 209. 1907, with this family, but I cannot find it. The conserved name is that of Engler and Gilg (Syll. 9—Io, 1924). It has been put in Sapindales by Tang (1935), Gundersen (195o), and Scholz (in Syll. 12, 1964); in Rutales by Thorne (1968); and in Rhoeadales (Papaverales, Brassicales) by Skottsberg (1940), Pulle (1952) and Benson (1957). It has also been included in Hippocastanaceae, Moringaceae, Caesalpiniaceae, Sapindaceae and (doubtfully) in Capparidaceae! See Sapindales Brexiaceae: J. Lindley, Introd. Nat. Syst. 183o, p. 112. This little family (or group) is usually considered to include Brexia, Ixerba, Roussea and (by some) Argophyllum. There seem to be three views as to relationships. Lindley (183o) considered Brexia, at least, to approach Celastrineae, and v.T. & C. (1918) put B. in Celastrales. Lindley later (1836) had an order Brexiales; while Burnett (1835), who included Pittosporidae in his family, put it in Acerinae.

914 CHEMOTAXONOMY OF FLOWERING PLANTS

A second view would place these plants in Saxifragaceae (Emberger, in C. & E., 196o; Schulze-Menz, in Syll. 12, 1964); in Escalloniaceae (Hutchinson, 1969); or as a family in an order Saxifragales (Takhtajan, 1969). The third view puts Brexieae in Cambogiaceae (Horaninow, 1833) or Clusiaceae (Horaninow, 1847)—our Guttiferae! See Saxifragaceae Bromaceae: G. T. Burnett, Outlines of Bot. 1835, pp. 82o, 1119. B. had Br. (including Dombeyidae, Hermannidae, Buttneridae, and Sterculidae) in his Malvinae. He said that Br. is a better name than Sterculiaceae (q.v.) because not all are smelly! Brunelliaceae n.c.: A. Engler, in EP1, Nachtr. zu IH., 2a, 1897, p. 182. It is generally agreed that the family has Brunellia only, and that its relationships are with Rosales (s.l.), and more narrowly with Cunoniaceae. Thus we have: Rosales—Hallier (1912), Bessey (1915), Wettstein (1935) Skottsberg (194o), Pulle (1952), Emberger (in C. & E., 1960), Schulze-Menz (in Syll. 12, 1964) and Thorne (1968). CunonialesNakai (1943), and Boivin (1956). Saxifragales—Takhtajan (1969). Cephalotales—v.T. & C. (1918). Soo (1953) put Brunellia in Cunoniaceae. The family has been monographed by Cuatrecasas (in press, 1969). See Rosales for discussion Bruniaceae n.c.: R. Brown in Abel, Narr. your. China, App. B (1816-17) 1818, p. 374. Brown included at least 5 genera and suggested affinity with Hamamelidaceae. Bruniaceae A. P. de Candolle (1825) is conserved. Most taxonomists put Br. in Rosales or a segregate order. Some see relationship to Umbelliflorae (which are supposed to be related to Rosales). Thus we have: Rosales—Hallier (1912), Bessey (1915), Wettstein (1935), Skottsberg (194o), Pulle (1952), Benson (1957), Emberger (in C. & E., 196o), Schulze-Menz (in Syll. 12, 1964), and Cronquist (1968). Saxifragales—Takhtajan (1969). HamamelidalesGundersen (1950), Soo (1953), Boivin (1956) and Hutchinson (1969). Pittosporales—Thorne (1968). Bruniales—Nakai (1943). Umbelliflorae (or equiv.)—Lindley (1853), Caruel (1881), and v.T. & C. (1918). Araliastra—Horaninow (1843, 1847). Celastrinae—Burnett (1835). See Rosales for discussion Brunoniaceae n.c.: R. Brown, Trans. Linn. Soc. Lond. 12: 132. 1818 (read 1816) (without name).

FAMILIES OF DICOTYLEDONS 915

Brown wrote: `It will be attended with similar advantage to form a separate family of Brunonia, as a link of equal importance [to Calyceraceae], connecting Compositae with Goodeniaceae, but from both of which it is in many respects very distinct.' Brunoniaceae Dumortier (1829) is conserved. Most taxonomists see a relationship to Campanulales (or to equivalent or segregate orders), and particularly to Goodeniaceae. Thus we have: Campanulales (or equiv.)—Endlicher (1836-40), Bromhead (1838), Caruel (1881), Wernham (1911-12), Skottsberg (194o), Pulle (1952), Benson (1957), Wagenitz (in Syll. 12, 1964), Cronquist (1968) and Takhtajan (1969). Goodeniales—Hutchinson (1969). It has been put in Goodeniaceae—Burnett (1835), Gundersen (1950) and M. & C. (195o). Brunoniales—Lindley (1833, 1836). Compositae (as order)— Grisebach (1854). A few see a relationship to families of the Tubiflorae (s.l.). Thus: Echiales—Lindley (1853). Solanales—v.T. & C. (1918). In Bontiaceae—Horaninow (1843). See Campanulales Bryoniaceae: M. Adanson, Fam. des Pl. 1763, II: II, 135 (`Bryoniae'). See Cucurbitaceae Bucklandiaceae: J. G. Agardh, Theoria, 1858, p. 155 (`Bucklandieae'). A. placed his family near Hamamelidaceae; Nakai (1943) has a fam. B. in Hamamelidales; Hutchinson (1969) includes B. in Hamamelidaceae. We follow Schulze-Menz (in Syll. 12, 1964) in placing Exbucklandia (Bucklandia, Symingtonia) in Hamamelidaceae (q.v.). Buddlejaceae n.c.: Bullock (1959), and the International Code credit Wilhelm (Samenpfl. 1910, p. 90) with this family. I have not seen Wilhelm. Bromhead (1838) had `Buddleieae-Buchnereae' in his Rhinanthales, and several authors—including Emberger (1960), Melchior (in Syll. 12, 1964), Cronquist (1968) and Takhtajan (1969)—see a relationship to the Tubiflorae (Scrophulariales, Tubiflorales). Others—Wettstein (1935), Skottsberg (1940), Pulle (1952), Crete (1959) and Hutchinson (1969)—have B. in Contortae or equivalent orders. See Tubiflorae Buettneriaceae, Buttneriaceae—see Byttneriaceae Bugainville(ace)ae—see B(o)ugainville(ace)ae

916 CHEMOTAXONOMY OF FLOWERING PLANTS

Buglossaceae: J. C. Compte de Hoffmannsegg and H. F. Link, Fl. Port., 1: 163 ('Buglossinae' ). See Boraginaceae Bumeliaceae: J. H. Barnhart, Bull. Torrey Bot. Club, 22: 21. 1895 (`Bumeliaceae (nom. nov.)' as a synonym for Sapotaceae Reichb., 1828). See Sapotaceae Burseraceae n.c.: C. S. Kunth, Ann. des Sci. Nat. Bot., Ser. 1, 2: 346. 1824. K.'s family is conserved. D. Don (1832) has the spelling Burseriaceae. Most agree that B. belongs in `the core of the dicotyledons', but in which order? We have: Terebinthales (or equiv.)—Burnett (1835), Martins (1835), Endlicher (1836-40), Drude (1887), Wettstein (1935), Skottsberg (1940) and Soo (1953). Rutales—Rendle (1938), Gundersen (1950), Pulle (1952), Boivin (1956), Benson (1957), Scholz (in Syll. 12, 1964), Thorne (1968), Hutchinson (1969) and Takhtajan (1969). Geraniales—Bessey (1915), and v.T. & C. (1918). RhamnalesLindley (1836), and Bromhead (1838). Sapindales—Cronquist (1968). See Rutales Buxaceae n.c.: J. L. A. Loiseleur-Deslongchamps, Man. pl. us. indig. 1819 (1818?): pt. 1 (cont'd), p. 495 (`Buxacees'). L. had B. with Buxus, Mercurialis. The conserved name is that of Dumortier (1822). The family is difficult to place, but most authors put B. in or near Euphorbiaceae. Thus we have: Tricoccae—Klotzsch (1859-60), Wettstein (1935), Rendle (1938), Sob (1953) and Crete (1959)• Euphorbiales (or equiv.)—Caruel (1881), Gundersen (1950), Benson (1957), Cronquist (1968), Thorne (1968) and Takhtajan (1969). At least 3 authors put B. in Euphorbiaceae. Geraniales—v.T. & C. (1918). On the other hand we have: Celastrales: Bessey (1915), Skottsberg (1940), Pulle (1952), and Scholz (in Syll. 12, 1964). Baillon (1880) put B. in Celastraceae. Hamamelidales—Boivin (1956), and Hutchinson (1969). Both Hallier (1912) and Croizat (1952) also see a close relationship to Hamamelidaceae. See Celastrales Byblidaceae n.c.: Domin, Act. Bot. Bohem. 1: 3. 1922 (I have not checked this). This little family, with Byblis and sometimes Roridula, has been variously placed.

FAMILIES OF DICOTYLEDONS 917

Most authors put it in Rosales (si.); some in segregate orders. Thus we have: Rosales—Wettstein (1935), Skottsberg (1940), Pulle (1952), Soo (1953), Benson (1957), Emberger (in C. & E., 1960), SchulzeMenz (in Syll. 12, 1964) and Cronquist (1968). PittosporalesBoivin (1956), Thorne (1968) and Hutchinson (1969). Hamamelidales —Gundersen (1950). Saxifragales—Takhtajan (1969). ByblidalesNakai (1943). In Droseraceae—Burnett (1835). See Rosales Byttneriaceae n.c.: R. Brown in Flinders, Troy. Terra Austr. 2: 540. 1814 (`Buttneriaceae'). Brown had Buttneriaceae—the conserved spelling is Byttneriaceae, and one finds also Büttneriaceae and Buettneriaceae—with genera which we now put in Sterculiaceae. All seem to agree that relationship to Malvales (or equiv.) is indicated. Thus we have: Malvales (Columniferae, etc.)—Martius (1835), Endlicher (1836-40), Grisebach (1854) and Pulle (1952). Included in Malvaceae—Horaninow (1843, 1847) and Baillon (1875). Included in Sterculiaceae—many, including Schultze-Motel (in Syll. 12, 1964), Airy Shaw (in W. 1966), Takhtajan (1966) and Hutchinson (1969). See Sterculiaceae Cabombaceae n.c.: A. Richard, Nouv. Elem., 4th ed., 1828, p. 42o (`Cabombeae'). R.'s family had Cabomba and Hydropeltis (Brasenia). He had suggested a family, without name, in 1811. Most authors have a family C. in Ranales (or equiv.), or they include Cabomba and Brasenia in Nymphaeaceae. Thus we have: Ranales (Polycarpicae, or equiv.)—Caruel (1881), Bessey (19,5), Skottsberg (194o), Li (1955), Boivin (1956), Emberger (in C. & E., 1960) and Hutchinson (1969). Ranunculales—Pulle (1952). NymphaealesTakhtajan (1969). Included in Nymphaeaceae—Agardh (1822), Lindley (1836), Hallier (1912), Gundersen (1950), Soo (1953) Benson (1957) Buchheim (in Syll. 12, 1964) and Thorne (1968). In Paeoniaceae—Burnett (1835). See Nymphaeaceae Cactaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 310 (`Cacti'). J.'s family included Ribes and Cacti! The modern view—supported by the occurrence of betacyanins—is that the Cactaceae belong in or near the Centrospermae (or equiv.). Many, however, who have had an order Cactales, have suggested other

918 CHEMOTAXONOMY OF FLOWERING PLANTS

placings. Yet others see relationship to Cucurbitaceae. Thus we have: Centrospermae (Caryophyllales, Chenopodiales, or equiv.)Hallier (1912), Wettstein (1935(?)), Rendle (1938), Pulle (1952), Airy Shaw (in W. 1966), Thorne (1968), Cronquist (1968) and Takhtajan (1969). Cactales (Opuntiales, or equiv.)-Dumortier (1829), Endlicher (1836-40), Drude (1887), Bessey (1915, from Myrtales!), v.T. & C. (1918), Skottsberg (1940), Gates (1940), Gundersen (1950), Soo (1953), Boivin (1956), Buchheim (in Syll. 12, 1964-next to Centrospermae), and Hutchinson (1969). Cucurbitales (Peponiferae, or equiv.)Lindley (1833, 1836), and Grisebach (1854). See Cactales, Centrospermae Caesalpiniaceae n.c.: R. Brown in Flinders, Voy. Terra Austr. II: 551. 1814 (`Lomentaceae or Caesalpineae'). Brown's name is conserved as Caesalpiniaceae. A surprisingly large number of botanists have recognized the family as belonging to an order Leguminales (or equiv.). We have: Leguminales (Fabales, or equiv.)-Brown (1814), Martius (1835), Bromhead (1838), Klotzsch & Garcke (1862), Drude (1887), Soo (1953), Jones (1955), Emberger (in C. & E., 1960), Takhtajan (1969) and Hutchinson (1969). Some recognize a family Leguminosae (Fabaceae) and include Caesalpineae as a sub-family-Schulze-Menz (in Syll. 12, 1964), for example. The family is then placed in Rosales. See Lomentaceae, Leguminosae (Fabaceae); Rosales for discussion. Calendulaceae: H. F. Link, Handb. I: 776. 1829. Link had C. with Calendula, Silphium and Arctotis, which we would put in 3 tribes of the Compositae. Reichenbach (1828), who has been credited with it, did not have a family C. See Compositae Callicomaceae: J. G. Agardh, Theoria, 1858, p. 146 (`Callicomeae'). A. had his family next to Cunoniaceae and we include Callicoma in that family. It has been put in Codiaceae and in Saxifragaceae. See Cunoniaceae, Codiaceae, Saxzfragaceae Callitrichaceae n.c.: H. F. Link, Enum. pl. Beroli., 1821-2, 1: 7. 1821 (`Callitrichinae'). This little family is obviously hard to place. Some botanists have it in the neighbourhood of Euphorbiaceae. Thus we have: Tricoccae (Euphorbiales, or equiv.)-Lindley (1853), Baillon (1878), Camel (1881), Drude (1886-7), Wettstein (1935),

FAMILIES OF DICETYLEDONS 919

Rendle (1938), Soo (1953) and Crete (1959)• Geraniales-Bessey (1915), and Gates (1940). Another school sees a relationship to the Tubiflorae (s.l.) and we have : Tubiflorae (Lamiales, Boraginales, etc.)-Gundersen (195o), Copeland (1957), Melchior (in Syll. 12, 1964), Thorne (1968), Cronquist (1968) and Takhtajan (1969). Yet others see a relationship to the Myrtales (s.l.), and we have: Myrtales (Lythrales, Myrtiflorae, Onagrales)-Boivin (1956), and Hutchinson (1969). Burnett (1835) included Callitriche in Hippuridaceae. Finally, several authors, including Pulle (1952), have an order Callitrichales! See Tubiflorae Calophyllaceae: K(C). F. P. von Martius, Consp. reg. veg. 1835, p. 41 (`Calophylleae'-name only). Agardh (1858) has been credited with the family. See Guttiferae Calthaceae : Barnhart (1895) lists `Calthaceae Presl. 1826', but Presl (Fl. sic. 2o, 1826) had Calthaceae as tribus IV of Ranunculaceae (q.v.), not as a family. Calycanthaceae n.c.: J. Lindley, Bot. Reg. 5: sub t. 404, 1819 (`Calycantheae'). L. included Calycanthus and Chimonanthus, as have all (?) who have recognized the family. There seem to be two schools of thought. Many see relationship with Polycarpicae (Ranales, Magnoliales and segregates) and more particularly with Monimiaceae; others opt for Rosales (or equiv.). Thus we have: Polycarpicae, etc.-Bromhead (1838), Caruel (1881), Hallier (1912), Bessey (1915), v.T. & C. (1918), Wettstein (1935), Rendle (1938), Skottsberg (1940), Gates (194o), Pulle (1952), Gundersen (195o), Sob (1953), Benson (1957), Crete (1959), Emberger (in C. & E., 196o), Buchheim (in Syll. 12, 1964), Thorne (1968) and Takhtajan (1969). Rosales (or equiv.)-Dumortier (1829), Endlicher (1836-40), Lindley (1853), Agardh (1858 ?-next to Pomaceae), Boivin (1956), and Hutchinson (1969). Burnett (1835) included C. in Punicaceae! See Magnoliales for discussion Calyceraceae n.c.: R. Brown, Trans. Linn. Soc. Lond. 12: 132. 1818 (read 18,6) (`Calycereae'). B. wrote: `I shall venture to propose this group as a distinct natural

920 CHEMOTAXONOMY OF FLOWERING PLANTS

family to be placed between Compositae and Dipsaceae. This family... may be called Calycereae...'. On pp. 135-6, however, he would give Boopideae Cassini priority. The name C. L. C. Richard (1820) is conserved. Many believe Calyceraceae to be related to the Compositae. Thus we have: Campanulales (or equiv.)-Wernham (1911-12), Hallier (1912), Bessey (1915), Benson (1957) and Wagenitz (in Syll. 12, 1964). Asterales (or equiv.)-Burnett (1835), Lindley (1836), Grisebach (1854), Caruel (1881), Drude (1887), Gundersen (1950), Pulle (1952), Boivin (1956) and Crete (1959)• Calycerales-Takhtajan (1969, next to Asterales). Others see a relationship to Rubiaceae, Valerianaceae, etc. Thus we have: Rubiales-v.T. & C. (1918), Wettstein (1935), and Skottsberg (1940). Dipsacales-Bromhead (1838), Thorne (1968) and Cronquist (1968 (?) ). Valerianales-Hutchinson (1969). See Boopidaceae, Campanulales Calycrateaceae: B. C. Dumortier, Comm. bot. 1822(3), p. 58 (`Caly-

crateae'). See Tropaeolaceae Camarandraceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 332. D. had C. as a synonym of Rhamneae R.Br. Cambogiaceae: P. Horaninow, Prim. lin., etc. 1834, p. 98. H. had `Cambogiaceae (Guttiferae)'. Hutchinson (1969) has Camfogiaceae, clearly a misprint. See Guttiferae Camelliaceae: B. C. Dumortier, Comm. bot. 1822(3), p. 62 (`Camel-

lideae'). See Theaceae Campanulaceae n.c.: M. Adanson, Fam. Pl. 2: I I, 132. 1763 (`Cam-

panulae'). A.'s family had several genera of our modern Campanulaceae, but Jussieu's 1789 name is conserved. Most taxonomists have an order Campanulales (or equiv.) and many include the Compositae in the order. Others see a less close relationship. Thus we have: Campanulales (Asterales, or equiv.)-Dumortier (1829), Burnett (1835), Lindley (1836), Endlicher (1836-40), Bromhead (1838), Horaninow (1843), Grisebach (1854), Caruel (1881), Wernham (1911-12), Hallier (1912), Bessey (1915), Rendle (1938), Skottsberg

FAMILIES OF DICOTYLEDONS 92I

Gundersen (1950), Pulle (1952), Soo (1953), Boivin (1956), Benson (1957), Wagenitz (in Syll. 12, 1964), Thorne (1968), Cronquist (1968), Hutchinson (1969) and Takhtajan (1969). V.T. & C., 1918 saw a relationship with Rubiales. There is no close agreement as to the limits of the family and most groups within the Campanulaceae (s.l.) have been made separate families. See (add -aceae) : Cyananth., Cyphi., Cyphocarp., gasion., Limb., Lobeli., Nemaclad., Pentaphragmat., Pongati., Sphenocle.; Campanulales for discussion. (1940),

Candolleaceae-S. Schönland, in EP,, 4(5): 79. 1889 (1894)• S. had Candolleaceae with Stylidiaceae as a synonym. See Stylidiaceae Canellaceae n.c.-K. F. P. von Martius, Nov. gen. spec. III: 168, 17o. 1832. Many authors put C. (Winteranaceae) in Polycarpicae, or equiv., or segregates. Thus we have: Polycarpicae (or equiv.)-Wettstein (1935), Pulle (1952), Copeland (1957), and Emberger (in C. & E., 196o). Magnoliales-Baillon (1871, in Magnoliaceae), Gundersen (1950), Soo (1953), Buchheim (in Syll. 12, 1964), Cronquist (1968), Hutchinson (1969) and Takhtajan (1969). Annonales-Hallier (1912), and Thorne (1968). Other taxonomists put C. in the Parietales (or equiv. or segregates such as Guttiferales, Violales)-Endlicher (1836-40), Skottsberg (1940), Lawrence (1851), Boivin (1956), Benson (1957) and Crete (1959)Only Caruel (1881, Tiliiflorae ?) ; v.T. & C. (1918, Polygonales) ; Lindley (1853, near Pittosporaceae); and Horaninow (1843; Canella, at least, in Meliaceae), seem to have different views. See Magnoliales for discussion Cannabaceae n.c.: S. L. Endlicher, Gen. pl. 1836-40, p. 286, 1837 (`Cannabineae'). E. had `Cannabineae' with Cannabis and Humulus. `Cannabaceae Endl.' is conserved. Bullock (1958, 2) has argued that the spelling Cannabiaceae is correct. One also finds Cannabinaceae! Those who recognize the family are fairly well agreed, so we have: Urticales (or equiv.)-Lindley (1853), Ascherson (1864), Caruel (1881), Drude (18867), Wettstein (1935), Rendle (1938), Skottsberg (1940), Pulle (1952), Soo (1953), Boivin (1956), Benson (1957), Crete (1959), Cronquist (1968), Hutchinson (1969) and Takhtajan (1969).

922 CHEMOTAXONOMY OF FLOWERING PLANTS

Some—including Melchior (in Syll. 12, 1964)—put Cannabis and Humulus in Moraceae. See Moraceae, Urticales Canop(i)(od)aceae: K(C). B. Presl, Epimel. Bot. 1852, p. 248 (`Canopiaceae'). Bullock (1958, i) has Canopaceae Pfeiffer; Hutchinson (1969) has Canopodaceae Presl. See Santalaceae Canotiaceae: Hutchinson (1969) includes `Canotiaceae Britton 1908' in Celastraceae. I have not seen Britton. Airy Shaw (1965) has `Canotiaceae Airy Shaw fam. nov.'. Had he not seen Britton ? Cansjer(ac)eae: J. G. Agardh, Theoria, 1858, p. 238 (`Cansiereae'). The type is Cansjera Juss. See Opiliaceae Cantuaceae: J. G. Agardh, Theoria, 1858, p. 392 (table) ? Although A. has Cantuaceae in the table on p. 392, he discusses Cantuae under Polemoniaceae on p. 391. See Polemoniaceae Capitat(ace)ae: A. J. G. K. Batsch, Tab. affin., etc. 18oz, p. 251 (`Capitatae'). B. had C., with Carduus, Cynara, etc., as the only fam. of Cynarocephalae (part of our Compositae (q.v.)). Cappar(id)aceae n.c.: Bernard de Jussieu (1759) in A. L. de Jussieu, Gen. pl. 1789 (`Capparides'). J.'s family is a mixed bunch. Necker (1770) had `Canoaceae'. Capparaceae A. L. de Jussieu (1789) is conserved. Nearly all botanists recognize a family Cappar(id)aceae and nearly all put it with Resedaceae, Cruciferae, Moringaceae, etc. in orders variously named. Thus we have: Rhoeadales (Papaverales, Cruciales, Cappar(id)ales, Brassicales, etc.)—Dumortier (1829), Burnett (1835), Lindley (1836), Endlicher (1836-40), Caruel (1881), Drude (1887), Hallier (1912), Bessey (1915), Wettstein (1935), Rendle (1938), Skottsberg (1940), Gates (1940), Barkley (1948), Pulle (1952), Sod (1953), Boivin (1956), Benson (1957), Copeland (1957), Melchior (in Syll. 12, 1964), Cronquist (1968), Thorne (1968) and Takhtajan (1969).

FAMILIES OF DICOTYLEDONS 923

A few separate the family (or in Hutchinson's case part of it) from this position. Thus we have: Parietales—Crete (1959, but with above families). Cistales—v.T. & C. (1918, without above families). Capparidales—Hutchinson (1969, Capparidaceae without Cleome, etc., but with Moringaceae). We shall see that the chemistry of Capparaceae (s.l.) is in line with relationship to Cruciferae, Resedaceae, Tovariaceae, etc. See Cleomaceae, Koeberliniaceae, Oxystylidiaceae, Papaverales Caprariaceae: Barnhart (1895) lists `Caprariaceae Reichb., 1828', but H. G. L. Reichenbach, Consp. reg. veg. 1828, p. 124, has C. as part of a family Personatae, not as a family. See Scrophulariaceae Caprifoliaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 210 ('Caprifolia'). J.'s family is conserved. Many authors place the family in Rubiales (or equiv.) but the modern view is rather to place it in Dipsacales, away from Rubiaceae. Thus we have: Rubiales (or equiv.)—Grisebach (1854), Hallier (1912), Wernham (1911-12), Bessey (1915), v.T. & C. (1918), Wettstein (1935), Rendle (1938), Skottsberg (1940), Gates (1940), Gundersen (1950), Pulle (1952), Soo (1953), Boivin (1956), Benson (1957), Copeland (1957) and Crete (1959)• Dipsacales—Wagenitz (in Syll. 12, 1964), Thorne (1968), Cronquist (1968) and Takhtajan (1969). Hutchinson (1969) has C. in Araliales with Cornaceae, Alangiaceae, Nyssaceae, Garryaceae and Araliaceae! Some taxonomists remove Sambucus, Viburnum, Alseuosmia etc. See Alseuosmiaceae, Loniceraceae, Sambucaceae, Viburnaceae; Dipsacales for discussion. Capusiaceae : F. Gagnepain, Bull. Soc. Bot. France, 87 : 272. 1941. Hutchinson (1959) says that Capusia (Siphonodon) is `clearly related and very close to Hippocrateaceae'. In 1969 he has a family C. in Celastrales. Scholz (in Syll. 12, 1964) includes Siphonodon in

Celastraceae. See Siphonodontaceae, Celastraceae Carcerulaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 231. C. as a synonym of Tiliaceae (q.v.). Cardamind(ace)ae: H. F. Link, Handb. II : 326. 1831 (`Cardamindae'). Cardamindum Tourn. ex Adans. = Tropaeolum L. See Tropaeolaceae

924 CHEMOTAXONOMY OF FLOWERING PLANTS

Cardiopteridaceae n.c.: C. L. Blume, Rumphia, 3: 205. 1847 (?), 4: t. 177. 1848 (?) (`Cardiopterideae'). Blume included Cardiopteris Wall. only. His name is conserved. Scholz (in Syll. 12, 1964) has Cardiopteridaceae in Celastrales, as have Cronquist (1968), and Hutchinson (1969). Thorne (1968), and Takhtajan (1969) have the family in Santalales. See Icacinaceae, Peripterygiaceae; Celastrales for discussion Cardiopterygaceae: Blume corrected by van Tieghem (see below). Airy Shaw (in W. 1966) has C. Bl. corr. van Tieghem and says `Only genus: Peripterygium ... probably related to the Convolvulaceae.' I believe that Peripterygium = Cardiopteris and Cardiopterygaceae = Cardiopteridaceae = Peripterygiaceae! Carduaceae: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 465. 1770. Carduaceae with Carduus, Centaurea and Serratula—all in our Compositae-Cardueae. It was maintained by Small (1903). See Compositae Caricaceae n.c.: B. C. Dumortier, Anal. 1829, pp. 37, 42. D. had `Caricaceae (=Cariceae Bl. non Dmrt.)' with Carica (only?) next to Passifloraceae. His name is conserved. There seems to be more than one view as to relationship. Many, from Dumortier on, place C. near Passifloraceae in Parietales (or equiv., or segregate orders). Thus: Parietales (Guttiferales, Violales, Passiflorales, Cistales, etc.)—Bromhead (1838), Hallier (1912), Wettstein (1935), Rendle (1938), Skottsberg (1940), Pulle (1952), Soo (1953) Copeland (1957), Crete (1959), Melchior (in Syll. 12, 1964), Thorne (1968), Cronquist (1968) and Takhtajan (1969). Gundersen (19So) included C. in Passifloraceae. Caricales—Benson (1957, near Violales). Some relate C. to Cucurbitaceae. Thus we have: CucurbitalesSingh (1953) Boivin (1956) and Hutchinson (1969). Finally van Tieghem (1903), and v.T. & C. (1918) have C. in Plumbaginales. See Papayaceae; Violales for discussion Carlemanniaceae: Airy Shaw, 1965 ? I have not seen this. Hutchinson (1969) and Takhtajan (1969, doubtfully) include C. in Caprifoliaceae (q.v.). Carpinaceae: L. A. Kuprianova, Taxon, 12: 12. 1963. K. distinguishes C.—with Carpinus, Ostrya and Ostryopsis—as a new family of 'Amentiferae'. The pollen is supposed to be distinctive.

FAMILIES OF DICOTYLEDONS 925

The paper is called ' On a hitherto undescribed family belonging to the Amentiferae'-surely the sloppiest title ever published in a journal of taxonomy! See Betulaceae Carpodet(ac)eae: E. Fenzl, Regensb. Denkschr. 3: 155, t. 1-2. 1841 (`Carpodeteae'). (I have not been able to check this.) See Escalloniaceae, Saxifragaceae Caryocaraceae n.c.: Ign. v. Szyszylowicz, in EP1, 3 (6): 153. 1893 (1895). S.'s family had Caryocar and Anthodiscus. It is conserved. Almost all put C. in Guttiferales (or equiv.). Thus we have: Guttiferales (Clusiales, Theales, etc.)-Bessey (1915), Wettstein (1935), Skottsberg (1940), Gundersen (195o), Pulle (1952), Boivin (1956), Benson (1957), Copeland (1957), Melchior (in Syll. 12, 1964), Thorne (1968), Cronquist (1968), Hutchinson (1969) and Takhtajan (1969). Hallier (1912) sees relationship to Myrtales; while van Tieghem and Constantin (1918) put C. in Primulales. Burnett (1835) included Caryocar in his Aesculaceae. See Rhizobolaceae, Guttiferales Caryophyllaceae n.c.: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 484. 1770 (`Caryophylleae'). N. had Boottia (= Saponaria, Caryophyllaceae) and Linum (Linaceae) in his family. C. Jussieu (1789) is conserved. Virtually all put Caryophyllaceae in Centrospermae (or equiv.). Thus we have: Centrospermae (Caryophyllales, Chenopodiales, etc.)-Martius (1835), Endlicher (1836-40), Grisebach (1854), Hallier (1912), Bessey (1915), Wettstein (1935), Rendle (1938), Skottsberg (194o), Gates (1940), Gundersen (1950), Pulle (1952), Soo (1953) Boivin (1956), Benson (1957), Crete (1959), Eckardt (in Syll. 12, 1964), Airy Shaw (in W. 1966), Thorne (1968), Cronquist (1968), Hutchinson (1969) and Takhtajan (1969). Van Tieghem & Constantin (1918) put C. in Geraniales. The family is often split. See (add -aceae) : Alsin., Circum., Corrigiol., Dianth., Illecebr., Paronychi., Queri., Scleranth., Silen., Stellari., Telephi.; Centrospermae for discussion. Cassiaceae: H. G. L. Reichenbach, Consp. reg. veg. 1828, pp. 139, 153. R.'s family Cassiaceae (p. 139) or Cassieae (p. 153) included `Genisteae, Sophoreae, and Cassieae genuinae' .

926 CHEMOTAXONOMY OF FLOWERING PLANTS

The family has been maintained by Burnett (1835, in Cicerinae); Bessey (1915), Gates (1940, in Rosales), and Nakai (1943, in Fabales). See Caesalpiniaceae, Leguminosae Cassiniaceae: C. H. Schultz, Flora, 35 (1): 129. 1852. S. named his family for A. H. G. von Cassini, the famous student of the Compositae. See Compositae Cassipoure(ace)ae: J. G. Agardh, Theoria, 1858, p. 246 (`Cassipoureae'). Airy Shaw (in W. 1966) says that C. = Rhizophoraceae–Macairisieae Baill. See Rhizophoraceae Cassuvi(ace)ae: R. Brown in Tuckey, Narr. Exped. Congo, 1818, p. 431 (`Cassuviae'). Brown says the order (fam.) was proposed by de Jussieu. Brown includes several genera of our Anacardiaceae, and Airy Shaw (in W. 1966) says that B.'s family = Anacardiaceae (q.v.). Cassyt(h)(e)aceae n.c.: Bartling ex J. Lindley, Nix. pl. 1833, p. 15 ('Cassyteae'). L. (1833), whose name is conserved, had C. Bartling in Laur(e)ales, as had Bromhead (1838). Later (1853) Lindley put C. in Daphnales. Barnhart (1895) lists Cassythaceae Dum., 1829 and Cassytaceae Horan., 1843. We include C. in Lauraceae (q.v.). Castaneaceae (I): H. F. Link, Enum. pl. Beroli. 1821-2. 1: 354. 1821. L. had Castaneaceae with Aesculus. See Hippocastanaceae Castaneaceae (2): N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 491. (`Castaneae'). N. had Castaneae with Quercus, Fagus, etc.; van Tieghem and Constantin (1918) had Castaneaceae (5/35o) with Castanea, Quercus, Fagus, etc. in Castaneales. See Fagaceae 1770

Castel(ac)eae: J. G. Agardh, Theoria, 1858, p. 181 (`Casteleae'). See Simaroubaceae Casuar(in)aceae n.c.: Mirbel, Ann. Mus. d' Hist. Nat. Paris, 16: 451. 1810 (`Casuarinees') and R. Brown in Flinders, Voy. Terra Austr. II: 571. 1814 (`Casuarineae')—conserved.

FAMILIES OF DICOTYLEDONS 927

This isolated group, with Casuarina (4o-5o) only or C. and Gymnostoma (Airy Shaw, in W. 1966) has been and is a great puzzle. Some—such as Treub (1891) and Lam (1948)—have seen it as a transitional group between gymnosperms and angiosperms. Others such as Engler have regarded it as the most primitive family of the dicotyledons. Most have made it an order of its own, calling it Casuar(in)ales or Verticillatae. Bessey (1915) and Moseley (1948-9) saw relationship to Hamamelidaceae; v.T. & C. (1918) put it in Piperales; Caruel (1881) in Euphorbiflorae; Grisebach (1854) in Terebinthinae! Several have grouped it with catkin-bearing families in Amentales, Quercinae, etc. See Casuarinales for discussion Cathedraceae: Ph. van Tieghem, Bull. Soc. Bot. France, 43: 565. 1896 (`Cathedraceas'). Van Tieghem says `Ensemble, ces deux genres [Anacolosa, Cathedra] doivent constituer une familie autonome, les Cathedracees.' See Olacaceae Cedrel(ac)eae: R. Brown in Flinders, Voy. Terra Austr. II: 595. 1814 (`Cedreleae'). Br. separates C. from Meliaceae, as does Adr. de Jussieu (183o). See Meliaceae Celastraceae n.c.: R. Brown in Flinders, Voy. Terra Austr. II: 554. 1814 (`Celastrinae'). B.'s name is conserved. Most authors have C. as the type family of an order. Thus we have: Celastrales (or equiv.)—Burnett (1835), Grisebach (1854), Caruel (1881), Bessey (1915), v.T. & C. (1918), Wettstein (1935), Rendle (1938), Skottsberg (194o), Gates (194o), Gundersen (195o), Pulle (1952), Soo (1953), Boivin (1956), Crete (1959), Scholz (in Syll. 12, 1964), Cronquist (1968), Hutchinson (1969) and Takhtajan (1969). A few authors seem to have other views: Gutt(ifer)ales—Hallier (1912). Sapindales—Benson (1957). Euphorbiales—Lindley (1836) and Bromhead (1838). Santalales—Thorne (1968). Several taxonomists, for example Airy Shaw (in W. 1966), would combine Celastraceae and Hippocrateaceae. The Code says that if this is done the name Celastraceae must be used. See (add -aceae): Canoti., Capusi., Chingithamn., Dipentodont., Goupi., Leptolob., Lophopyxid., Siphonodont.; Celastrales for discussion.

928 CHEMOTAXONOMY OF FLOWERING PLANTS

Celtidaceae: H. F. Link, Handb. II : 441. 1831 (`Celtideae'). The few who have recognized a family C. have put it near Ulmaceae. Airy Shaw (in W. 1966) says that C. Link = Ulmaceae-Celtideae Gaud. See Ulmaceae Centaureaceae: Barnhart (1895) lists `C. Pfeiffer, 1873', but Pfeiffer lists `C. Bartling, 1830', and Fr. Th. Bartling, Ord. nat. pl. 183o, P. 144 has Centaureaceae (sic) as part of a family Synanthereae, not as a family. Cephalanth(aceae): C. S. Rafinesque, Ann. Gen. Sci. Phys. 6: 86. 1820. (`Cephalantia', Cephalanthees'). Raf. had C. as family 3 of his Sphanidia, with sub-families Nauclidia (Cephalanthus, Nauclea, Morinda) and Cephelidia (Cephaelis, etc.). Dumortier (1822(3)) had Cephalanthidiae in his Fructitubia. See Rubiaceae Cephalotaceae n.c.: B. C. Dumortier, Anal. 1829, pp. 59, 61 (`Cephaloteae'). D.'s family—he included Cephalotus only—is conserved. D. put the C. with monocotyledons, as have some others. Most authors, from Martius (1834) to Hutchinson (1969), have seen relationship to Saxifragaceae and Crassulaceae (Rosales)—and Burnett (1835) put Cephalotus in the Crassulaceae—but the family has also been put in Nepenthales, Sarraceniales and Cephalotales. See Rosales for further discussion Cerantheraceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 416. C. as a synonym for Ericineae Desv. Ceratoni(ac)eae: H. F. Link, Handb. 1829-33, II: 135. 1831 (`Ceratonieae'). C. with Ceratonia and Copaifera as an order (family) of Leguminosae (treated as a subclass). See Leguminosae Ceratophyllaceae n.c.: S. F. Gray, Nat. Arr. Brit. Pl. II : 395, 554. 1821 (`Ceratophyllae'). This little family—with Ceratophyllum only—is conserved. Most taxonomists put it in the Polycarpicae (or equiv.); others are more specific and say Ranunculales (or equiv.); yet others have different views. Thus we find: Polycarpicae (Ranales, or equiv.)—Hallier (1912), Bessey (1915), Wattstein (1935), Skottsberg (1940), Gates (1940), Gundersen (1950), Pulle (1952), Soo (1953), Boivin (1956), Benson

FAMILIES OF DICOTYLEDONS 929

(1957), Emberger (in C. & E., 1960) and Airy Shaw (in W. 1966 (?) ). Ranunculales (Nymphaeales, or equiv.)—Buchheim (in Syll. 12, 1964), Thorne (1968), Cronquist (1968), Hutchinson (1969) and Takhtajan (1969). Urticales (or equiv.)—Lindley (1853), and Crete (1959). Myricales—v.T. & C. (1918). Euphorbiales (or equiv.)Caruel (1881). Piperales (or equiv.)—Baillon (1874), and Drude (1887). Hippurinae—Burnett (1835). Horaninow (1843) put it among the monocotyledons! See Cercaceae; Ranunculales for discussion Cercaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 152. C. as a synonym of Ceratophyllaceae (q.v.). Cercidiphyllaceae n.c.: Ph. van Tieghem, your. de Bot. 14: 274. 1900 (` Cercidiphyllees '). C. Engler (1909) is conserved. This little family—with Cercidiphyllum only—is a puzzling one. It is associated by many with Ranales (or equiv.); by some with Magnoliales (or equiv.); by a few with Hamamelidales (or even in Hamamelidaceae); is made an order of its own (Takhtajan, 1969); and has been put in Piperales (v.T. & C., 1918). See Magnoliales Cercocarp(ac)eae: J. G. Agardh, Theoria, 1858, p. 287 (`Cercocarpeae'). See Rosaceae-Cercocarpinae Cercodi(ace)ae: A. de Jussieu, Dict. des Sci. Nat. 7: 441. 1817 (`Cercodianae'). J. included genera we now put in Haloragaceae (q.v.). Cestraceae: J. Lindley, Nixus pl. 1833, p. 19. Bullock (1958) credits Martius (1835) with the family, but Lindley had Cestrineae Schlecht. as family 2 of Solanales in 1833. Hutchinson (1969) includes `Cestraceae Schlechtendal (1833)' in Solanaceae (q.v.). Cevalliaceae: A. Grisebach, Grundr. syst. Bot. 1854, p. 134. G. had Cevalliaceae as a family of Compositae (treated as an order). Hutchinson (1969) has Cavalliaceae (a misprint?). We put Cevallia Lagasca in Loasaceae (q.v.). Chailletiaceae: R. Brown in Tuckey, Narr. Exped. Congo, 1818, p. 442 (` Chailleteae'). See Dichapetalaceae

930 CHEMOTAXONOMY OF FLOWERING PLANTS

Chamaelauciaceae: F. K(C). L. Rudolphi, Syst. orb. veg. 183o, p. II (`Chamaelaucieae Dec.'). R. had Ch. as a family, but gives no genera. Lindley (1846) had Ch. with genera which we should put in Myrtaceae (q.v.). Charianthaceae: A. Kerner von Marilaun, Pflanzenl. II: 697. 1891. C. as family 2 of Melastomeae. See Melastomataceae Chaunochit(on)aceae: Ph. van Tieghem, Bull. Soc. Bot. France, 43: 565. 1896 (`Chaunochitacees'). V.T. proposed C. with Chaunochiton. Airy Shaw (in W. 1966) has Chaunochit(on)aceae v.T. = Olacaceae.Heisterieae Engl. See Olacaceae Cheiranthodendraceae: Hutchinson (1969) includes `Cheiranthodendraceae A. Gray (1887)' in Sterculiaceae (q.v.). I have not seen Gray. Chelidoniaceae: ?T. Nakai, Bull. Nat. Sci. Mus. Tokyo, no. 31, 1952, p. 51. I have not seen this. See Papaveraceae Chelon(ac)eae: D. Don, Edinb. New Phil. y. 19: 109, 113. 1835 (`Cheloneae'). One of six families in Don's Personatae. See Scrophulariaceae Chenopodiaceae n.c.: E. P. Ventenat, Tabl. reg. veg. 1799, 2: 253 (`Chenopodees; Chenopodae'). V.'s family (conserved) included genera we now place in Chenopodiaceae, Phytolaccaceae, Basellaceae and Salvadoraceae, at least. All—from Dumortier (1829) to Hutchinson (1969)—have put C. in Centrospermae (Curvembryae, Caryophyllales, Chenopodiales). We shall see that the chemistry is in line with such placing. See (add -aceae): Atriplic., Bet., Blit., Corisperm., Dysphani., Farin., Halophyt., Salicorni., Salsol.; Centrospermae for discussion. Chicoraceae: N. J. de Necker, Acta Acad. Theodoro-Palat.

2: 463.

1770.

N. had C. with 6 genera of the Compositae. Dumortier (1822(3)) had the same spelling. See Cichoriaceae, Compositae

FAMILIES OF DICOTYLEDONS 931

Chingithamnaceae: H. Handel-Mazzetti, Sinensia 2: 126. 1932. H.-M. said that Chingithamnus can be placed in no known family, and that it is nearest to Celastrales. Gundersen (195o) suggested

Olacaceae. See Celastraceae Chironiaceae: P. Horaninow, Tetractys, 1843, p. 27. H.'s family included Villarsieae, Gentianae, Loganieae, and Strychneae. See Gentianaceae, Menyanthaceae Chisanth(ac)eae: B. C. Dumortier, Comm. bot. 1822(3), p. 57 (`Chis-

antheae'). D. included Lobelia (Campanulaceae) and Goodenia (Goodeniaceae). See Campanulaceae, Goodeniaceae Chl(a)enaceae: Bullock (1958) credits Thouars (Hist. Veg. Iles Austr.Afr. 1807, p. 46) with this family. I have not seen this. Most authors—from Burnett (1835) to Emberger (1960)—have associated the family with the equivalent of our Malvales; but some— from Lindley (1833) to Boivin (1956)—have put it in the Guttiferales or its equivalent. See Sarcolaenaceae Chloanthaceae: J. Hutchinson, Fam. Fl. Pl., 2nd ed. 1: 396, fig. 245. 1959. H.'s family is carved out of the Verbenaceae. He lists To genera, all Australian. In 1969 he has it as family 4 of Verbenales. Takhtajan (1969) includes it in Verbenaceae, as does Melchior (in Syll. 12, 1964). Airy Shaw (in W. 1966) says that H.'s family _ Dicrastylidiaceae J. Drumm. ex Harv. See Dicrastylidiaceae, Verbenaceae Chloranthaceae n.c.: R. Brown ex Lindley, Collect. Bot., sub. t. 17. 1821, is conserved. I have also R. Brown ex Sims, Bot. Mag. 48, t. 219o. 1821 (o ?) (`Chlorantheae'). Sims writes: `Brown makes it [Chloranthus] the type of a new order [family], to be called Chlorantheae...To this family belong also Ascarina of Forster, and Hedyosmum of Swartz...'. Most taxonomists have C. near to (or even in) Piperaceae. Thus we have: Piperales (or equiv.)—Burnett (1835), Lindley (1836), Grisebach (1854), Drude (1887), Wettstein (1935, doubtfully), Rendle (1938), Gundersen (195o), Pulle (1952), Soo (1953), Boivin (1956), Benson

932 CHEMOTAXONOMY OF FLOWERING PLANTS

(1957), Melchior (in Syll. 12, 1964), Cronquist (1968, or in Magnoliales), and Hutchinson (1969). In Piperaceae—Baillon (1874). Other placings include: Ranales (or equiv.)—Bessey (1915, but near Piperaceae), and Copeland (1957). Annonales—Hallier (1912), and Thorne (1968). Laurales—Takhtajan (1969). Castaneales—v.T. & C. (1918). Allied to Gnetaceae!—Croizat (1952). See Piperales Chordari(ace)ae: A. J. G. K. Batsch, Tab. affin., etc. 1802, p. 242 (`Chordariae'). B. had C.—with Cuscuta, Cassytha and Basella—in his Polymorphae. Chrysobalanaceae n.c.: R. Brown in Tuckey, Narr. Exped. Congo 1818, p. 433 (`Chrysobalaneae'). All are agreed that this group forms a family within the Rosales (or equiv.), or a section of the Rosaceae itself. See Hirtellaceae, Rosaceae; Rosales for discussion. Chylaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 205. C. as a synonym of Fumariaceae (q.v.). Chymaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 207. D., who included Hypecoum here, had C. as a synonym of Papaveraceae (q.v.). Cichor(i)aceae n.c.: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 463. 1770 (`Cichoraceae'). N.'s family Cichoraceae included 6 genera of our CompositaeCichorioideae. Although B. de Jussieu (1759, in A. L. de J., 1789) and A. L. de J. also had the same spelling, the conserved name is given as Cichoriaceae Juss., 1789. Several authors have maintained the family. See Compositae Ciliat(ace)ae: A. J. G. K. Batsch, Tab. affin. 1802, p. 31 (`Ciliatae'). C.—with Dionaea, Drosera, Roridula and Aldrovanda—in Difformariae. See Droseraceae Ciliovallaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 459. As a synonym of Lobeliaceae (q.v.).

FAMILIES OF DICOTYLEDONS

933

Cinarocephalaceae: B. de Jussieu (1759) in A. L. de Jussieu, Gen. Pl. 1789 (`Cinarocephalae'). B. de Jussieu included Echinops, Cinara (Cynara), Carlina, etc. Martius (1835) had `Cynarocephaleae Juss.' as one of the two `families' in his ordo Compositae L. Hutchinson (1969) includes Cinarocephalaceae Juss. in his Asteraceae (Compositae). See Compositae Cinchon(ac)eae: A. J. G. K. Batsch, Tab. affin., etc. 18o2, p. (`Cinchoneae'). Family 4 of Rigidae (q.v.). See also Rubiaceae.

234

Circaeaceae: J. Lindley, Synops. Brit. Flora, 1829, p. 109. L. had Circaeaceae with Circaea only, related to Onagrarieae. Martius (1835), Burnett (1835), and Kerner (1891) maintained the family. See Onagraceae Circaeasteraceae n.c.: C. J. Maximowicz, Bull. Acad. Imp. Sd. St. Petersb. 27: 558. 1881 (without name). M. on p. 558 had (translated from the Latin) : ` So it is proper [ ?] to establish a separate family [for Circaeaster—named on p. S56] to be placed close to the Chloranthaceae unless you would prefer to have an anomalous genus of this family, disregarding the structure of the [ ?] embryo.' Hutchinson `made' the family Circaeasteraceae in 1926 (conserved) and placed it in Berberidales. Several have followed Hutchinson, but others (Buchheim, in Syll. 12, 1964, for example) put C. in the Ranunculaceae (q.v.). Circumaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 244. D. had C. as a synonym of Alsineae, a family distinct from Onychiaceae (Sileneae). See Caryophyllaceae Cissaceae: P. Horaninow, Char. ess. fam., etc., 1847, p. 184 (`Cissaceae (Ampelideae)'). See Vitaceae Cistaceae n.c.: A. L. de Jussieu, Gen. pl. 1789, p. 294 (`Cisti'). J. had Cistus and Helianthemum in his family, which is conserved. Virtually all taxonomists since Jussieu have recognized a family Cistaceae and have placed it in an order—variously named Parietales,. Cistales, Guttiferales, Violales, Bixales, etc.—but with much the

934

CHEivIOTAXONOMY OF FLOWERING PLANTS

same families. Many seem to see particularly close relationship to

Bixaceae. See Violales Citraceae: 0. Drude, Phanerogam. 1879, p. 391. (I have not checked this.) See Rutaceae Cleom(e)aceae: P. Horaninow, Prim. lin., etc. 1834, p.

92

(`Cleomeaceae

(Capparid.)'). Later (1847) H. had `Cleomaceae s. Capparideae' in his Violastra. H. K. Airy Shaw (Kew Bull. 18(2): 256. 1965) has Cleomaceae (Pax) Airy Shaw stat. nov.' with 12/275, `almost exactly intermediate' between the Capparidaceae (s.s.) and the Cruciferae—Stanleyeae. Hutchinson (1969) has Cleomaceae in his Cruciales and puts the Capparidaceae far away on his `woody' side! See Cappar(id)aceae and Papaverales for discussion Clethraceae n.c.: J. F. Klotzsch, Linnaea, 24: 12. 1851. Virtually all, from Klotzsch to Hutchinson (1969), either recognize the family and put it in Ericales (Bicornes) or put Clethra in the

Ericaceae. Cronquist (1968) says C. is more or less intermediate between Theales and Ericales; and Thorne (1968) has the family in his Theales. Wodehouse says the pollen of Clethra is very distinct from that of the

Ericaceae. See Ericales Cliffortiaceae : ?B. C. Dumortier, Anal. 1829, p. 18. (I do not find C. as a family in D.) Martius (1835) is usually credited with this family, but Barnhart (1895), who is not always accurate, lists C. Dum., 1829. See Rosaceae Clusiaceae n.c.: J. Lindley, Introd. Nat. Syst. Bot., and ed., 1836, p. 74. The name Clusiaceae, conserved as an alternative name for Guttiferae, has usually been used in that sense. See Guttiferae Cneoraceae n.c.: H. F. Link, Handb. 1829-33, II: Øo. 1831. L., whose name is conserved, had Cn. with Cneorum only. We now have Cneorum and Neochamaelea. The placing of this little family illustrates very well the difficulties

FAMILIES OF DICOTYLEDONS

935

encountered by taxonomists in the ` core of the dicotyledons' (to use again Good's phrase). Thus we find it in: Gruinales—Wettstein (1935, doubtfully). Terebinthales (or equiv.)—Hallier (1912), Skottsberg (1940) and Copeland (1957). Geraniales—Bessey (1915), and Sod (1953)• Rutales—Gundersen (1950), Pulle (1952), Benson (1957), Scholz (in Syll. 12, 1964), Thorne (1968) and Takhtajan (1969). Sapindales—Cronquist (1968). Rhamnales—v.T. & C. (1918). Celastrales—Boivin (1956) and Hutchinson (1969). CneoralesEmberger (in C. & E., 196o). See Rutales for discussion Cob(a)eaceae: D. Don, Edinb. Phil. Y. Io: 109. 1824 (`Cobeaceae'). D. said that Cobaea should not be in Bignoniaceae, but that it is very near to, but distinct from, Polemoniaceae. Agardh (1858) had Cobaeaceae next to Bignoniaceae. Airy Shaw (in W. 1966) has C. D. Don with Cobaea only `somewhat intermediate between Bignoni. and Polemoniac.' . Hutchinson (1969) puts C. in his Bignoniales, far from Polemoniaceae. Many include C. in Polemoniaceae (q.v.). Coccolobaceae : F. A. Barkley, Rev. Facult. Nat. Agron. [Colombia], 8: 163. 1948. Barkley—who does not claim this to be a new family—has C. as family 4 of his Polygonales with a dozen genera, all (?) of which we would put in Polygonaceae—Coccoloboideae. See Polygonaceae; Polygonales for discussion Cochlospermaceae n.c.: J. E. Planchon in Hooker, Lond. Your. Bot. 6: 305. 1847 (`Cochlospermees'). Planchon, whose name is conserved, included Amoreuxia M. & S. and Cochlospermum Kth. Two views seem to find favour. Most put C. in the Parietales (or equiv. or segregate orders) and near or even in the Bixaceae; a few see a relationship to the Malvales. We find: Parietales (Guttiferales, Violales, Cistales, Bixales, etc.)—Bessey (1915), Wettstein (1935), Skottsberg (1940), Pulle (1952), Boivin (1956), Benson (1957), Copeland (1957), Melchior (in Syll. 12, 1964), Takhtajan (1969) and Hutchinson (1969). In Bixaceae—Baehni (1934), Gundersen (195o) and Sod (1953). Malvales (Columniferae)—Grisebach (1854), v.T. & C. (1918), and Keating (1965 ?). See Violales for discussion Codiaceae: Hutchinson (1969) has Codiaceae van Tieghem (1900). I have not seen this. IO

GCO tI

936 CHEMOTAXONOMY OF FLOWERING PLANTS

V.T. and C. (1918) included Callicoma, Codia and Pancheria in the family and saw a relationship with Cunoniaceae. Airy Shaw (in W. 1966) and Hutchinson (1969) include C. in Cunoniaceae (q.v.). Coelostigmataceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 224. C. as a synonym of Berberideae. Coffeaceae: A. J. G. K. Batsch, Tab. affin. reg. veg. 1802, p. 233. Fam. 3 of Rigidae, with Coffea, Psychotria, Ixora, etc. Agardh (1858) is usually credited with the family. Airy Shaw (in W. 1966) equates Agardh's fam. with Rubiaceae-Ixoreae of B. & H.f. See Rubiaceae Coleogyn(ac)eae: J. G. Agardh, Theoria, 1858, p. 171 (` Coleogyneae'). Airy Shaw (in W. 1966) says that C. Agardh = Rosaceae-Cercocarpeae T. & G. See Rosaceae Colubr(in)(ace)ae: A. J. G. K. Batsch, Tab. affin., etc. 1802, p. 203 ('Colubrinae'). C., with Strychnos, Theophrasta, etc., in Nudae. Dumortier (1822(3)) had Colubrineae, with Strychnos and Theophrasta, in Thalamitubia. Columellaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 152. D., who included Buxus here, had C. as a synonym of Euphorbiaceae (q.v.). Columelliaceae n.c.: D. Don, Edinb. New Phil. y. 6: 46. 1828 (v. for Oct. 1828-Mar. 1829) (` Columellieae'). Don, whose name is conserved, regarded the Columellieae as an `osculant group' between Oleineae and Jasmineae. Most taxonomists put C. in Tubiflorae (or equivalent or segregate orders), but Lindley (18J3) and v.T. & C. (1918) had C. in Rubiales (Cinchonales). Cronquist (1968) puts the family in Rosales, and Hallier (1912) had included it in Saxifragaceae of that order. See Tubiflorae Columnifer(ace)ae : A. J. G. K. Batsch, Tab. affin. 18oz, p. 22 (` Columni-

ferae'). What did B. include in this family ? He had it, distinct from Malvaceae and Festivae (± Sterculiaceae), in his Columnariae.

FAMILIES OF DICOTYLEDONS

937

Comaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 181. C. as a synonym of Tamaricaceae (q.v.). Combretaceae n.c.: R. Brown, Prodr. 181o, p. 351. Almost without exception botanists have accepted Brown's family and put it in the Myrtales (or equiv.). Burnett (1835) excluded Terminaliaceae (q.v.), and included Alangium. Exell and Stace (1966) have revised the family. They say it is an `extremely natural one', the characteristic compartmented hairs being found in every genus. Its nearest relatives are the Myrtaceae. See Myrtales Compositae n.c.: M. Adanson, Fam. des Pl. II: 1o, 103. 1763. Although Adanson seems to have been the author of this great family, the conserved name is that of ` Giseke, Praelect. Ord. Nat. Pl. 1792, p. 538'. Asteraceae is an accepted alternative name. It would require volumes to go into all the taxonomic history here. Many botanists have regarded this as a single, completely natural family. Others have split it into two, or into as many families as there are tribes in Compositae (s.l.). Some have treated it as an order. Most of the moderns have it as a family but there is some disagreement as to relationships. Many put it in an order Campanulales (or equiv.) with Campanulaceae, Goodeniaceae, Calyceraceae, etc.; others consider this unnatural and have an order Asterales (or equiv.) with Compositae only, or sometimes with Calyceraceae. See (add -aceae): Acarn., Ambrosi., Anthemid., Arctotid., Aster., Calendul., Cardu., Cassini., Chicori., Cichori., Cinarocephal., Coreopsid., Corymbifer., Cynar., Cynarocephal., Echinopsid., Elichrys., Eupatori., Heleni., Helianth., Helichrys., Inu1., Lactuc., Mutisi., Nucament., Nuculari., Partheni., Perdici., Ritron., Semiflosculos., Senecionid., Spurionuc., Synanther., Syngenetic., Vernoni.; Campanulales for discussion. Confluaceae: J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 428. C. as a synonym of Globulariaceae (q.v.). Congregat(ace)ae: A. J. G. K. Batsch, Tab. affin., etc. 180.2, p. 236 (` Congregatae'). C., with Mitchellia (sic), Cephaelis, etc., in Rigidae. See Rubiaceae Connaraceae n.c.: R. Brown in Tuckey, Narr. Exped. Congo, 1818, p. 431• Brown, whose name is conserved, separated C. from ` Terebintaceae', I 0.2

938 CHEMOTAXONOMY OF FLOWERING PLANTS

including in his fam. Connarus, Cnestis and Rourea. He saw connections with Leguminosae and with Averrhoa (Oxalid.). Today we recognize a family of about 2s/300-400. Most authors put C. in Rosales (or equiv.) and stress relationship to the Leguminosae. Thus we have: Rosales (or equiv.)—Lindley (1836), Bessey (1915), Wettstein (1935), Rendle (1938), Skottsberg (194.0), Gundersen (195o), Pulle (1952), Soo (1953), Benson (1957), Emberger (in C. & E., 1960), Schulze-Menz (in Syll. 12, 1964), and Thorne (1968). Fabales (or equiv.)—Burnett (1835), Bromhead (1838) and Nakai (1943)• Connarales—Takhtajan (1969). Others stress rather a relationship with Oxalidaceae, etc. Thus we find: Geraniales—v.T. & C. (1918, but related to Legum.). Aesculinae —Hallier (1912, but related to Legum. and Oxalid.). Rutales (or equiv.)—Lindley (1853), and Caruel (1881). Terebinthales (or equiv.) —Dumortier (1829), Endlicher (1836-4o), Drude (1887) and Copeland (1957). Sapindales—Boivin (1956), and Cronquist (1968, but a link between Rosales and Sapindales). Finally: Dilleniales—Hutchinson (1969). See Rosales for discussion Conocephalaceae: A. Kerner von Marilaun, Pflanzenl. II: 680. 1891. Fam. 6 of Viridiflorae, very nearly equivalent to our Urticales. See Moraceae Contort(ace)ae(i): A. J. G. K. Batsch, Tab. affin., etc. 1802, p. zoi (` Contortae'). C., with Vinca, Asclepias, Periploca, etc., in Nudae. See Apocynaceae, Asclepiadaceae Contortaceae (z): J. Dulac, Fl. Dept. Hautes-Pyren. 1867, p. 438. C. as a synonym of Convolvulaceae (q.v.). Convolvulaceae n.c.: N. J. de Necker, Acta Acad. Theodoro-Palat. 2: 477. 1 77o (`Convolvuleae'). N. had C. with Convolvulus. Convolvulaceae Juss., 1789 (`Convolvuli') is conserved. Almost all have C. in Tubiflorae, or equivalent, or segregate orders, and many see a close relationship to Polemoniaceae. Horaninow (1847) put C. in Polemoniaceae. Some segregate Cuscuta, as Cuscutaceae, from the family, and Hutchinson (1959, 1969) has it in a different order! For other segregates see (add -aceae): Contort., Cuscut., Dichondr., Erycib., Humberti., Nolan., Poran.; Tubiflorae for discussion.

FAMILIES OF DICOTYLEDONS

939

Cordiaceae n.c.: R. Brown ex Dumortier, Anal. 1829, pp. 20, 25. Brown's name is conserved. Link (Handb.) also had Cordiaceae in the same year. Almost all see a close relationship to the Boraginaceae. Several authors—including Gundersen (195o), Melchior (in Syll. 12, 1964), and Takhtajan (1969)—include C. in the B.; others put it in Solanales, Boraginales (or equiv.). Hutchinson (1969) has C. in his Verbenales, far from the Boragin-

aceae. There is some argument as to the limits of the family, if retained. Some include Ehretia and its relatives: others make a separate family

Ehretiaceae. See Boraginaceae, Ehretiaceae, Heliotropaceae, Sebestenaceae; Tubiflorae for discussion Coreopsid(ac)eae: H. F. Link, Handb. 1829-33, 1: 768. 1829 (` Coreops-

ideae').

L. included Ageratum, Coreopsis, etc. in his family, which Airy Shaw (in W. 1966) would equate with Compositae-Heliantheae DC. See Compositae Coriandraceae: G. T. Burnett, Outlines of Bot. 1835, pp. 772, 783, 1128. C., with Coriandrum, Bifora (incl. Atrema), and Astoma, in Angelicinae (Umbellatae). See Umbelliferae Coriariaceae n.c.: A. P. and A. de Candolle, Prodr. 1: 739. 1824 (` Cori-

arieae').

This little family (conserved), with Coriaria (about is) only, has defied the taxonomists. We find it in Sapindales—several, including Scholz (in Syll. 12, 1964); Terebinthales (or equiv.)-3 authors, at least; Rutales (or equiv.)—several, from Dumortier (1829) to Gundersen (195o); Hamamelidales (or equiv.)—Hallier (1912); Euphorbiales; Geraniales; Rosales—Thorne (1968); Coriariales—including Hutchinson (1969, near Dilleniales ?); and Ranunculales—Cronquist (1968), and Croizat (1952, related to Ranunculaceae ?). Burnett (1835) included C. in Ochnaceae in Rutinae. See Sapindales Cori(d)(ac)eae: J. G. Agardh, Theoria, 1858, p. 332 (`Corideae'). A. put his little fam. near Primulaceae, and Airy Shaw (in W. 1966) says that it is more or less intermediate between Primulaceae and

Lythraceae.

940 CHEMOTAXONOMY OF FLOWERING PLANTS

Most authors, including Melchior (in Syll. 12, 1964), put Coris in

Primulaceae. See Primulaceae, Primulales Corisperm(ac)eae: H. F. Link, Handb. 1829-31, II: 407. 1831 (`Corispermeae'). L. had Corispermum and Agriophyllum in his family. See Chenopodiaceae Cornaceae n.c.: B. C. Dumortier, Anal. 1829, pp. 33, 34. (`Corneae'). D., whose family is conserved, mentions only Cornus and Aucuba. Harms (in EP1, 1897) included 15 genera in 7 sub-families. Almost every author has had an individual idea of the limits of the family and I have discussed it elsewhere (p. 3o) as a prime example of `chaos in taxonomy'. We are concerned here only with the placing of Cornaceae, whatever its limits. Most a