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Handbook of Biochemistry: Section C Lipids Carbohydrates & Steroids, Volume l [1 ed.]
 9780429487293, 9780429945533, 9780429945526, 9780429945540, 9781138596900

Table of contents :

1. Physical and Chemical Data - Ion Exchange, Chromatography, Buffers 2. Nomenclature � Physical and Chemical Data

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Handbook of Biochemistry and Molecular Biology

Handbook of Biochemistry and Molecular Biology 3rd Edition

Lipids, Carbohydrates, Steroids EDITOR

Gerald D. Fasman, Ph. D. Rosenfield Professor of Biochemistry Graduate Department of Biochemistry Brandeis University Waltham, Massachusetts

Boca Raton London New York

CRC Press is an imprint of the Taylor & Francis Group, an informa business

First published 1975 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 Reissued 2018 by CRC Press © 1975 by Taylor& Francis © 1970, 1968 by The Chemical Rubber Co.

CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organiza-tion that provides licenses and registration for a variety ofusers. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Publisher's Note The publisher has gone to great lengths to ensure the quality of this reprint but points out that some imperfections in the original copies may be apparent. Disclaimer The publisher has made every effort to trace copyright holders and welcomes correspondence from those they have been unable to contact. ISBN 13: 978-I-138-59690-0 (hbk) ISBN 13: 978-0-429-48729-3 (ebk) Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com

Handbook of Biochemistry and Molecular Biology 3rd Edition

Lipids, Carbohydrates, Steroids Editor Gerald D. Fasman, Ph. D. Rosenfield Professor of Biochemistry Graduate Department of Biochemistry Brandeis University Waltham, Massachusetts The following is a list of the four major sections of the Handbook, each consisting of one or more volumes Proteins —Amino Acids, Peptides, Polypeptides, and Proteins Nucleic, Acids — Purines, Pyrimidines, Nucleotides, Oligonucleotides, tRNA, DNA, RNA Lipids, Carbohydrates, Steroids Physical and Chemical Data, Miscellaneous —Ion Exchange, Chromatog­ raphy, Buffers, Miscellaneous, e.g., Vitamins

ADVISORY BOARD Gerald D. Fasman Editor Herbert A. Sober (deceased) Consulting Editor MEMBERS Bruce Ames Professor, Department of Biochemistry University of California Berkeley, California 94720 Sherman Beychok Professor, Department of Biological Sciences Columbia University New York, New York 10027 Waldo E. Cohn Senior Biochemist, Biology Division Oak Ridge National Laboratory Oak Ridge, Tennessee 37830 Harold Edelhoch National Institute Arthritis, Metabolism and Digestive Diseases Department of Health, Education, and Welfare National Institutes of Health Bethesda, Maryland 20014 John Edsall Professor Emeritus, Biological Laboratories Harvard University Cambridge, Massachusetts 02138

Victor Ginsburg Chief, Biochemistry Section, National Institute of Arthritis, Metabolism and Digestive Diseases Department of Health, Education, and Welfare National Institutes of Health Bethesda, Maryland 20014 Walter Gratzer MRC Neurobiology Unit Department of Biophysics Kings College University of London London England Lawrence Grossman Professor, Department of Biochemical and Biophysical Sciences School of Hygiene and Public Health The Johns Hopkins University Baltimore, Maryland 21205 Frank Gurd Professor, Department of Chemistry Indiana University Bloomington, Indiana 47401

Gary Felsenfeld Chief, Physical Chemistry Laboratory Laboratory of Molecular Biology National Institute of Arthritis, Metabolism, and Digestive Diseases National Institutes Of Health Bethesda, Maryland 20014

William Harrington Professor, Department of Biology The Johns Hopkins University Baltimore, Maryland 21218

Edmond H. Fischer Professor, Department of Biochemistry University of Washington Seattle, Washington 98195

William P. Jencks Professor, Graduate Department of Biochemistry Brandeis University Waltham, Massachusetts 02154

ADVISORY BOARD (continued)

0 . L. Kline Executive Officer American Institute of Nutrition 9650 Rockville Pike Bethesda, Maryland 20014

Julius Marmur Professor, Department of Biochemistry and Genetics Albert Einstein College of Medicine New York, New York 10461

1. M. Klotz Professor, Department of Chemistry Northwestern University Evanston, Illinois 60201

Alton Meister Professor, Department of Biochemistry Cornell University Medical College New York, New York 10021

Robert Langridge Professor, Department of Biochemistry Princeton University Princeton, New Jersey 08540 Philip Leder Chief, Laboratory of Molecular Genetics National Institute of Child Health and Human Development National Institutes of Health Bethesda, Maryland 20014 I. Robert Lehman Professor, Department Biochemistry School of Medicine Stanford University Stanford, California 94305 Lawrence Levine Professor, Graduate Department of Biochemistry Brandeis University Waltham, Massachusetts 02154 John Lowenstein Professor, Graduate Department of Biochemistry Brandeis University Waltham, Massachusetts 02154 Emanuel Margoliash Professor, Department of Biological Sciences Northwestern University Evanston, Illinois 60201

Kivie Moldave Professor, Department of Biochemistry California College of Medicine University of California Irvine, California 92664 D. C. Phillips Professor, Laboratory of Molecular Biophysics Department of Zoology Oxford University Oxford England William D. Phillips The Lord Rank Research Centre Ranks Hove, McDougall Ltd. Lincoln Road, High Wycombe Bucks England

G. N. Ramachandran Professor, Molecular Biophysics Unit Indian Institute of Science Bangalore India Michael Sela Professor, Department of Chemical Immunology The Weizmann Institute of Science Rehovot Israel

ADVISORY BOARD (continued)

Waclaw Szybalski Professor, McArdle Laboratory for Cancer Research The University of Wisconsin Madison, Wisconsin, 53706 Serge N. Timasheff Professor, Graduate Department of Biochemistry Brandeis University Waltham, Massachusetts 02154

Ignacio Tinoco, Jr. Professor, Department of Chemistry University of California Berkeley, California 94720 Bert L. Vallee Professor, Biophysics Research Laboratory Peter Bent Brigham Hosoital Harvard Medical School Boston, Massachusetts 02115

CONTRIBUTORS R. G. Ackman Environment Canada Fisheries and Marine Research and Development Directorate Halifax Laboratory Halifax, Nova Scotia Canada Waldo E. Cohn Senior Biochemist, Biology Division Oak Ridge National Laboratory Oak Ridge, Tennessee 37830 Isidore Danishefsky Professor, Department of Biochemistry New York Medical College New York, New York 10029 Glyn Dawson Associate Professor, Department of Pediatrics The University of Chicago Chicago, Illinois 60637 Sen-itiroh Hakamori Fred Hutchinson Cancer Research Center 2D-08 Seattle, Washington 98104 Ineo Ishizuka Department of Biochemistry Faculty of Medicine Tokyo University Tokyo Japan Akira Kobata Chairman, Department of Biochemistry Kobe University School of Medicine Ikuta-ku, Kobe Japan

Fred A. Kummerow Burnsides Research Laboratory University of Illinois Urbana, Illinois 61801 Su-Chen Li Department of Biochemistry Tulane University New Orleans, Louisiana 70112 Yu-Teh Li Department of Biochemistry Tulane University New Orleans, Louisiana 70112 Irving Listowski Department of Biochemistry Albert Einstein College of Medicine Yeshiva University New York, New York 10461 Donald L. MacDonald Department of Biochemistry and Biophysics Oregon State University Corvallis, Oregon 97331 George G. Maher Research Chemist Northern Utilization Research and Development Division Agricultural Research Service U.S. Department of Agriculture Peoria, Illinois 61604 Hiroshi Nikaido Department of Bacteriology and Immunology University of California Berkeley, California 94720 Rudolf A. Raff Department of Biology Massachusetts Institute of Technology Cambridge, Massachusetts 02319

CONTRIBUTORS (continued)

V. S. R. Rao Molecular Biophysics Unit Indian Institute of Science Bangalore India

Robert W. Wheat Department of Microbiology and Immunology Duke University Medical Center Durham, North Carolina 27706

F. Edward Roberts Merck Sharp & Dohme Research Laboratories Merck & Company, Inc. Rahway, New Jersey 07065

Thomas R. Windholz Merck Sharp & Dohme Research Laboratories Merck & Company, Inc. Rahway, New Jersey 07065

PREFACE The rapid pace at which new data is currently accumulated in science presents one of the significant problems of today — the problem of rapid retrieval of information. The fields of biochemistry and molecular biology are two areas in which the information explosion is manifest. Such data is of interest in the disciplines of medicine, modern biology, genetics, immunology, biophysics, etc., to name but a few related areas. It was this need which first prompted CRC Press, with Dr. Herbert A. Sober as Editor, to publish the first two editions of a modern Handbook o f Biochemistry, which made available unique, in depth compilations of critically evaluated data to graduate students, post-doctoral fellows, and research workers in selected areas of biochemistry. This third edition of the Handbook demonstrates the wealth of new information which has become available since 1970. The title has been changed to include molecular biology; as the fields of biochemistry and molecular biology exist today, it becomes more difficult to differentiate between them. As a result of this philosophy, this edition has been greatly expanded. Also, previous data has been revised and obsolete material has been eliminated. As before, however, all areas of interest have not been covered in this edition. Elementary data, readily available elsewhere, has not been included. We have attempted to stress the areas of today’s principal research frontiers and consequently certain areas of important biochemical interest are relatively neglected, but hopefully not totally ignored. This third edition is over double the size of the second edition. Tables used from the second edition without change are so marked, but their number is small. Most of the tables from the second edition have been extensively revised, and over half of the data is new material. In addition, a far more extensive index has been compiled to facilitate the use of the Handbook. To make more facile use of the Handbook because of the increased size, it has been divided into four sections. Each section will have one or more volumes. The four sections are titled: Proteins —Amino Acids, Peptides, Polypeptides, and Proteins Nucleic Acids - Purines, Pyrimidines, Nucleotides, Oligonucleotides, tRNA, DNA, RNA Lipids, Carbohydrates, Steroids Physical and Chemical Data, Miscellaneous - Ion Exchange, Chromatography, Buffers, Miscellaneous, e.g., Vitamins By means of this division of the data, we can continuously update the Handbook by publishing new data as they become available. The Editor wishes to thank the numerous contributors, Dr. Herbert A. Sober, who assisted the Editor generously, and the Advisory Board for their counsel and cooperation. Without their efforts this edition would not have been possible. Special acknowledgments are due to the editorial staff of CRC Press, Inc., particularly Ms. Susan Cubar Benovich, Ms. Sandy Pearlman, and Mrs. Gayle Tavens, for their perspicacity and invaluable assistance in the editing of the manuscript. The editor alone, however, is responsible for the scope and the organization of the tables. We invite comments and criticisms regarding format and selection of subject matter, as well as specific suggestions for new data (and their sources) which might be included in subsequent editions. We hope that errors and omissions in the data that appear in the Handbook will be brought to the attention of the Editor and the publisher.

Gerald D. Fasman Editor August 1975

PREFACE TO LIPIDS, CARBOHYDRATES, STEROIDS This volume contains the complete section of the Handbook o f Biochemistry and Molecular Biology with data pertaining to Lipids, Carbohydrates, and Steroids. The subsection of Carbohydrates contains information on monosaccharides, disac­ charides, oligosaccharides, phosphate esters, amino sugars, glycolipids, and glycohydrolases. X-Ray and optical activity data are also included. The subsection on Lipids lists data on fatty acids (physical and chemical data, densities, specific volumes, temperature coefficients, refractive indices), alkyl monoesters of carboxylic and diesters of dicarboxylic acids, triglycerides, and long chain aliphatic acids. Information on fats and oils, chromatographic separation, physical data such as NMR, proton chemical shifts, and mass spectra are included. The subsection on Steroids contains information on adrogens, bile acids, corticoids, estrogens, progestagens, and sterols. Although far from complete, this volume will hopefully be of assistance to researchers in these areas. Gerald D. Fasman Editor September 1975

THE EDITOR Gerald D. Fasman, Ph.D., is the Rosenfield Professor of Biochemistry, Graduate Department of Chemistry, Brandeis University, Waltham, Massachusetts. Dr. Fasman graduated from the University of Alberta in 1948 with a B.S. Honors Degree in Chemistry, and he received his Ph.D. in Organic Chemistry in 1952 from the California Institute of Technology, Pasadena, California. Dr. Fasman did postdoctoral studies at Cambridge University, England, Eidg. Technische Hochschule, Zurich, Switzerland, and the Weizmann Institute of Science, Rehovoth, Israel. Prior to moving to Brandeis University, he spent several years at the Children’s Cancer Research Foundation at the Harvard Medical School. He has been an Established Investigator of the American Heart Association, a National Science Foundation Senior Postdoctoral Fellow in Japan, and recently was a John Simon Guggenheim Fellow. Dr. Fasman is a member of the American Chemical Society, a Fellow of the American Association for the Advancement of Science, Sigma Xi, The Biophysical Society, American Society of Biological Chemists, The Chemical Society (London), the New York Academy of Science, and a Fellow of the American Institute of Chemists. He has published 180 research papers.

The Editor and CRC Press, Inc. would like to dedicate this third edition to the memory of Eva K. and Herbert A. Sober. Their pioneering work on the development of the Handbook is acknowledged with sincere appreciation.

TABLE OF CONTENTS NOMENCLATURE Biochemical Nomenclature .......................................................................................................................3 Nomenclature of Labeled C o m p o u n d s.....................................................................................................13 The Citation of Bibliographic References in Biochemical Journals Recommendations (1971) . . 14 IUPAC Tentative Rules for Nomenclature of Organic Chemistry Section E. Fundamental S tereochem istry.....................................................................................................................................18 Definitive Rules for Nomenclature of Steroids .................................................................................... 56 Nomenclature of Cyclitols Recommendations (1973) 89 Tentative Rules for Carbohydrate Nomenclature Part I (1969) 100 CARBOHYDRATES Natural Alditols, Inositols, Inososes, and Amino Alditols and In o s a m in e s ...................................... 139 Natural Acids of Carbohydrate Derivation .......................................................................................... 153 Natural Aldoses .......................................................................................................................................181 Natural Ketoses ...................................................................................................................................... 226 Chromatographic Conditions for Chromatography Data in Tables 1—4 243 Carbohydrate Phosphate E s te r s .............................................................................................................. 253 Carbohydrate Phosphate E s te r s .............................................................................................................. 262 Structure of Disaccharide Units Isolated from Complex Carbohydrates of Mammalian Origin . . 278 Carbohydrate-Amino Acid Linkages Found in Mammalian Glycoproteins and Related Gly coconjugates.................................................................................................................................. 281 Oligosaccharides (including D isacch arid es).......................................................................................... 283 Oligosaccharides (including D isacch arid es).......................................................................................... 327 Mucopolysaccharides (Glycosaminoglycans) ...................................................................................... 356 Naturally Occurring Amino Sugars ...................................................................................................... 359 Gly colipids of Bacteria ............................... 373 Lipopolysaccharides of Gram-negative B a c t e r i a .................................................................................. 396 Gly c o l i p i d s ................................ 416 G lycohydrolases...................................................................................................................................... 426 Isolation and Enzymatic Synthesis of Sugar Nucleotides .................................................................. 446 Optical Activity of S u g a r s ...................................................................................................................... 459 Average Dimensions of a Monosaccharide Unit .................................................................................. 472 Electronic Charge Distribution in Monosaccharides and Some of Their Derivatives and P oly sacch arides.................................................................................................................................. 474 LIPIDS Fatty Acids: Physical and Chemical C h ara ctertistic s........................................................................ 484 Densities, Specific Volumes, and Temperature Coefficients of Fatty Acids from C8 to Ci 2 . . 492 Refractive Indices and Equations for Some Fatty Acids and Their Methyl E s t e r s ........................ 493 Refractive Indices of Two Series of Alkyl Esters at Various T em p e ratu re s.................................... 493 Refractive Index, nD20 C, of Alkyl Monoesters of Carboxylic and Diesters of Dicarboxylic Acids .................................................................................................................................................. 494 Dielectric Constants of Some Fats, Fatty Acids, and E s t e r s ............................................................ 494 Solubilities of Fatty Acids in W a t e r .................................................................................................... 495 Approximate Solubilities of Water in Saturated Fatty Acids at Various T e m p e ra tu re s................ 495 Solubility of Simple Saturated Triglycerides ......................................................................................496 Solubilities of Mixed TriacidTriglycerides at 25°C 497 Force-area and Related Data from Monomolecular Film Measurements of Linseed Oil Acids and Esters .......................................................................................................................................... 497

Molecular Dimensions of Long-chain Aliphatic Acids and Related Compounds Calculated from Monomolecular M easurem ents.......................................................................................................... 498 NMR Spectra of Some Unsaturated Methyl E s t e r s ............................................................................ 498 Proton Chemical Shifts .......................................................................................................................... 499 Mass Spectra of Methyl Oleate, Methyl Linoleate, and Methyl L in o le n a te .................................... 500 Properties and Fatty Acid Composition of Fats and Oils ................................................................ 502 Composition of Acids of Beeswax Fractions ......................................................................................504 ECL of Methyl Octadecadienoates andOctadecatrienoates ............................................................... 505 Columns Used for Determination of ECL Values ............................................................................ 505 Key Fragments in the Spectra of Pyrrolidides of Monounsaturated Fatty Acids ........................ 506 The Lipid Composition of Various Parts of Adult Human Skin .................................................... 507 Twenty-one of the Fatty Acids of Human Skin Surface L ip id s ........................................................ 508 Fatty Acids of Wax Esters and Sterol Esters from Vernix Caseosa and from Human Skin Surface Lipid .................................................................................................................................................. 509 The Analysis of Fatty A c i d s .................................................................................................................. 511 Sunflower Hull C o m p o sitio n .................................................................................................................. 511 Content of Unsaponifiables in Vegetable Oils and Yield of Four Fractions From Unsaponifiables by Thin Layer Chromatography .......................................................................................................... 512 Solubility of Selected Lipids in Organic Solvents ...................................................................... 512 Isomers in Rat Cardiac Lipids .............................................................................................................. 513 Solubility of Selected Lipids in Chlorinated Hydrocarbon S o lv e n ts ................................................ 514 Solubility of Selected Lipids in Chlorinated Hydrocarbon Mixtures with 33% Methanol . . . .5 1 4 Surface Areas for Pure Methyl Esters and Triglycerides Measured at Constant Surface Pressure Using TTP as the Piston O i l .............................................................................................................. 515 Properties of Polyol E s te r s ...................................................................................................................... 515 Physical Constants of the Methyl Esters of Some Synthetic Alkenyl- and Alkyl-substituted Fatty Acid Methyl E s t e r s .................................................................................................................. 516 Normalized Intensities of Key Fragments in the Mass Spectra of Methyl Esters of Alkenyl Branched Chain Acids ...................................................................................................................................... 517 Comparison of Surface Pressure at Transition and Collapse of Various «-Saturated Fatty Acid M on o lay ers.......................................................................................................................................... 518 Content of Total Lipids, Cholesteryl Esters, and Phospholipids ...................................................... 519 Mass Spectrum of a-Tocotrienol .......................................................................................................... 520 Individual Tocopherol Contents of Vegetable Oils (Average of Three D eterm inations).................. 521 Effect of Dietary Fat on Fatty Acid Composition inPlasma and Erythrocyte Lipids ................... 522 Properties of Some Atlantic Herring and Two Other Oils with Weight Percent Compositions of The Fatty Acid Methyl Esters Derived from the Oils .............................................................. 523 Chain Length Composition of Some Atlantic Herring Oils, of Some Other Herring Oils, and of Pilchard O i l .......................................................................................................................................... 525 Comparisons of Properties of Interest of Some Atlantic Herring Oils, for Some Other Herring Oils, and for Pilchard Oil .......................................................................................................................... 526 STEROIDS Androgens .............................................................................................................................................. 531 Bile A c id s .................................................................................................................................................. 534 Corticoids .............................................................................................................................................. 536 E s tro g e n s .................................................................................................................................................. 539 Progestagens .......................................................................................................................................... 541 S t e r o l s ...................................................................................................................................................... 544 INDEX

563

Nomenclature

3

BIOCHEMICAL NOMENCLATURE This synopsis of the recommendations of the IUPAC-IUB Commission on Biochemical Nomenclature (CBN) was prepared by Waldo E. Cohn, Director, NAS-NRC Office of Biochemical Nomenclature (OBN, located at Biology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37830), from whom reprints of the CBN publications listed below and on which the synopsis is based are available. The synopsis is divided into three sections: Abbreviations, symbols, and trivial names. Each section contains material drawn from the documents (A1 to C l, inclusive) listed below, which deal with the subjects named. Additions consonant with the CBN Recommendations have been made by OBN throughout the synopsis. RULES AND RECOMMENDATIONS AFFECTING BIOCHEMICAL NOMENCLATURE AND PLACES OF PUBLICATION (AS OF FEBRUARY 1975) I.

IUPAC-IUB Commission on Biochemical Nomenclature A l. Abbreviations and Symbols [General; Section 5 replaced by A6 ] A2. Abbreviated Designation of Amino-acid Derivatives and Peptides (1965) [Revised 1971; Expands Section 2 of A l] A3. Synthetic Modifications o f Natural Peptides (1966) [Revised 1972] A4. Synthetic Polypeptides (Polymerized Amino Acids) (1967) [Revised 1971] A5. A One-letter Notation for Amino-acid Sequences (1968) A6. Nucleic Acids, Polynucleotides, and their Constituents (1970) B l.

B2. B3.

(Nomenclature of Vitamins, Coenzymes, and Related Compounds) a. Miscellaneous [A, B’s, C, D’s, tocols, niacins; see B2 and B3] b. Quinones with Isoprenoid Side-chains: E, K, Q [Revised 1973] c. Folic Acid and Related Compounds d. Corrinoids: B-12’s [Revised 1973] Vitamins B-6 and Related Compounds [Revised 1973] Tocopherols (1973)

C l. C2.

Nomenclature o f Lipids (1967) [Amended 1970; see also II, 2] Nomenclature of α-Amino Acids (1974) [See also II, 5]

D l.

Conformation of Polypeptide Chains (1970) [See also III, 2]

E l. E2. E3. E4.

Enzyme Nomenclature (1972)a [Elsevier (in paperback); Replaces 1965 edition.] Multiple Forms of Enzymes (1971) [Chapter 3 of E l] Nomenclature of Iron-sulfur Proteins (1973) [Chapter 6.5 of El ] Nomenclature of Peptide Hormones (1974)

II.

Documents Jointly Authored by CBN and CNOC [See III] 1. Nomenclature of Cyclitols (1968) [Revised 1973] 2. Nomenclature of Steroids (1968) [Amended 1971; Revised 1972] 3. Nomenclature of Carbohydrates-I (1969) 4. Nomenclature of Carotenoids (1972) [Revised 1975] 5. Nomenclature of α-Amino Acids (1974) [Listed under I, C2 in the following table]

III.

IUPAC Commission on the Nomenclature of Organic Chemistry (CNOC) 1. Section A (Hydrocarbons), Section B (Heterocyclics): J. Am. Chem. Soc., 82, 5545;a Section C (Groups containing N, Hal, S, Se/Te): Pure Appl. Chem., 11, Nos. l - 2 a [A, B, and C Revised 1969:a Butterworth’s, London (1971)] 2. Section E (Stereochemistry):15 J. Org. Chem., 35, 2489 (1970); Biochim. Biophys. Acta, 208, 1 (1970); Eur. J. Biochem., 18, 151 (1970) [See also I, D l]

aNo reprints available from OBN; order from publisher. bReprints available from OBN (in addition to all in IA to ID and II).

4

Handbook o f Biochemistry and Molecular Biology

RULES AND RECOMMENDATIONS AFFECTING BIOCHEMICAL NOMENCLATURE AND PLACES OF PUBLICATION (AS OF FEBRUARY 1975)(continued) IV.

Physiochemical Quantities and Units (IUPAC)a J. Am. Chem. Soc., 82, 5517 (1960) [Revised 1970: Pure Appl. Chem., 21, 1 (1970)]

V.

Nomenclature of Inorganic Chemistry (IUPAC) J. Am. Chem. Soc., 82, 5523a [Revised 1971: Pure Appl. Chem., 28, No. 1 (1971)]a Drugs and Related Compounds or Preparations 1. U.S. Adopted Names (USAN) No. 10 (1972) and Supplement [U.S. Pharmacopeial Convention, Inc., 12601 Twinbrook Parkway, Rockville, Md.] 2. International Nonproprietary Names (INN) [WHO, Geneva]

VI.

14,449 9,3471

123,409

145,405

147,1 160,355

128,269* 136,13 147,4

Dl*

E2 E3 E4

II,I(Revised) II, 2f Amendments 11,3 11,4 Amendments 8,2227 10,4994 10,3983 10,4827 14,1803

112,17* 113,5 127,613 125,673 127,741 151,507

* First, unrevised v. sion. (R) = revised version.

aReprints available from OBN. bNo reprints available from OBN; order from publisher. cIn French. dIn Russian. eIn German.

10,4825 12,3582 14,2559

6,3287

126,769 135,5 151,1

121,577

105,897 116(5)

5,1* 10,1 25,2 21,455 25,397

24,1 35,1

258,1 310,295

165,1* 164,453 248,387 244,223 286,217

17,193

2,127 12,1 53,1

2,1 53,15(R) 45,7(R) 40,325(R) 46,217(R)

1,259 27,201(R) 1,379* 26,301(R) 5,151 15,203

Eur. J. Biochem.

229,1

152,1 202,404

354,155(R)

107,l(a—c) 387,397(R)

263,205(R) 133,1* 278,211(R) 168,6 247,1

Biochim. Biophys. Acta

fAlso in other journals. gAlso in Biopolymers, 11, 321. hJ. Mol B io l, 55, 299. V. M ol Biol, 52, 1.

13,1555(R) 13,1056(R)

Clf Amendments C2

102,15 147,15(R) 147,1(R) 137,417(R) 147,11(R)

118,505 165.1(R) 161(2),iii(R) 162,1(R) 165,6(R)

5,1445 11,1726(R) 6,362* 11,942(R) 7,2703 9,4022

B l* Blb( Revised) Bld(Revised) B2( Revised) B3(Revised)

101,1 126,773(R) 104,17* 127,753(R) 113,1 120,449

Biochemistry

136,1 150,1(R) 121,6 * 151,597(R) 125(3),i 145,425

Biochem. J.

A lf A2(Revised) A3 (Revised) A4(Revised)g A5 A6h

Arch. Biochem. Biophys.

247,613 247,2633

243,5809* N

246,6127 248,5907 250,3215

245,6489

242,4845 245,1511

245,4229*

31,285(R)

37,285(R)

33,447(R)

38,439

4 0 ,(R) 31,649(R) 33,439(R) 31,641 40,

241,527 247,977(R) 242,555* 247,323(R) 243,3557 245,5171 241,2987

Pure Appl. ChemS

J. Biol. Chem.

}

CBN RECOMMENDATIONS APPEAR IN THE FOLLOWING PLACESa

51,3* 51,819

54,123

50,1363

49,331

50,3 49,121* 49,325* 51,205* 50,1577

Biochimie (Bull. Soc.)c

7,289

2,784

1,872 2,282* 2,466* 5,492(R) 3,473 6,167

Molek. Biol.d

350,523* 351,663

353,852

350,279

351,1165

348,266

348,245 348,256* 348,262* 349,1013 350,793 351,1055

Z. Phys. Chem. e

5

6

Handbook o f Biochemistry and Molecular Biology

ABBREVIATIONS Abbreviations are distinguished from symbols as follows (taken from Reference Al): a. Symbols, for monomeric units in macromolecules, are used to make up abbreviated structural formulas (e.g., Gly-Val-Thr for the tripeptide glycylvalylthreonine) and can be made fairly systematic. b. Abbreviations for semi-systematic or trivial names (e.g., ATP for adenosine triphosphate; FAD for flavinadenine dinucleotide) are generally formed of three or four capital letters, chosen for brevity rather than for system. It is the indiscriminate coining and use of such abbreviations that has aroused objections to the use of abbreviations in general. [Abbreviations are thus distinguished from symbols in that they (a) are for semi-systematic or trivial names, (b) are brief rather than systematic, (c) are usually formed from three or four capital letters, and (d) are not used —as are symbols —as units of larger structures. ATP, FAD, etc., are abbreviations. Gly, Ser, Ado, Glc, etc., are symbols (as are Na, K, Ca, 0 , S, etc.); they are sometimes useful as abbreviations in figures, tables, etc., where space is limited, but are usually not permitted in text. The use of abbreviations is permitted when necessary but is never required.] 1. Nucleotides (N = A, C, G, 1, Ο, T, U, X, φ - see One-letter Symbols) NMP NDP NTP

Nucleoside 5'-phosphate Nucleoside 5'-di(or pyrojphosphate Nucleoside 5'-triphosphate

Prefix d indicates deoxy.

2. Coenzymes, vitamins CoA(or Co ASH) CoASAc DPNa FAD FMN GSH GSSG NADb NADPb NMN TPNC

Coenzyme A Acetyl Coenzyme A Diphosphopyridine nucleotide Flavin-adenine dinucleotide Riboflavin 5'-phosphate Glutathione Oxidized glutathione Nicotinamide-adenine dinucleotide (cozymase, Coenzyme I, diphosphopyridine nucleotide) Nicotinamide-adenine dinucleotide phosphate (Coenzyme II, triphosphopyridine nucleotide) Nicotinamide mononucleotide Triphosphopyridine nucleotide

3. Miscellaneous ACTH CM-cellulose DEAE-cellulose DDT EDTA Hb,HbC0,Hb02

pi

Adrenocorticotropin, adrenocorticotropic hormone, or corticotropin #-(Carboxymethyl)cellulose 0-(Diethylaminoethyl)cellulose 1,1 ,l-Trichloro-2,2-bis(p-chlorophenyl)ethane Ethylenediaminetetraacetate Hemoglobin, carbon monoxide hemoglobin, oxyhemoglobin Inorganic orthophosphate

aReplaced by NAD (also DPNT by NAD+, DPNH by NADH). bGeneric term; oxidized and reduced forms are NAD+, NADH (NADP+, NADPH). Replaced by NADP (also TPN+ by NADP\ TPNH by NADPH).

7

PFj TEAE-cellulose Tris

Inorganic pyrophosphate 0-(Triethylaminoethyl)cellulose Tris(hydroxymethyl)aminomethan (2-amino-2-hydroxymethylpropane-l ,3-diol)

4. Nucleic Acids DNA, RNA hnRNA mtDNA cRNA mRNA nRNA rRNA tRNA tRNAAla AA-tRNA Ala-tRNA or Ala-tRNAAla tRNAMet tR N A ^ et or tRNA^et fMet-tRNA

Deoxyribonucleic acid, ribonucleic acid (or -nucleate) Heterogeneous RNA Mitochondrial DNA Complementary RNA Messenger RNA Nuclear RNA Ribosomal RNA Transfer RNA (generic term; sRNA should not be used for this or any other purpose) Alanine tRNA; tR N A ^ a, tRNA^la: isoacceptor alanine tRNA’s Aminoacyl-tRNA; aminoacylated tRNA; “charged” tRNA (generic term) Alanyl-tRNA Methionine tRNA (not enzymically formylatable) Methionine tRNA, enzymically formylatable to . . . Formylmethionyl-tRNA (small f, to distinguish from fluorine F)

SYMBOLS Symbols are distinguished from abbreviations in that they are designed to represent specific parts of larger molecules, just as the symbols for the elements are used in depicting molecules, and are thus rather systematic in construction and use. Symbols are not designed to be used as abbreviations and should not be used as such in text, but they may often serve this purpose when space is limited (as in a figure or table). Symbols are always written with a single capital letter, all subsequent letters being lower-case (e.g., Ca, Cl, Me, Ac, Gly, Rib, Ado), regardless of their position in a sequence, a sentence, or as a superscript or subscript. Some abbreviations expressed in symbols as examples of the use of symbols: Dimethylsulfoxide Tetranitromethane Guanidine hydrochloride Guanidinium chloride Cetyltrimethylammonium bromide Ethyl methanesulfonate Methylnitronitrosoguanidine -nitrosourea -nitrosamine -fluorene Aminofluorene Acetylaminofluorene Acetoxyacetylaminofluorene A-Acetylneuraminic acid aReplaces DMSO. b Replaces TNM. cReplaces Gu, Gd, and G. d Replaces CTAB (similarly compounds). eReplaces NU. f Replaces NA. gReplaces AAF. hNot NANA.

for

Me, SO a (N 0 2)4C b Gdn · HC1 c GdmCl CtMe3 NBr d MeS03Et MeN20 3Gdn -Nur e -Nam ^ -Fin NH2 Fin AcNHFln g Ac(AcO)NFln AcNeu b

other

ammonium

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Handbook o f Biochemistry and Molecular Biology

I.

Phosphorylated Compounds (Reference A l) -P{or P-) (“p” in Nucleic Acids) -^-(hyphen in Nucleic Acids) -P-P or -PP or PP- (cf. PPj in Abbreviations)

-P03 H2 (or its ions) -P02 H-(or its ion) -P02 H-PO3H2 (or ions)

Examples:3 Glucose 6-phosphate Phosphenolpyruvate (pyruvenol phosphate) Fructose 1,6-bisphosphate (not di) Creatine phosphate Phosphocreatine

Glucose^-P (or Glc-6-p; see II below). P-enol?yx\xv'd\e or ewo/Pyruvate-/>or e Prv-Pb Fructose- 1,6-P2 (or Fru-1,6-P2; see II below). Creatine-P ^-Creatine

aNote that symbols are hyphenated even where names are not. bRecommended by OBN.

II. Carbohydrates (Reference A l) Sugars3 Fructose Galactose Glucose Mannose

Fru Gal Glc b Man

Arabinose Lyxose Ribose Xylose

Ara c Lyx Rib d xyi

Prefix d indicates 2-deoxy; 3-d, etc., indicates 3-deoxy, etc. aAlways one capital, two small letters (i.e., never glc or GLC). bTo distinguish from Glu = glutamic acid; G is permitted only where confusion is minimal, and in the special case of IJDPG (uridinediphosphoglucose). cBecomes ara or a when used as a modifier, as before C e.g., araC or aC. dNever R (= purine nucleoside; see Nucleic Acids).

Derivatives Using glucose, Glc, as an example Gluconic acid Glucuronic acid Glucosamine TV-Acety lgluco sami ne but A-Acetylneuraminic acid

GlcA GlcU GlcN GlcNAc AcNeu (not NANA)

Using ribose, Rib, as an example Ribulose Ribitol Ribityl

Rbu Rbo Rby

Configuration PS

pyranose, furanose (suffixes)

D,L

(prefixes)

used without hyphenation (see examples). D may be omitted.

Sequence and direction -*· (1 -* 4), etc. (1 -4 ), etc.

glycoside glycoside glycoside glycoside

link, pointing away from hemiacetal carbon. link, assumes hemiacetal carbon at left. link, from hemiacetal carbon (C-l) to C-4, etc. link, assumes hemiacetal carbon (C-l) at left, etc.

9

Examples Maltose, G lcp(al-4)G lc Lactose, Galp(01 -4)G lc Stachyose, Galp(al-6)G alp(al-6)G al/?( b > c > d , where > denotes “is preferred to.” The first step, however, in considering a model is to identify the nature and position of each chiral element that it contains. There are three types of the chiral element, namely, the chiral center, the chiral axis, and the chiral plane. The chiral center, which is very much the most commonly met, is exemplified by an asymmetric carbon atom with the tetrahedral arrangement of ligands, as in (1). A chiral axis is present in, for instance, the chiral allenes such as (2) or the chiral biaryl derivatives. A chiral plane is exemplified by the plane containing the benzene ring and the bromine and oxygen atoms in the chiral compound (3), or by the underlined atoms in the cycloalkene (4). Clearly, more than one

* Ligancy refers to the number of bonds from an atom, independently of the nature of the bonds, tcahn, R. S., Ingold, C., and Prelog, V., Artgew. Chem. Int: Ed., 5, 385 (1966); errata, 5, 511 (1966); Angew. Cherru, 78, 413 (1966). Earlier papers: Cahn, R. S. and Ingold, C. K Chem. Soc. (Lond.), 612 (1951); Cahn, R. S., Ingold, C., and Prelog, V., Experientia, 12, 81 (1956). For a partial, simplified account see Cahn, R. S., J. Chem. Educ., 41, 116 (1964); errata, 41, 503 (1964).

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Handbook o f Biochemistry and Molecular Biology

type of chiral element may be present in one compound; for instance, group “a” in (2) migh be a sec-butyl group which contains a chiral center.

The Chiral Center Let us consider first the simplest case, namely, a chiral center (such as carbon) with four ligands, a, b, c, and d, which are all different atoms tetrahedrally arranged as in CHFCIBr. The four ligands are arranged in order of preference by means of the sequence rule; this contains five subrules, which are applied in succession so far as necessary to obtain a decision. The first subrule is all that is required in a great majority of actual cases; it states that ligands are arranged in order of decreasing atomic number, in the above case (a) Br > (b) Cl > (c) F > (d) H. There would be two (enantiomeric) forms of the compound and we can write these as (5) and (6). In the sequence-rule procedure the model is viewed from the side remote from the least-preferred ligand (d), as illustrated. Then, tracing a path from a to b to c in (5) gives a clockwise course, which is symbolized by (R) (Latin rectus, right; for right hand); in (6) it gives an anticlockwise course, symbolized as (S) (Latin sinister, left). Thus (5) would be named (/?)-bromochlorofluoromethane, and (6) would be named (iS')-bromochlorofluoromethane. Here already it may be noted that converting one enantiomer into another changes each R to S , and each S to R , always. It will be seen also that the chirality prefix is the same whether the alphabetical order is used, as above, for naming the substituents or whether this is done by the order of complexity (giving fluorochlorobromomethane).

Next, suppose we have H3C-CHC1F. We deal first with the atoms directly attached to the chiral center; so the four ligands to be considered are Cl > F > C (of CH3) > H. Here the H’s of the CH3 are not concerned, because we do not need them in order to assign our symbol. However, atoms directly attached to a center are often identical, as, for example, the underlined C’s in H3C—CHC1—CH2OH. For such a compound we at once establish a preference (a) Cl > (b, c) C,C > (d) H. Then to decide between the two C’s we work outward, to the atoms to which they in turn are directly attached and we then find which we can conveniently write as C(H,H,H) and C(0,H,H). We have to compare Η,Η,Η with Ο,Η,Η, and since oxygen has a higher atomic number than hydrogen we have Ο > H

49

and thence the complete order Cl > C (of CH2OH) > C (of CH3) > H, so that the chirality symbol can then be determined from the three-dimensional model.

We must next meet the first complication. Suppose that we have a molecule (7).

To decide between the two C’s we first arrange the atoms attached to them in their order of preference, which gives C(C1,C,H) on the left and C(F,0,H) on the right. Then we compare the preferred atom of one set (namely, Cl) with the preferred atom (F) of the other set, and as Cl > F we arrive at the preferences a > b > c > d shown in (7) and chirality (S). If, however, we had a compound (8) we should have met C(C1,C,H) and C(C1,0,H) and, since the atoms of first preference are identical (Cl), we should have had to make the comparisons with the atoms of second preference, namely, O > C, which to the different chirality (R) as shown in (8).

Branched ligands are treated similarly. Setting them out in full gives a picture that at first sight looks complex but the treatment is in fact simple. For instance, in compound (9) a first quick glance again shows (a) Cl > (b, c) C,C > (d) H: When we expand the two C’s we find they are both C(C,C,H), so we continue exploration. Considering first the left-hand ligand we arrange the branches and their sets of atoms in order thus: C(C1,H,H) > C(H,H,H). On the right-hand side we have C(0,C,H) > C(0,H,H) (because C > H). We compare first the preferred of these branches from each side and we find C(C1,H,H) > C(0,C,H) because Cl > 0 , and that gives the left-hand branch preference over the right-hand branch. That is all we need to do to establish chirality (S) for this highly branched compound (9). Note that it is immaterial here that, for the lower branches, the right-hand C(0,H,H) would have been preferred to the left-hand C(H,H,H); we did not need to reach that point in our comparisons and so we are not concerned with it; but we should have reached it if the two top (preferred) branches had both been the same CH2C1. Rings, when we met during outward exploration, are treated in the same way as branched chains.

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Handbook o f Biochemistry and Molecular Biology

With these simple procedures alone, quite complex structures can be handled; for instance, the analysis alongside Formula (10) for natural morphine explains why the specification is as shown. The reason for considering C-12 as C(C,C,C) is set out in the next paragraphs.

Now, using the sequence rule depends on exploring along bonds. To avoid theoretical arguments about the nature of bonds, simple classical forms are used. Double and triple bonds are split into two and three bonds, respectively. A > C =0 group is treated as (i) (below) where the (0) and the (C) are duplicate representations of the atoms at the other end of the double bond. —C^CH is treated as (ii) and —C=N is treated as (iii).

51

Thus in D-glyceraldehyde (11) the CHO group is treated as C(0,(0),H) and is thus preferred to the C(0,H,H) of the CH2OH group, so that the chirality symbol is (/?).

Only the doubly bonded atoms themselves are duplicated, and not the atoms or groups attached to them; the duplicated atoms may thus be considered as carrying three phantom atoms (see below) of atomic number zero. This may be important in deciding preferences in certain complicated cases. Aromatic rings are treated as Kekule structures. For aromatic hydrocarbon rings it is immaterial which Kekule structure is used because “splitting” the double bonds gives the same result in all cases; for instance, for phenyl the result can be represented as (12a) where “(6)” denotes the atomic number of the duplicate representations of carbon.

For aromatic hetero rings, each duplicate is given an atomic number that is the mean of what it would have if the double bond were located at each of the possible positions. A complex case is illustrated in (13). Here C-l is doubly bonded to one or other of the nitrogen atoms (atomic number 7) and never to carbon, so its added duplicate has atomic number 7; C-3 is doubly bonded either to C-4 (atomic number 6) or to N-2 (atomic number 7), so its added duplicate has atomic number 6xh \ so has that of C-8; but C-4a may be doubly bonded to C-4, C-5, or N-9, so its added duplicate has atomic number 6.33. One last point about the chiral center may be added here. Except for hydrogen, ligancy, if not already four, is made up to four by adding “phantom atoms” which have atomic number zero and are thus always last in order of preference. This has various uses but perhaps the most interesting is where nitrogen occurs in a rigid skeleton, as, for example, in a-isosparteine (14). Here the phantom atom can be placed where the nitrogen

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Handbook o f Biochemistry and Molecular Biology

SOME COMMON GROUPS IN ORDER OF SEQUENCE-RULE PREFERENCE2 A. Alphabetical Order (Higher Number Denotes Greater Preference) 64 Acetoxy 36 Acetyl 48 Acetylamino 21 Acetylenyl 10 Allyl 43 Amino 44 Ammonio +H3N 37 Benzoyl 49 Benzoylamino 65 Benzoyloxy 50 Benzyloxycarbonylamino 13 Benzyl 60 Benzyloxy 41 Benzyloxycarbonyl 75 Bromo 42 fer-Butoxycarbonyl 5 «-Butyl 16 sec-Butyl 19 ferf-Butyl

38 Carboxyl 74 Chloro 17 Cyclohexyl 52 Diethylamino 51 Dimethylamino 34 2,4-Dinitrophenyl 28 3,5-Dinitrophenyl 59 Ethoxy 40 Ethoxycarbonyl 3 Ethyl 46 Ethylamino 68 Fluoro 35 Formyl 63 Formyloxy 62 Glycosyloxy 7 «-Hexyl 1 Hydrogen 57 Hydroxy 76 Iodo

9 Isobutyl 8 Isopentyl 20 Isopropenyl 14 Isopropyl 69 Mercapto 58 Methoxy 39 Methoxycarbonyl 2 Methyl 45 Methylamino 71 Methylsulfinyl 66 Methylsulfinyloxy 72 Methylsulfonyl 67 Methylsulfonyloxy 70 Methylthio 11 Neopentyl 56 Nitro 27 «ί-Nitrophenyl 33 o-Nitrophenyl 24 p-Nitrophenyl

55 Nitroso 6 «-Pentyl 61 Phenoxy 22 Phenyl 47 Phenylamino 54 Phenylazo 18 Propenyl 4 «-Propyl 29 1-Propynyl 12 2-Propynyl 73 Sulfo 25 w-Tolyl 30 o-Tolyl 23 p -Tolyl 53 Trimethylammonio 32 Trityl 15 Vinyl 31 2,6-Xylyl 26 3,5-Xylyl

B. Increasing Order of Sequence Rule Preference 1 Hydrogen 2 Methyl 3 Ethyl 4 «-Propyl 5 «-Butyl 6 «-Pentyl 7 «-Hexyl 8 Isopentyl 9 Isobutyl 10 Allyl 11 Neopentyl 12 2-Propynyl 13 Benzyl 14 Isopropyl 15 Vinyl 16 sec-Butyl 17 Cyclohexyl 18 1-Propenyl 19 ferf-Butyl

20 Isopropenyl 21 Acetylenyl 22 Phenyl 23 p-Tolyl 24 p-Nitrophenyl 25 «7-Tolyl 26 3,5-Xylyl 27 m-Nitrophenyl 28 3,5-Dinitrophenyl 29 1-Propynyl 30 o-Tolyl 31 2,6-Xylyl 32 Trityl 33 o-Nitrophenyl 34 2,4-Dinitrophenyl 35 Formyl 36 Acetyl 37 Benzoyl 38 Carboxyl

39 Methoxycarbonyl*5 40 Ethoxycarbonyl*5 41 Benzyloxycarbonyl*5 42 re/T-Butoxycarbonyl*5 43 Amino 44 Ammonio +H3N 45 Methylamino 46 Ethylamino 47 Phenylamino 48 Acetylamino 49 Benzoylamino 50 Benzyloxycarbonylamino 51 Dimethylamino 52 Diethylamino 53 Trimethylammonio 54 Phenylazo 55 Nitroso 56 Nitro 57 Hydroxy

58 59 60 61 62 63 64 65

Methoxy Ethoxy Benzyloxy Phenoxy Glycosyloxy Formyloxy Acetoxy Benzoyloxy 66 Methylsulfinyloxy 67 Methylsulfonyloxy 68 Fluoro 69 Mercapto H S70 Methylthio CH3S 71 Methylsulfinyl 72 Methylsulfonyl 73 Sulfo H 0 3S 74 Chloro 75 Bromo 76 Iodo

3ANY alteration to structure, or substitution, etc., may alter the order of preference. These groups are R 0 C (= 0 )-

lone pair of electrons is; then N-l appears as shown alongside the formula; and the chirality ( R ) is the consequence. The same applies to N -l6. Phantom atoms are similarly used when assigning chirality symbols to chiral sulfoxides (see example to Rule E-5.9).

53

Symbolism In names of compounds, the R and S symbols, together with their locants, are placed in parentheses, normally in front of the name, as shown for morphine (10) and sparteine (14), but this may be varied in indexes or in languages other than English. Positions within names are required, however, when more than a single series of numerals is used, as for esters and amines. When relative stereochemistry is more important than absolute stereochemistry, as for steroids or carbohydrates, a local system of stereochemical designation may be more useful and sequence-rule symbols need then be used only for any situations where the local system is insufficient. Racemates containing a single center are labeled (RS). If there is more than one center the first is labeled (RS) and the others are (RS) or (SR) according to whether they are R or S when the first is R . For instance, the 2,4-pentanediols CH3—CH(OH)—CH2CH(OH)—CH3 are differentiated as one chiral form (2R,4R)~ other chiral form (2 5 ,4 5 )meso compound (2/? ,45)— racemic compound (2RS,4RS)~

Finally the principles by which some of the least rare of other situations are treated will be very briefly summarized. Pseudoasymmetric Atoms A subrule decrees that R groups have preference over S groups and this permits pseudoasymmetric atoms, as in abC(c-R)(c-S) to be treated in the same way as chiral centers, but as such a molecule is achiral (not optically active) it is given the lower case symbol r or s. Chiral Axis The structure is regarded as an elongated tetrahedron and viewed along the axis —it is immaterial from which end it is viewed; the nearer pair of ligands receives the first two positions in the order of preference, as shown in (15) and (16).

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Handbook o f Biochemistry and Molecular Biology

Chiral Wane The sequence-rule-preferred atom directly attached to the plane is chosen as “pilot atom.” In compound (3) this is the C of the left-hand CH2 group. Now this is attached to the left-hand oxygen atom in the plane. The sequence-rule-preferred path from this oxygen atom is then explored in the plane until a rotation is traced which is clockwise (R ) or anticlockwise (S) when viewed from the pilot atom. In (3) this path is 0 -►C -►C(Br) and it is clockwise (R). Other Subrules Other subrules cater for new chirality created by isotopic labeling (higher mass number preferred to lower) and for steric differences in the ligands. Isotopic labeling rarely changes symbols allotted to other centers. Octahedral Structures Extensions of the sequence rule enable ligands arranged octahedrally to be placed in an order of preference, including poly dentate ligands, so that a chiral structure can then always be represented as one of the enantiomeric forms (17) and (18). The face 1—2—3 is observed from the side remote from the face 4 —5—6 (as marked by arrows), and the path 1 2 3 is observed; in (17) this path is clockwise (R), and in (18) it is anticlockwise (S).

Conformations The torsion angle between selected bonds from two singly bonded atoms is considered. The selected bond from each of these two atoms is that to a unique ligand, or otherwise to the ligand preferred by the sequence rule. The smaller rotation needed to make the front ligand eclipsed with the rear one is noted (this is the rotatory characteristic of a helix); if this rotation is right-handed it leads to a symbol P (plus); if left-handed to M (minus). Examples are

55

Details and Complications For details and complicating factors the original papers should be consulted. They include treatment of compounds with high symmetry or containing repeating units (e.g., cyclitols), also π bonding (metallocenes, etc.), mesomeric compounds and mesomeric radicals, and helical and other secondary structures.

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Handbook o f Biochemistry and Molecular Biology

DEFINITIVE RULES FOR NOMENCLATURE OF STEROIDS* IUPAC Commission on the Nomenclature of Organic Chemistry and IUPAC-IUB Commission on Biochemical Nomenclature GENERAL Rule 2S—1 (Expanded from Rules S—1 and S—2) 1.1. Steroids are numbered and rings are lettered as in Formula (1). If one of the two methyl groups attached to C-25 is substituted it is assigned the lower

number (26); if both are substituted, that carrying the substituent cited first in the alphabetical order is assigned the lower number [cf. IUPAC Rule** C—15.11(e)]. For trimethyl steroids see Rule 2S—2.3, Note c. 1.2. If one or more of the carbon atoms shown in (1) is not present and a steroid name is used, the numbering of the remainder is undisturbed. 1.3. For a steroid the name, including stereochemical affixes, and its structural formula (see Rule 2S-1.4), denote the absolute configuration at each asymmetric center (see also Rule 2S—1.5). When the configuration at one or more centers is not known, this is indicated by Greek letter(s) £ (xi) prefixed by the appropriate numeral(s).

1.4. When the rings of a steroid are denoted as projections on to the plane of the paper the formula is normally to be oriented as in (2). An atom or group attached to a ring de­ picted as in the orientation (2) is termed a(alpha) if it lies below the plane of the paper or j3(beta) if it lies above the plane of the paper. In formulas, bonds to atoms or groups lying below the plane of the paper are shown as broken (---------- ) lines, and bonds to atoms or groups lying above the plane of the paper are shown as solid lines preferably thickened (---------- ). Bonds to atoms or groups whose configuration is not known are denoted by wavy lines ( ).

*From IUPAC Commission on the Nomenclature of Organic Chemistry and IUPAC-IUB Commission on Biochemical Nomenclature, A /re/!/?/?/. Chem., 31, 2 8 3 -3 2 2 (1972). With permission. **IUPAC Nomenclature of Organic Chemistry, Sections A, B, and C, Butterworths, London, 1971.

57

Notes: (1) Projections of steroid formulas should not be oriented as in Formula (3), (4), or (5) unless circumstances make it obligatory.

(2) With the preferred orientation (2), and with (3), a bonds appear as broken lines and β bonds as solid (thickened) lines. The reverse is true for (4) and (5). Wavy lines denote ξ bonds for all orientations of the formula. (3) A perspective representation of the stereochemistry of Formula (2) as in (2a) or (2b) may also be used.

(For the significance of the prefixes 5 a- and 5 β- see Rule 2S-1.5.) When steroid formulas are drawn in this way, bonds pointing upwards are, by convention, drawn bold and bonds pointing downwards are drawn broken; these representations correspond to the β and a bonds of projection formulas such as (2) and do not conform to the general practice that bold and broken lines denote bonds projecting, respectively, above and below the plane of the paper. Note, however, that the general practice is followed with chair and boat forms of spirostans (see Rule 2S-3.3). (4) All hydrogen atoms and methyl groups attached at ring-junction positions must always be inserted as H and CH3, respectively (Me may be used in place of CH3 if editorial conventions require it). The practice, sometimes followed, of denoting methyl groups by bonds without lettering is liable to cause confusion and should be abandoned. This is essential in view of customs in other fields and applies also to other groups of compounds such as cyclic terpenes and alkaloids for which steroid conventions are commonly used. 1.5 Unless implied or stated to the contrary (see Rules 2S—3, 2S—4.3, 2S—5, and 2 S -1 1), use of a steroid name implies that atoms or groups attached at the ring-junction positions 8, 9, 10, 13, and 14 are oriented as shown in Formula (2) (i.e., 8/3, 9a, 10/3, 13/3, 14a), and a carbon chain attached at position 17 is assumed to be /3-oriented (see Notes below). The configuration of hydrogen (or a substituent) at the ring-junction position 5 is always to be designated by adding a, /3, or ξ after the numeral 5, this numeral and letter being placed immediately before the stem name. The configuration of substituents attached at other centers of asymmetry in the tetracyclic system A—D is stated by adding a, /3, or ξ after the respective numerals denoting their position.

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Handbook o f Biochemistry and Molecular Biology

Notes: For the purpose of this Rule a carboxyl group at position 17 is not considered to constitute a carbon “chain” (for the nomenclature used see Rule 2S—4.3). For pentacyclic and hexacyclic derivatives see Rule 2S -3, and for stereochemical modi­ fications see Rule 2S—5. If two carbon chains are attached at position 17, see Notes (d) and (e) to Rule 2S-2.3. 1.6. When the configuration at position 20 in the sidechain of a pregnane derivative* is as depicted in the projection Formula (6) (i.e., a Fischer projection but with the highest number at the top), substituents shown to the right of C-20 are termed a and those to the left are termed β.

Examples:

Notes: (1) The 20a/20j3-nomenclature is continued because of long tradition. When a longer sidechain is present at C-17 the sequence-rule procedure^ is more generally convenient (see Rule 2S-1.7) and it may also be used to designate stereochemistry at C-20 in pregnanes, being particularly useful for 20-substituents that may cyclize with a substituent at another position [e.g., carboxylic acids as in Example (12)]. For 20-hydroxy-, 20-alkoxy-, 20-acyloxy-, 20-amino-, and 20-halogeno- derivatives of pregnane without a substituent on C-17 or C-21, 20a- is equivalent to (205)-, and 2Q3- to (20R)-; however, these equivalences are sometimes reversed when additional substituents are present, e.g., on C-17 or C-21, and in such cases the references below t should be consulted. *For the name “pregnane” see Rule 2S -2 .3 . ’t'Cahn, R. S., Ingold, C. K., and Prelog, V.,Angew. Chem. Int. Ed., 5, 385 (\966)\A ngew . Chem., 78, 413 (1966); for a partial simplified account see Cahn, R. S.,y. Chem. Educ., 41, 116 (1964). See also IUPAC 1968 Tentative Rules for the Nomenclature of Organic Chemistry, Sections E, Fundamental Stereochemistry, IUPAC Inf. Bull., No. 35, 71 (1969).

59

(2) When stereochemistry at C-20 is denoted by a Fischer-type projection, as in (6) to (11) or for cardenolides as (37) or bufanolides as (43), the 17,20-bond is preferably denoted by an ordinary line; the stereochemistry at C-17 is then

adequately denoted by a thick or a broken bond to the H or to the other substituent (e.g., OH) at position 17. In such formulas, representing the 17,20-bond by a thick or a broken line cannot be correct for both C-17 and C-20; this has, however, frequently been done, then involving the additional convention that the way in which this bond is written is neglected when considering the stereochemistry at C-20. 1.7. The stereochemistry at C-20 and other positions in steroid sidechains longer than ethyl is described by the sequence-rule procedure.^ Examples:

tcahn, R. S., Ingold, C. K., and Prelog, V.,Angew. Chem. Int., Ed., 5, 385(1966); Angew. Chem., 78, 413 (1966); for a partial simplified account see Cahn, R. S., J. Chem. Educ., 41, 116 (1964). See also IUPAC 1968 Tentative Rules for the Nomenclature of Organic Chemistry, Sections E, Funda­ mental Stereochemistry, I UPAC Inf. Bull., No. 35, 71, (1969). ♦For the name “cholestane” see Rule 2S -2.3. These systematic names are preferred to the trivial names given below them.

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Handbook o f Biochemistry and Molecular Biology

Notes: (1) The sequence-rule procedure is also used when the sidechain is cyclized (see Rules 2S—3.3 and 2S—3.4). (2) The backbone of a 17-side chain is best denoted as in the plane of the paper (lines of ordinary thickness), the 17,20-bond being similarly denoted. Except for pregnane derivatives, stereochemistry due to substituents on the chain is then indicated by the customary thick or broken lines denoting bonds that project, respectively, above and below the plane of the paper. FUNDAMENTAL CARBOCYCLES Rule 2S—2 (Expanded from Rules S—3.1 to S—3.5) 2.1. The parent tetracyclic hydrocarbon without methyl groups at C-10 and C-13 and without a sidechain at C-17 is named “gonane.”

2.2. The hydrocarbon with a methyl group at C-13 but without a methyl group at C-10 and without a sidechain at C-17 is named “estrane.”

Note: Names of compounds having a methyl group attached to C-10 and a hydrogen atom attached to C-13 are to be based on 18-norandrostane (see Rules 2S—2.3 and 2S-6.1) and not on 10-methylgonane. 2.3. The following names are used for the hydrocarbons (20) and (21) with methyl groups at both C-10 and C-13.

61

R

(20) 5a-Series

(21) 50-Series

H

5a-Androstane

C2H5

CH(CH3)CH2CH2CH2CH(CH3 )2 *

5a-Pregnane (.not allopregnane) 5o:-Cholane (not allocholane) 5o:-Cholestane

24t CH(CH3)CH2CH2CH(CH3)CH(CH3)2 *

5crErgostane

50-Ergostane

24+ CH(CH3)CH2CH2CH(C2 H5 )CH(CH3)2 *

5a-Stigmastane

5/?-Stigmastane

CH(CH3)CH2CH2CH3 *

50-Androstane (not testane) 50-Pregnane 50-Cholane 50-Cholestane (not coprostane)

*20R Configuration. 1245 Configuration. *24R Configuration.

Notes: (a) Unsaturation and substituents are denoted in the names of steroids by the usual methods of organic chemistry (cf. Rule 2S—4). Examples (22) to (25) illustrate some simple cases.

(b) The names “cholane,” “cholestane,” “ergostane,” and “stigmastane” imply the configuration at C-20 shown in partial Formula (26); this is (20R) except for some derivatives containing additional substituents (cf. Notes to Rule 2S—1.6).

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(c) Tetracyclic triterpenoids may be regarded as trimethyl steroids, the three additional methyl groups being numbered 30 (attached to C-4 with a configuration), 31 (attached to C-4 with β configuration), and 32 (attached to C-14); for example, 5a-lanostane (27) is 4,4,14a-trimethyl-5a-cholestane, the former name implying 14a, 20R configuration. Trivial names are common in this series of compounds, and some are illustrated in Examples (27) to (31 A).

(d) If a steroid has two carbon chains attached at position 17 and one of them is included in the table under Rule 2S—2.3, the compound is named as a 17-alkyl derivative of the steroid in the table carrying that substituent [e.g., 17-methyl-5a-pregnane (3 IB); 17-propyl-5a, 17a-cholestane (31 C)1. (e) If a steroid has two carbon chains attached at position 17, neither of which is

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included in the table under Rule 2S—2.3, the compound is named as a 17,17-disubstituted androstane [e.g., 17,17-dimethyl-5o:-androstane, (31D); 17a-methyl-17j3-propyl5a-androstane, (3IE )].

2.4. When an additional ring is formed by means of a direct link between any two carbon atoms of the steroid ring system or the attached sidechain, the name of the steroid is prefixed by “cyclo,” this prefix is preceded by the numbers of the positions joined by the new bond and the Greek letter (α, β, or ξ) denoting the configuration of the new bond, unless that designation is already implicit in the name. Examples:

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PENTACYCLIC AND HEXACYCLIC MODIFICATIONS Rule 2 S -3 (Amended Versions of Rules S—3.6 to S—3.9) 3.1. (a) The name “cardanolide” is used for the fully saturated system (37) of digitaloid lactones whose configuration is as illustrated (the configuration at position 20 is shown as a Fischer-type projection* and is the same as that in cholesterol, i.e., 20/?). Notwithstanding Rule 2S—1.5, the configuration at position 14 must always be stated as an affix to the names of these compounds. (b) Names such as “ 20(22)-cardenolide” are used for the naturally occurring unsaturated lactones of this type. (c) The names “ 14,21-” and “ 16,21-epoxycardanolide” are used for the compounds containing a 14,21- or a 16,21-oxygen bridge, respectively. Note: Statement of the configuration at C-14 for all cardanolides is a change from the earlier steroid Rules and is in line with current practice. Examples:

*This method of drawing is customary for the steroids. Since the highest-numbered atom is at the top, the usual Fischer projection has been rotated in the plane of the paper through 180°. t Denotes a trivial name; the systematic name is preferred.

65

3.2. The name “bufanolide” is used for the fully saturated system (43) of the squill-toad poison group of lactones, with the configuration at position 20 shown [this configuration is drawn as a Fischer-type projection (see Note to Rule 2S—3.1(a)) and is the same as in cholesterol, i.e., 20/?]. Notwithstanding Rule 2S-1.5, the configuration at position 14 must always be stated as an affix to the names of these compounds. Unsaturated derivatives are named by replacing the suffix -anolide by -enolide, -adienolide etc.; thus, the name “20,22-bufadienolide” is used for the naturally occurring doubly unsaturated lactones. Note: Statement of the configuration at C-14 for all bufanolides is a change from the earlier steroid Rules and is in line with current practice. Examples:*

* Denotes a trivial name; the systematic name is preferred, f Denotes a previous trivial name now considered unacceptable.

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3.3. The name “spirostan” is used for the compound of Structure (47) (this is a 16,22:22,26-diepoxycholestane); this name specifies the configurations shown for all the asymmetric centers except positions 5 and 25. A prefix 5a- or 5/3- is added in the usual way (see Rule 2S-1.5). Configurations at C-16 and C-17, if different from those shown in Formula (47), are designated as 16/3(H) and 17/3(H). Configurations at C-20 andC -22,if different from those shown in Formula (47), are designated by the sequence-rule proceduret or, if unknown, by ξ. Steric relations of substituents at C-23, C-24, C-25, or C-26 are in all cases designated by the sequence-rule procedure t or, if unknown, by if. ^Denotes a trivial name; the systematic name is preferred. ^Cahn, R. S., Ingold, C. K., and Prelog, V.,Angew. Chem. Int. Ed., 5, 385 (1966);>l«gew. Chem., 78, 413 (1966); for a partial simplified account see Cahn, R. S., J. Chem. Educ., 41, 116 (1964). See also IUPAC 1968 Tentative Rules for the Nomenclature of Organic Chemistry, Sections E, Fundamental Stereochemistry, IUPAC Informat ion Bulletin, No. 35, 71 (1969).

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Examples:

Notes: Several other methods have been used in the past for designating stereo­ chemistry at C-22 and C-25 in the spirostans and related series; all involve serious difficulties (cf. The Basle Proposals, IUPAC Information Bulletin, No. 11; also Fieser, L. F. and Fieser, M., The Steroids, Reinhold, New York, 1959, chap. 21). The sequence-rule procedure is adopted in these Rules because it gives an unequivocal symbolism. It is to be noted that, although ring E, like rings, A, B, C, and D, can conveniently be shown by projection on to the plane of the paper, yet ring F cannot be adequately represented in this way since the oxygen atom, C-26,C-24, and C-23 lie in one plane that is perpendicular to the plane of the paper. Ring F is conveniently drawn as in Formulas (47) to (51); in Formula (47), for instance, the broken line from C-22 to oxygen denotes that the oxygen atom and C-26 of ring F lie behind the plane of the paper and that consequently, C-23 and C-24 lie in front of the plane of the paper (configuration R at C-22). In partial Formula (48) the configuration at C-22 is reversed and must be stated in ♦Denotes a trivial name; the systematic name is preferred.

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the name (,S). It is conventional to draw ring F as a chair, but this conformation is not implied in the name “spirostan,” whatever the conformation of ring F, C-27 and the 25-hydrogen atom both lie in the plane of the paper and so cannot be denoted by broken or thickened lines or designated a or β. In (47) the methyl group is axial (above the general plane of ring F), and in (48) it is equatorial (in the general plane of ring F); in both these cases the configuration at C-25 is S, but this identity of R,S designation arises only because the configuration at C-22 has also been reversed between (47) and (48); a 25R configuration is shown in (51). IThe wavy lines in (49) denote unknown configurations at both C-22 and C-25. The R ,S specification may also be affected by substituents attached to ring F or C-27, as in Compounds (A) and (B).

3.4. The name “furostan” is used for the compound of Structure (52) (160,22-epoxy cholestane); this name specifies the configurations at all the asymmetric centers except positions 5, 22, and (if position 26 is substituted) also 25. Configuration at C-5 is designated by use of a or β in the usual way (see Rule 2S—1.5), and configurations at C-22 and, if necessary, C-25 by the sequence-rule procedure, or in all these cases by ξ if unknown.

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Example:

Note: Representative examples of the new standard names and old names (standard names are preferred) for some common types of spirostan, furostan and derived structures are given in Table 1 and Formulas (53) to (59).

Table 1 SPIROSTANS AND FUROSTANS Formula type

Standard name

Configurations implied in standard name

47

(255)-Spirostan

205,22/?

51

(25/?)-Spirostan

205,22/?

54 55 56

(20/?,225,255)-Spirostan (20/?,25/?)-Spirostan (22/?) (or 5 or %) (25/?) (or 5 or £)-Furostan

57

(25/?) (or 5 or £)Furost-20(22)-en

aThe standard name is preferred.

-

205

Old names (with trivial names for particular compounds in brackets)3 Sapogenin (without prefix) Neogenin 25-L-Genin [Sarsasapogenin is (53)] Isogenin 25-D-Genin [Smilagenin is (25/?)-5d-spirostan-3j3-ol; Tigogenin is (25/?)-5a-spirostan-3/3-ol] Cyclopseudoneogenin Cyclopseudoisogenin Dihydrogenin (26-ol) and dihydropseudogenin (26-ol) [Dihydrosarsasapogenin is 5/3,22^,255furostan-3/3,26-diol; dihydropseudotigogenin is (58); cf. (57).] Pseudogenin [Pseudotigogenin is (57); pseudosarsasapogenin is (59); pseudosmilagenin is (25/?)-50-furost2O(22)-en-30,26-diol].

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*The standard name is preferred.

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DERIVATIVES Rule 2 S -4 (Extended Version of Rule S -4 ) 4.1. Steroid derivatives that can be considered to be formed by modification of, or introduction of substituents into, a parent compound are named by the usual methods of organic chemistry (see IUPAC Nomenclature o f Organic Chemistry, Sections A, B, and C, 1971). Notes: For the benefit of the specialist, those rules of general substitutive nomenclature that apply most often to steroids are outlined here. For full details the IUPAC Rules cited above should be consulted. I. Unsaturation is indicated by changing terminal “-ane” to “-ene,” “ adiene,” “-yne,” etc. or “-an” to “-en,” “-adien,” “-yn,” etc.;e.g., 5a-cholest-6-ene, 5j3-cholesta-7,9(l 1)diene, 5-spirosten; see also the names of Examples (22) to (25) t II. Most substituents can be designated either as suffixes or as prefixes; a few can be named only as prefixes, the commonest of these being halogens, alkyl and nitro groups. When possible, one type of substituent must be designated as suffix. When more than one type is present that could be designated as suffix, one type only may be so expressed and the other types must be designated as prefixes. Choice for suffix is made according to an order of preference that is laid down in the Rules cited above; the most important part of this order, for steroids, is as follows, in decreasing preference: Onium salt, acid, lactone, ester, aldehyde, ketone, alcohol, amine, ether. Suffixes are added to the name of the saturated or unsaturated parent system, the terminal “e” of “-ane,” “-ene,” “-yne,” “-adiene,” etc. being elided before a vowel (presence or absence of numerals has no effect on such elisions). The following examples illustrate the use of these principles. (a) Acids. Suffix for -C H 3 -> -COOH: -oic acid, suffix for CH C-COOH: -carboxylic acid. Examples: 1 l-Oxo-5a-cholan-24-oic acid (205')-3o!-Hydroxy-5-pregnene-20-carboxylic acid

(b) Lactones, other than cardanolides and bufanolides. The ending “-ic acid” or “-carboxylic acid” of the name of the hydroxy acid i§ changed to “-lactone” or “-carbolactone,” respectively, preceded by the locant of the acid group and then the locant of the hydroxyl group: the prefix “hydroxy” is omitted for the lactonized hydroxyl group. Examples: 3/3-Hydroxy-5a-cholano-24,17a-lactone (2O/?)-30-Hydroxy-5-pregnene-20,18-carbolactone

(c) Cardanolides and bufanolides. The -olide ending of these names denotes the lactone grouping, and substituents must be named as prefixes. (d) Esters o f steroid alcohols. Special procedures are used. For esters of monohydric steroid alcohols, the steroid hydrocarbon radical name is followed by that of the acyloxy group in its anionic form. The steroid radical name is formed by replacing the terminal “e” of the hydrocarbon name by “yl” and inserting before this the locant and Greek letter, with hyphens, to designate the position and configuration.

1*For uniformity with the IUPAC Rules cited above, the conventions of Chemical Abstracts are used also in the present Rules for the position of locants (positional numerals) and designation of unsaturation. In such matters, and in use of Δ to designate unsaturation (which is not recommended by IUPAC), authors should respect the house customs of the journals to which their papers are submitted.

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Example: 5a-Cholestan-3j3-yl acetate

For esters of polyols the name of the polyol [cf. (g) below] is followed by that of the acyloxy group(s) in its anionic form, with locants when necessary. Examples: 5/3-Cholestane-3a,l 2a-diol diacetate 5|3-Cholestane-3a,12a-diol 3-acetate 12-benzoate Estradiol-17/3 17-monoacetate

When an acid, lactone or spirostan group is also present, the ester group is designated by an acyloxy prefix. Example: (25S)-3/3-Acetoxy-5j3-spirostan

(e) Aldehydes. Suffixes: -al (denotes change of —CH3 to -CHO, i.e., without change in the number of carbon atoms); -aldehyde (denotes change of —COOH to —CHO, i.e., without change in the number of carbon atoms; name derived from that of the acid). Prefix: oxo- (denotes change o f> C H 2 to > C O , thus also of —CH3 to —CHO, with no change in the number of carbon atoms). Examples: 5a-Androstan-l 9-al 5or-Cholan- 24-aldehyde 19-Oxo-5a, 17a(H)-etianic acid

Other methods are used for introduction of additional carbon atoms as —CHO groups. (f) Ketones. Suffix: -one; prefix: oxo-. Examples: 5/3-Androstan-3-one 5-Pregnene-3,20-dione ll-Oxo-5a-cholan-24-oic acid

(g) Alcohols. Suffix: -ol; prefix: hydroxy-. Examples: 5/3-Cholestane-3a, 11/3-diol 3a-Hydroxy-5a-androstan-l 7-one

Notes: (1) Composite suffixes -olone and -onol, to denote simultaneous presence of hydroxyl and ketonic groups, are not permitted by IUPAC Rules and should not be used. (2) A few trivial names exist for hydroxy ketones, such as testosterone for 17j3-hydroxy4- androsten-3-one (see Rule 2S—4.2). (h) Amines. Suffix: -amine; prefix: amino-. The suffix may be attached to the name of the parent compound or of its radical. Examples: 5- Androsten-3/3-amine or 5-Androsten-3j3-ylamine 30-(Dimethylamino)-5crpregnan-2Oa-ol

(i) Ethers. Ethers are named as alkoxy derivatives when another group is present that has priority for citation as suffix.

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Examples: 30-Ethoxy-5a-cholan-24-oic acid 17/3-Methoxy-4-androsten-3-one

When no such other group is present, ethers of steroid monoalcohols may be named by stating the name of the steroid hydrocarbon radical, followed by the name of the alkyl (or aryl, etc.) radical, and lastly by “ether;” in English these three parts of the name are printed as separate words, for example, 5a-androstan-3j3-yl methyl ether. For ethers of steroid polyols the same system may be used but with the name of the steroid hydrocarbon radical replaced by the name of the polyol; for partially etherified polyols, locant(s) precede the names of the alkyl (or aryl, etc.) group(s); for example, 5a-pregnene-3j3,17,20a-triol trimethyl ether, 5a-pregnene-3j3,17,20a-triol 3,17-dimethyl ether, cortisol 21-methyl ether. 4.2. The following are examples of trivial names retained for important steroid derivatives, these being mostly natural compounds of significant biological activity. Aldosterone Androsterone Cholecalciferol* Cholesterol Cholic acid

18,11-Hemiacetal of 11/3,2 l-dihydroxy-3,20-dioxo-4-pregnene-18-al 3a-Hydroxy-5a-androstan-l 7-one 9,10-Seco-5,7,10(19)-cholestatrien-3j3-ol (for seco see Rule 2 S -8 ) 5-Cholesten-3/3-ol 3α,7α,12a-Trihydroxy-5/3-cholan-24-oic acid

Corticosterone Cortisol Cortisol acetate Cortisone Cortisone acetate

11/3,2 l-Dihydroxy-4-pregnene-3,20-dione 1l/3,17,21-Trihydroxy-4-pregnene-3,20-dione Cortisol 21-acetate 17,2 l-Dihydroxy-4-pregnene-3,l 1,20-trione Cortisone 21-acetate

Deoxycorticosterone Ergocalciferol* Ergosterol Estradiol-17a Estradiol-17/3

21-Hydroxy-4-pregnene-3,20-dione (i.e., the 11-deoxy derivative of corticosterone) 9,10-Seco-5,7,10(19),22-ergostatetraen-3/3-ol (for seco see Rule 2 S -8 ) 5,7,22-Ergostatriene-3/3-ol 1,3,5(10)-Estratriene-3,17a-diol 1,3,5 (10)-Estratriene-3,17/3-diol

Estriol Estrone Lanosterol Lithocholic acid Progesterone Testosterone

l,3,5(10)-Estratriene-3,16a,17/3-triol 3- Hydroxy-1,3,5 (10)-estratrien-17-one 8,24-Lanostadien-3/3-ol 3a-Hydroxy-5j3-cholan-24-oic acid 4- Pregnene-3,20-dione 170-Hydroxy-4-androsten-3-one

♦Included in the List of Trivial Names for Miscellaneous Compounds of Biochemical Importance published by the IUPAC-IUB Commission of Biochemical Nomenclature: see, for example,IUPAC Inf. Bull., No. 25, 19 (1966), J. Biol Chem., 241, 2987 (1966), or Biochim. Biophys. Acta, 107, 1 (1965).

Note: If these trivial names are used as a basis for naming derivatives or stereoisomers, the derived trivial name must make the nature of the modification completely clear and is preferably accompanied at first mention by the full systematic name. For example, in steroid papers “epi” is often used with trivial names to denote inversion at one center; the name “ 11-epicortisol” defines the compound fully since cortisol is already defined as the 1 Ιβ-alcohol; but the name “epicortisol” does not define the compound and is inadequate. 4.3. Androstane-17-carboxylic acids may be called “etianic acids,” although the former (systematic) name is preferred. The orientation of the hydrogen atoms at

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positions 5 and 17 must in all cases be indicated as 5a or 5/3, and 17a(H) or 17/3(H), respectively. Examples:

STEREOCHEMICAL MODIFICATIONS Rule 2S—5 (Extended Version of Rule S—5) 5.1. If, as for instance in a synthetic compound, there is stereochemical inversion at all the asymmetric centers whose configurations do not require to be specified in a name, the italicized prefix ent- (a contracted form of enantio-) is placed in front of the complete name of the compound. This prefix denotes inversion at all asymmetric centers (including those due to named substituents) whether these are cited separately or are implied in the name. Examples:

Note: When Roman or Arabic numerals are used to enumerate formulae, the prefix ent- may be used to indicate the enantiomer. Thus, e.g., (65) above may be designated {ent- 64).

75

5.2. If there is stereochemical inversion at a minority of the asymmetric centers whose configurations do not require to be specified in a name, the configuration of the hydrogen atoms or substituents at the affected bridgeheads, or the carbon chain (if any) at position 17, are stated by means of a prefix or prefixes a or β, each with its appropriate positional numeral, placed before the stem name laid down in the preceding Rules. Examples:

Note: The prefix retro, indicating 9/3,1 Οα-configuration, is not recommended for systematic nomenclature. 5.3. The enantiomer of a compound designated as in Rule 2S—5.2 is given the same name preceded by ent-. Note: This Rule covers the compounds in which there is inversion at a majority, but not all, of the asymmetric centers that do not require to be specified in the name. Examples:

5.4. If there is stereochemical inversion at half of the asymmetric centers whose configurations are implied in the stem name of a “normal” steroid [e.g., (70)], the prefixes to be specified in the name of the stereoisomer are that set that includes the number occurring first in the series 8, 9, 10, 13, 14, 17, without or with the prefix ent- as appropriate. Configuration at asymmetric centers

Name

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Note: (72) could also logically be named “9)3,13a-androsta-5,14-diene;” this name might seem simpler, but it has the disadvantage that it does not indicate that (72) is the enantiomer of (71). 5.5. Racemates, as for instance obtained by synthesis, are named by use of an italicized prefix rac- (an abbreviation of racemo-), placed before the complete name of the compound, the enantiomer chosen for naming being that required by Rules 2S—5.1 to 2S-5.4. Example: A racemate composed of (64) and (65) ( = ^ - 6 4 ) is named: rac-170-Hydroxy-4-androsten-3-one or rac-testosterone

5.6. (a) When the relative, but not the absolute, configuration of two or more asymmetric centers in a steroid derivative is known, as for instance for a compound obtained by synthesis, the 10)3 configuration is taken as basis for the name; or, if C-10 is not asymmetric or is absent, the lowest-numbered asymmetric bridgehead is designated a (or R)\ the other asymmetric centers are then considered as a or β (or R or S) relative to that one; and the whole name is prefixed by rel- (italicized). Individual asymmetric centers may be referred to as α*, β*, R *, or S* (spoken as alpha star, R star, etc.) but these symbols are not used in the name of the compound. (b) When both enantiomers of known relative, but unknown absolute, configuration are prepared, they are distinguished by a prefix (+)-re/- or (-)-rel-, where the plus or minus sign refers to the direction of rotation of plane-polarized light (the wavelength, solvent, temperature, and/or concentration must be added when known to affect this sign).

The dextrorotatory form having either this or the enantiomeric configuration would be named: (+)-re/-17|3-Hydroxy-8a,9/3-androst-4-en-3-one

77

(74A) /*e/-(Ethyl-2-hydroxy-,4-nor-2,3-seco-5a:-gona-9,l 1,13(17), 15-tetraen-3-oate) (for seco see Rule 2 S -8 and for nor see Rule 2 S -7 ) (ο::

(74B) re/-((7/?,9aiS,9bS)-Ethyl 8,9,9a,9b-tetrahydro-6-(2-hydroxyethyl)-7//-

cyclopenta[tf ] -naphthalene-7-carboxylate ]

Note: At some stage in synthetic work on steroids, names of intermediates have to be changed from a system used in general organic chemistry to the steroid system. The names (74A) and (74B) illustrate such a change and it should be noted (i) that not merely the name but also the numbering are usually changed and (ii) that the steroid name usually avoids the need to specify the configuration at each asymmetric center. The latter factor will often indicate at what point in a synthesis the change of nomenclature is desirable. SHORTENING OF SIDECHAINS AND ELIMINATION OF METHYL GROUPS Rule 2 S -6 (Expanded from Rule S—6) 6.1. Elimination of a methylene group from a steroid sidechain (including a methyl group) is indicated by the prefix “ nor-,” which in all cases is preceded by the number of the carbon atom that disappears. When alternatives are possible, the number attached to nor is the highest permissible. Elimination of two methylene groups is indicated by the prefix “dinor-.” Examples:

Exceptions: By Rules 2S-2.1 and 2S-2.2 the names gonane (for 18,19-dinorandrostane) and estrane (for 19-norandrostane) constitute exceptions to the above Rule 2S—6.1. The names gonane and estrane are used also as parent names for their derivatives. However, 18-nor- and 19-nor- are used with other trivial names, as in 19-norpregnane, 18,19-dinorspirostan, 18-norestrone.

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The compound produced by shortening the 17-sidechain of pregnane is named 17-methylandrostane rather than 21-norpregnane, (see also Note to Rule 2S—2.2). RING CONTRACTION OR EXPANSION Rule 2 S -7 (Amended Version of Rule S -7 ) 7.1. Ring contraction and ring expansion (other than insertion of atoms between directly linked bridgeheads or, when a steroid sidechain is present, between C-13 and C-17) are indicated by prefixes “nor” and “homo,” respectively, preceded by an italic capital letter indicating the ring affected. For loss or insertion of two methylene groups, “ dinor” and “dihomo” are used. “Homo” and “ nor,” when occurring in the same name, are cited in alphabetical order.* Examples:

Notes: (a) By too extended use, this nomenclature can be applied to compounds whose steroid character is excessively modified. It is recommended that it be confined to steroids containing at least one angular methyl group, or a steroid 17-sidechain, or a *Alphabetical order is used for any combination of the prefixes cyclo, homo, nor, and seco; they are placed after any prefixes denoting substituents and before any stereochemical prefixes required by Rule 2S -1.5, or, if there are none of the latter, then immediately before the stem name.

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steroidal group on ring D (e.g., a spirostan); also that no more than two of the steroid rings may be altered by any combination of the operations denoted by “nor” and “homo.” When these conditions are not met, general systematic nomenclature should be used. (b) Names incorporating “homo” and “nor” are normally preferred to alternatives incorporating “ cyclo” and “seco” [cf. Example (86)]. 7.2. On ring contraction the original steroid numbering is retained, and only the highest number(s) of the contracted ring, exclusive of ring junctions, is deleted. Example:

7.3. On ring expansion (other than insertion of atoms between directly linked bridgeheads or, when a 17-sidechain is present, between C-13 and C-17), the letter a (and b etc. as necessary) is added to the highest number in the ring enlarged exclusive of ring junctions, and this letter and number are assigned to the last peripheral carbon atom in the order of numbering of the ring affected. Examples:

7.4. Ring expansion by formal insertion of a methylene group between directly linked bridgeheads is indicated as shown in the following table. The italic capital letters denote the ring(s) affected; the locants in parentheses (which are included in the name) are those of the inserted methylene groups. CH2 added between C-5 and C-10 C-8 and C-9 C-8 and C-14 C-9 and C-10 C-13 and C-14

Prefix used AB(10a)-Homo BC(8a)-WomQ> C(14a)-Homo B(9a)-Homo C D (13a)-H om o

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Examples:

7.5. Expansion of ring D by insertion of atoms between C-13 and C-17: The names “D-homopregnane,’' “D-homocholane,” etc. are used only for the isomer with the sidechain at position 17a [cf. Example (88)]. Isomers with the sidechain at position 17 (formed by formal insertion of a methylene group between C-13 and C-17) are named as derivatives of androstane, estrane, or gonane [cf. Example (89)]. As exceptions, furostans and spirostans into which a methylene group has been formally inserted between C-13 and C-17 are given these names with an added prefix “D(17aj-homo” [cf. Example (90)]. Examples:*

*This name is preferred to 9)3,19-cyclo-9,10-seco-5a,10a(H)-pregnane [see Note (b) to Rule 2 S -7 .1 ]. This skeleton is contained in some Buxus alkaloids.

81

RING FISSION Rule 2S—8 (Unchanged from Rule S—7.4) 8.1. Fission of a ring, with addition of a hydrogen atom at each terminal group thus created, is indicated by the prefix “seco-,” the original steroid numbering being retained.* Examples:

MODIFICATION BY BOND MIGRATION (abeo SYSTEM) Rule 2 S -9 9.1. A compound that does not possess a steroid skeleton but may be considered formally to arise from a steroid by bond migration may be given the name laid down in the preceding Rules for the steroid in question, to which is attached a prefix of the form x(y zjabeo-. This prefix is compiled as follows: A numeral denoting the stationary (unchanged) end of the migrating bond (x) is followed by parentheses enclosing (i) the number denoting the original position (y) from which the other end of this bond has migrated, (ii) an arrow, and (iii) the number (z) denoting the new position to which the * *If more than one ring is opened, general systematic nomenclature may be preferable. The principles of Note (a) to Rule 2S-7.1 apply also to seco-steroids. ^This trivial name is retained (see Rule 2S-4.2).

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bond has moved. The closing parenthesis is followed by abeo- (Latin, I go away) (italicized) to indicate bond migration. The original steroid numbering is retained for the new compound and is used for the numbers x, y, and z. Such of the customary letters as are necessary are added to specify the resulting stereochemistry. Note: The abeo nomenclature described in this Rule is permissive, not compulsory. It is most suitable for use in discussions of reaction mechanism and biogenesis. For registration in a general (nonsteroid) compendium the general systematic names may be preferable, particularly when names of steroid type can be conveniently assigned by the homo-nor method. Differences in numbering between abeo names and other systematic names should be particularly noted [cf. Example (96)]. Examples:*

**Nameaccording to Rule 2 S -7 .4 (“homo-nor” system): 9tf0-Methyl-i?/'90//-homo-,4-nor-5ar,lOor-estrane. tThe name of this compound according to Rule 2S -7 .4 (“homo-nor” system) is as follows: (4/?)4-(17a;-Methyl-Z>-homo-C-nor-18-nor-5/3-androst-17-en-17-yl)pentanoic acid, or 17-(l/?)-3-Carboxy-lmethylpropyl] -17tf-methyl-D-homo-C-nor-18-nor-5j3-androst-17-ene. *The configuration at C-9, if known, is assigned by the sequence-rule procedure. (97) cannot conveniently be named by the “homo-nor” system. tThe “homo-nor” system is not appropriate.

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HETEROCYCLIC MODIFICATIONS Rule 2S—10 (Unchanged from Rule S—7.5) 10.1. If hetero atoms occur in the ring system of a steroid the replacement (“oxa-aza”) system of nomenclature is used with steroid names and numbering (cf. IUPAC Rule B—4; also Introduction to IUPAC Rules C—0.6).** Example:

STEROID ALKALOIDS Rule 2 S -1 1 11.1 When readily possible, systematic names for steroid alkaloids are derived from pregnane or some other steroid parent name. Trivial names for other steroid alkaloids are chosen so that the name for the saturated system ends in “-anine.” In names for unsaturated compounds this ending is changed to “-enine,” “-adienine,” etc., as appropriate. When asymmetry exists at positions 8, 9, 10, 13, 14, 16, 17, 20 or 23, it is implied in the name, as set out in Table 2 and the following formulas, and divergences are designated as laid down in Rule 2S—5. Configurations at positions 5, 22, and 25 must be specified with the name. Sequence-rule symbols are used for positions numbered 20 or higher. Examples: Typical examples of parent names for groups of alkaloids are given in the table below and the corresponding formulas. It must be noted that substitution or unsaturation may alter the R ,S designations for derivatives. ^The “homo-nor” system is not appropriate. **IUPAC,Nomenclature o f Organic Chemistry, Sections A, B, and C, Butterworths, London, 1971.

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Table 2 PARENT NAMES FOR GROUPS OF STEROID ALKALOIDS3 Formula

Name of parent

100 102 103 104 105

Conanine Tomataninec Solanidanined Cevaninee Veratraninee’f

106

Jervaninee,f

Stereochemistry13 implied in the name, as shown in the formula

Stereochemistry to be indicated by sequence-rule prefixes (or ξ)

17q;H,20iS 16aH,17dH,2QS 16αΗ,17αΗ,20£ 13^Η,17αΗ,20/? 17aH,20S 1loiO ,20R

_ 22, 22, 22, 22, 22,

25 25 25 25 23, 25

aSome of the names in this table were suggested in the Introduction to O p tica l R o ta to r y Power, la S teroids, Tables des Constantes. Pergamon, Oxford, 1965, pp. 2a and 2f. ^Additional to that at positions 8, 9, 10, 13, and 14. cThe compounds are oxa-aza-analogues of the spirostans (which are dioxa spiro compounds). Formulae are conveniently drawn analogously to those of the spirostans. dThis group includes rubijervine and isorubijervane. eThese structures contain a D-homo-C-nor skeleton, with the stereochemistry shown. However, they are commonly considered as abeo structures and are numbered as such. Oervanine, as defined here, is the same as veratranine except for addition of an epoxy bridge, but it is convenient to have two separate names: the veratranine skeleton [see (105)] is present in the alkaloid veratramine. It should be noted that the name 5a-jervane has been used for the rearranged hydrocarbon skeleton (107) [Fried, J. and Klingsberg, A., J. A m . Chem . Soc., 75, 4934 (1953)], for which the a b e o -ty p e numbering given in (107) is here recommended.

H

*Cf. Haworth, R. D. and Michael, M., J. Chem. S oc., p. 4973 (1957).

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APPENDIX Guidelines for Steroids Containing Additional Rings 1. General When additional rings are formed within, or on, a steroid nucleus, situations often arise where either the resemblance to a normal steroid is obscured or the steroid-type name becomes so complex that recourse to general systematic nomenclature is preferable. On the other hand, the general rules, with one exception, are based on that form of each component that contains the maximum number of conjugated double bonds, the whole fused system is then renumbered, and the stereochemistry must be defined separately for each chiral position; the final name resulting is then cumbrous and in a form that is often barely recognizable by a steroid specialist chemist and even less so by a biochemist or biologist. The paragraphs below give suggestions as to how general nomenclature may be modified to incorporate steroid names, but without an attempt to legislate rigidly or to cover every case. The decision whether any one compound shall receive such a modified steroid name or a general systematic name is left to authors and editors in the particular circumstances of each case. Nor are the requirements of journals and compendia or abstracts necessarily identical. 2. Rings derived from functional groups. Bivalent functional groups such as - O - and - 0 —0 - linked to two different positions, thus forming additional rings, are named by the ordinary methods of organic chemistry; for example, (108) is 3a,9-epidioxy-5a-androstan17-one. Similarly, methylendioxy derivatives are best named as such, e.g., (109) 2a,3a-methylenedioxy-5-pregnene. In the same way, lactones and acetals formed by linkage between two different positions of a steroid skeleton are best named as such instead of by framing the name on the newly modified ring system.*

*Cf. Fried, J. and Klingsberg, A., J. Am. Chem. Soc., 75, 4934 (1953).

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3. Additional carbocyclic or heterocyclic fused rings. It is tempting to adapt the simple substitutive procedure for fusion of steroid nuclei with simple carbocyclic rings, particularly if the latter are saturated. Thus (110) might be named 2a,30-tetramethylene5a-androstane.* However, formation of additional rings by alkylene (— ) prefixes is not in accord with IUPAC nomenclature and is often difficult to apply when unsaturation is present. Alternatives are thus preferable.

The exceptional case (Rule A—23.5) referred to above enables 2,3-benz-5a-androst-2ene to be a name for (111), and a slight extension of the rule would allow (110) to be called 2P,3a-cyclohexano-5a:-androstane. Such methods might be used in simple cases but these too become difficult when complex ring systems are fused and often when unsaturation is present in the additional component. For a general procedure it is better to modify systematic IUPAC general practice to permit the steroid component to be cited in a reduced state, the reason why modification is necessary at all being of course the wish to keep the description of the stereochemistry as simple as possible. The suggestions below are closely similar to present practices of Chemical Abstracts. An additional carbocyclic component is cited in its most unsaturated form by its fusion name (usually ending in -o), placed in front of the name of the steroid component, and the position of fusion is indicated by numerals in square brackets; for instance, benz[2,3]-5a-androst-2-ene for (111). Here note that the unsaturation of the benzo ring causes unsaturation also in the steroid component and this must be cited (-2-ene). Similarly, (112) is naphth[2',3':2,3] -5a-androst-2-ene; the steroid A ring is still considered partially unsaturated even though it may be preferable to write the naphthalene double bonds as in the formula shown; note also that the locants for the nonsteroid component receive primes, and that, when choice is possible, its locants for ring fusion are as low as possible and in the same direction as in the steroid component (i.e., not 6\7':2,3 or 3',2':2,3).* *For simplicity, nomenclature in this Appendix is mostly described in terms of androstane, and partial formulas are to be understood accordingly. The principles, however, are general

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The reduced compound (110) is then 2/3,3a:,3',4',5',6,-hexahydrobenz[2,3]-5a-androstane. Note the citation of the configuration at the new ring junction positions and that the steroid component is now cited in its saturated state. Two further points can be illustrated with (113). Consider first the hydrocarbon where X = H. The additional ring is cited as cyclopropa- denoting an unsaturated threemembered ring as in (114). In (114) the position of the “extra” (indicated) hydrogen must be cited as 3'H. Reduction of (114) to (113; X = H) adds 2a,3a-dihydro to the name, which thus becomes 2a, 3a-dihydro-37/-cycloprop[2,3] -5a-androstane. If X were not hydrogen but, say, OH, the hydro prefixes would still be needed to show the state of hydrogenation and the OH group would be named additionally; in such cases it is preferable to state the configuration for the OH group that is present rather than that of the H atom that has been replaced; the name then becomes 2a,3-dihydro-3'//-cycloprop [2,3] -5j3-androstan-3a-ol. The same fundamental principle can be used for heterocyclic components, but conveniently modified to accord with general nomenclature as follows: (a) the heterocyclic component is cited after the steroid component (to permit modification of the ending for salt formation, etc.), and (b) the position of fusion of the heterocyclic component is cited by letters as in the standard IUPAC and Ring Index method. Thus, (115) is 2'-methyl-2,//-5a-androst-2-eno [3,2-c] pyrazole; note the numbering of the pyrazole ring so that numbers for ring fusion are as low as possible; if the methyl group in (115) were replaced by hydrogen, the double bonds would be placed in the mesomeric pyrazole ring just as in (115) so as to retain this low numbering for ring fusion. In the isomer (116) the steroid component is no longer unsaturated and is therefore cited as androstano-; the full name for (116) is l'-methyl-l7/-5a-androstano [3,2-c] pyrazole.

Further problems arise when ring fusion involves a quaternary carbon atom. The name for (117), for instance, could be built up as follows: To 5a-pregnane is fused an isoxazole skeleton, giving (118); into this, only one double bond can be introduced, so that one hydrogen atom must be added as indicated hydrogen, which gives a 4'j3H- prefix and a skeleton (119). The last step, inserting the double bond, gives the full name 4,|3//-5a-pregnano[16.\l-d] isoxazole, even though it appears in (117) as if the hetero­ cyclic ring should be named as the partly hydrogenated system isoxazoline.

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Not all such fusions cause all these complications. For instance, for (120) one fuses androstane to azirine, obtaining a skeleton into which one inserts a double bond as in the hypothetical compound (121); then, clearly, (120) is l',3'-dihydro-r-methyl-5a-androstano [5,6-6] azirine.

4. Stereochemistry. Stereochemistry in additional rings that lie in the approximate plane of rings A —D is cited as a or β, but in other cases by means of sequence-rule symbols. 5. Spiro derivatives. Spiro derivatives of steroids are named in accordance with the principles laid down in IUPAC Rules A—41, A—42, B—10, and B—11. Additional stereochemistry due to the spiro junction and substituents in the nonsteroid ring is designated by the sequence-rule procedure. Alternative names permitted by IUPAC Rules are illustrated for (122) and (123).

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NOMENCLATURE OF CYCLITOLS RECOMMENDATIONS (1973)* IUPAC Commission on the Nomenclature of Organic Chemistry and IUPAC-IUB Commission on Biochemical Nomenclature EVOLUTION OF CYCLITOL NOMENCLATURE The typical stereochemical feature of cyclitols is exemplified by Formula A, usually drawn more simply as B or C, in which the ring is considered as being planar and nearly perpendicular to the plane of the paper with hydrogen atoms and hydroxyl groups above or below the plane of the ring.

In 1900, Maquenne3 devised a fractional notation whereby numerals in the numerator denote hydroxyl or other groups (not hydrogen) above the plane of the ring while numerals in the denominator denote hydroxyl or other groups (not hydrogen) below that plane. Thus the above compound received a stereochemical prefix 1,2,4,5 which may be more conveniently printed as 1,2,4,5/3,6-. Maquenne did not, however, specify exactly how the numerals were to be assigned to the individual positions, and as the chemistry of cyclitols developed, these assignments were made in different ways. Several systems of nomenclature were proposed.4 ,s Most notably, a logical and self-consistent system was developed (but not assembled as a set of rules) by Posternak,6 and his system was widely used, though with occasional variants by others. The variety of names that resulted is illustrated in Table 1, which gives also the names derived by application of the Recommendations below. It is an advantage of the Posternak system that the resulting fractional prefix describes not only the relative positions of the substituents but also the absolute configuration of a compound; no additional prefix such as D or L, or R or S , is needed to differentiate enantiomers since pairs of enantiomers receive different fractional prefixes. This very feature, however, entails serious disadvantages. The fractional prefix gives no indication whether a compound so specified is chiral or achiral, and for a pair of enantiomers gives no indication that they have the same relative configuration, i.e., that they are enantiomers. This is contrary to the practice in the rest of chemical literature, whereby enantiomers receive identical names except for a specific prefix denoting the chirality. Also, specification of racemates becomes somewhat cumbrous by this system. An alternative method of assigning numerals, based in part on previous practice4 ’5 and on proposals made by McCasland,7 was recommended by a majority of the Joint Cyclitol Nomenclature Subcommittee, and was adopted by the parent IUPAC and IUPAC-IUB *From IUPAC Commission on the Nomenclature of Organic Chemistry and IUPAC-IUB Commission on Biochemical Nomenclature, Pure Appl. Chem., 37, 28 3 -2 9 7 (1974). With permission.

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Table 1 EXAMPLES OF CYCLITOLS NAMED BY DIFFERENT SYSTEMS3

aP-R P = FAL AG

= = = =

P-R: P: FAL: AG: Trivial name:

lD-l-O-Methyl-rayo-inositol 3-O-Methylmyoinositol L-l-O-Methyl-myo-inositol (lS)-l-O-Methyl-rayo-inositol

P-R: P: FAL: AG: Trivial name:

1L-1,2,4/3,5-Cyclohexanepentol 1,2,4/3,5-Cyclohexanepentol D-l-Deoxy-myo-inositol (1 R )-vz£>o-Quercitol (—)-Viburnitol

P-R: P: FAL: AG:

D-c/zz>o-Inositol (+)-Chiroinositol, 1,2,5/3,4,6-inositol D-Inositol (lS)-Inositol, (1S)-1,2,4/3,5,6-inositol

P-R: P: FAL: AG:

2,4,6/3,5-Pentahydroxycyclohexanone Scyllomesoinosose, mesoinosose-2 rayo-Inosose-2 scy//olnosose

P-R: P: FAL: AG:

ID-1-Amino-1-deoxy-zzeo-inositol Neoinosamine-3 L-zzeo-Inosamine-l (IS)- 1-Amino- 1-deox y-zzeo-inositol

P-R: P: FAL: AG:

DL-2-Amino-2-deoxy-epz-inositol (±)-2(4)-Amino-2(4)-deoxyepi-inositol DL-epz-Inosamine-2 (±)-2-Amino-2-deoxy-epz-inositol

(—)-Bornesitol

Present Recommendations Posternak6 Fletcher, Anderson, and Lardy4 Angyal and Gilham5

Nomenclature Commissions in 1967.1 By this method, enantiomers receive identical fractional prefixes that specify relative configuration, but they also receive an additional prefix D or L, which specifies the chirality. When the Tentative Rules were published in 1968,1 it seemed advisable to set out detailed Rules for Posternak’s system because it had been widely used in the literature up to that date. These nonpreferred Rules were, therefore, given in Part C of the Tentative Rules. However, this system has not been widely used during the past few years, and the “nonpreferred” Rules are therefore omitted from these Recommendations.

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The present Recommendations are essentially identical with the Tentative Rules, but they have been extensively rearranged in format for the convenience of their users. RECOMMENDATIONS A. Cyclitols with only Hydroxyl or Substituted Hydroxyl Groups 1. Inositols Rule 1-1. **Configuration Prefixes 1-1.1. 1,2,3,4,5,6-Cyclohexanehexols are termed generically “inositols.” Individual inositols are differentiated by use of an italicized prefix and hyphen, as follows, the locants (positional numbers) being assigned according to criteria ii. and vi. of Rule 1-4.

*1- (for Inositol) is attached to the Rule members as a general identifying prefix, tPreferred to “all-m-” in this and similar cases. The zero is inserted for clarity. **Throughout the examples, a simple vertical stroke standing alone signmes a bond to a hydroxyl group. *ftFor absolute configurational prefixes, see Rule MO.

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1-1.2. The numberings of Formulas (1) to (9) are retained for derivatives of the inositols. Within this framework, criteria iv. and v. of Rule 1-4 are used to decide between alternatives. These arise because (a) in several of the parent inositols [(1), (5), (6), (7), (8), and (9)] there are two or more fully equivalent starting points for numbering that may not be equivalent in the derivatives, and (b) criterion vi. of Rule 1-4 does not apply to chiral derivatives of the meso-inositols [(1) to (7)]. The application of criteria iv. and v. to a pair of enantiomers gives each pair of mirror-related positions the same number. Typically one enantiomer will be numbered clockwise, the other counterclockwise. 2 Other Cyclitols Rule 1-2. Trivial Names 1-2. The trivial name (+)-quercitol is permitted for lL-l,3,4/2,5-cyclohexanepentol (for derivation of this name see below). The generic name “quercitols” is abandoned.

Rule 1-3. Description of Structure 1-3. The structure of cyclitols other than the inositols are described by use of the IUPAC 1971 Rules for the Nomenclature of Organic Chemistry, Section C,8 with the proviso that cyclitols are named as substituted cycloalkanepolyols even when some or all of the hydroxyl groups are substituted. Rule 1-4. Assignment o f Locants (Positional Numbers) 1-4. Locants (positional numbers) are assigned to the carbon atoms of the ring, and thus the direction of numbering is described, with reference to the steric relations and nature of the substituents attached to the ring. The substituents lying above the plane of the ring constitute a set, and those lying below the plane another set. Lowest locants are related to one set of the substituents according to the following criteria, which are applied successively until a decision is reached: i. to the substituents considered as a numerical series, without regard to configuration; ii. if one set of substituents is more numerous than the other, to the more numerous; iii. if the sets are equally numerous and one of them can be denoted by lower numbers, to that set; iv. to substituents other than unmodified hydroxyl groups; v. to the substituent first in alphabetical order;9 vi. - for weso-compounds only—to those positions that lead to an L rather than a D designation when Rule I-10 is applied to the lowest-numbered asymmetric carbon atom. Notes: (1) “ Lowest numbers” are those that, when considered as a single ascending series, contain the lower number at the first point of difference, e.g., 1,2,3,6 is lower than 1,2,4,5. (2) Criterion vi. is needed only for compounds with weso-configuration, being

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required only for problems involving prochirality.10 It can be simply applied by noting that it causes numbering to be clockwise when the formula is oriented so that the substituent on the lowest-numbered asymmetric carbon atom of the ring projects upwards. (3) When two or more positions are fully equivalent it is immaterial which is chosen as the starting point. Rule /-5. Relative Configuration 1-5.1. The relative configurations at ring positions of a cyclitol, other than an inositol or a derivative thereof, are described by means of a fraction. The numerator of the fraction consists of the locants (assigned as described above) of the set of substituents that lies above or below the plane of the ring, these numbers being arranged in ascending order and separated by commas. The denominator contains the locants of the other set. Conventionally, the set of locants containing the lowest numbers is cited as numerator. 1-5.2. When only hydroxyl or substituted hydroxyl groups are involved, the fraction also serves as a list of locants. Its position in the name is that usually assigned to the list of locants (see examples). Note: (1) The fraction may be written with a horizontal or a sloping division line, e.g., 3^5 ^ or 152,4/3,5,6,-. Examples* (showing also which criteria of Rule 1-4 were applied):

*As exceptions to general nomenclature, but in accord with carbohydrate nomenclature, ethers and esters of cyclitols may be named either by using prefixes such as 1-O-methyl, 1-O-acetyl, etc., or by adding 1-methyl ether, 1-acetate, etc., after the name of the polyol. For simplicity, only the former alternative is used in these examples. tFor allocation of D and L to these and other enantiomers in the examples, see Rule 1-10.

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B. Cyclitols with Groups Other than Hydroxyl or Substituted Hydroxyl 1. Inositol Derivatives Rule 1-6. Trivial Names 1-6. x-Amino-x-deoxyinositols are termed generically “ inosamines,” individual compounds of this group are named according to Rule 1-7.1. Rule 1-7. Systematic Nomenclature 1-7.1. If one, two, or three hydroxyl groups of an inositol are replaced by other univalent substituents with retention of configuration, and if, according to the IUPAC 1971 Rules for the Nomenclature of Organic Chemistry, Section C,8 these substituents need not be named as suffixes; the compound is regarded as a substituted inositol and the “deoxy” nomenclature is used. The configurational prefix and the numbering of the parent inositol are retained. (For cyclitols, the most important part of the order of decreasing priority for citation as suffix is COOH and modified COOH, -Ο ,Ο Η , SH, NH2.) When this leaves alternatives criteria iv. to vi. of Rule 1-4 are applied. If a substituent that must be named as a suffix is present, the compound is named according to Rules 1-8 and 1-9. 1-7.2. Inositol derivatives in which one carbon atom carries a substituent additional to a hydroxyl are named as substituted inositols, provided that the substituent does not rank above hydroxyl for citation as suffix. (If it does, Rule 1-9.2 applies.) For the disubstituted position in such compounds the configurational prefix refers to the hydroxyl group.

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2. Other Cyclitols Role 1-8. Trivial Names 1-8. 2,3,4,5,6-Pentahydroxycyclohexanones are termed generically “ inososes;” the individual compounds are named according to Rule 1-9. The trivial name (—)-quinic or L-quinic acid is preferred for the following compound (see the last example to Rule 1-9):

Rule 1-9. Systematic Nomenclature 1-9.1. Cyclitols containing substituents other than hydroxyl or modified hydroxyl (excepting inositols covered by Rule 1-7) are named and numbered according to the above-mentioned IUPAC Rules, with the proviso that (9-substituents are named as such (see Rule 1-3). Substituted hydroxyl groups are not named as alkoxy, aryloxy, or acyloxy groups. When these rules leave alternatives available, the criteria ii. to vi. of Rule 1-4 are applied. Relative configuration is indicated as prescribed in Rule 1-5.1. Except when it is serving as a locant set, the fraction describing the configuration is placed in parentheses, and it becomes the first element in the name, except for the configurational prefix (Rule H O ). * *IUPAC Rule C-502 is compatible with a name lL-6-0-methyl-l-thio-c^z>o-inositol but that name does not accord with the instruction in Rule 1-7.1 to use the “deoxy” nomenclature. tThe prefix C- is added to denote substitution on carbon in accordance with carbohydrate nomenclature.1 1

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Notes: (1) The IUPAC Rule C-108 provides that one type of group be chosen as suffix, named as suffix, and given the lowest possible number(s), the remaining types being named as prefixes. For choice of suffix, see the penultimate (parenthetical) sentence in Rule 1-7.1. (2) When there are substituents other than hydroxyl groups, it is usually impracticable to use the fraction describing the relative configuration as a list of locants. In stipulating that, in such cases, the fraction be placed in front of the complete name of the compound (including O-substituents), the present Recommendations differ from the Tentative Rules. 1-9.2. Cyclitol derivatives in which one carbon atom carries a substituent additional to hydroxyl are named (a) as substituted cycloalkanepolyols or (b) as hydroxy derivatives, according as a substituent (a) does not or (b) does rank above hydroxyl for citation as suffix. When the Rule leaves alternatives available, the criteria ii. to vi. of Rule 1-4 are applied. For the disubstituted positions in such compounds, the fractional prefix refers to the hydroxyl group and this may be specified for clarity where necessary. Note: Replacement of the hydrogen of amino, mercapto, or hydroxyl groups by other atoms or groups does not change the numbering of cyclitol derivatives except when it affects criterion iv. or v. of Rule 1-4. However, the IUPAC Rules8 require that the ring carbon atom carrying as a substituent a trisubstituted ammonio (R 3N+)> acid, oxo, cyano, or acyl group, or a derivative thereof, receive the locant 1; such cases will be relatively rare in cyclitol chemistry. A convenient alternative for “ onium” salts is to use the terminology exemplified by methiodide, hydrochloride, sulfate, etc. Examples:

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C. Absolute Configuration Rule 1-10. Absolute Configuration I-10. The absolute configuration of a cyclitol is specified by making a vertical Fischer-Tollens type of projection of the structure, with C-l at the top and with C-2 and C-3 on the front edge of the ring. The configuration is then designated as D if the hydroxyl group at the lowest-numbered chiral center (or other substituent if no hydroxyl group is present there) projects to the right, and as L if it projects to the left (of Figure 1). The prefix D or L, followed by a hyphen, is written before the name of the compound and may be preceded by the locant of the defining center. Racemic compounds are designated by the prefix DL.

FIGURE 1.

Notes: (1) The mere absence of a prefix D, L, or DL indicates that the compound has a m eso -configuration; thus, the prefix D, L, or DL should not be omitted. (2) A simple way of applying this Rule is as follows: When the formula is drawn in such a way that the substituent on the /owesi-numbered asymmetric carbon atom is above the plane of the ring, and the numbering is clockwise, the compound is L; if anti-clockwise, it is D [see Examples (8) and (9)]. (3) In a great majority of cases the lowest-numbered chiral center is position 1, so that it would be reasonable that D or L should be preceded by the locant of the defining

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center only when it is not 1. However, according to another nomenclature system for cyclitols4 and also for the related carbohydrate field, the symbols D and L are assigned to the highest-numbered chiral center, which sometimes gives symbols different from those assigned according to Rule MO. It is, therefore, recommended that the numeral 1 be included (as in these Recommendations). (4) Small Roman capital letters should be used in print for D and L. For compounds containing cyclitols and protein or carbohydrate residues, Dc and Lc (c for cyclitol) may be used alongside D§, L§, D g , and Lg . 12 Cyclitol nomenclature may also be combined with the use of the sequence rule2 or the stereospecific numbering (sn) system,13 where necessary. (5) When many hydroxyl groups are replaced by other substituents, it may be simpler to use the sequence rule.2 Sequence-rule examples are given in Table 1, also in Reference

2.

Examples: Many examples of chiral compounds are named in the preceding examples [e.g., (11) to (16) and (26) to (29)]. The following are additional.

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REFERENCES 1.

2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

IUPAC-IUB, IUPAC Information Bulletin No. 32, 51 (1968); Eur. J. Biochem., 5, 1 (1968); Arch. Biochem. Biophys., 128, 269 (1968); J. Biol. Chem., 243, 5809 (1968); Biochem. J., 112, 17 (1969); Biochim. Biophys. Acta, 165, 1 (1968); Hoppe-Seyler's Z. Physiol. Chem., 350, 523 (1969) (German language version); Bull. Soc. Chim. Biol., 51, 3 (1969) (French language version). Cahn, R. S., Ingold, C., and Prelog, N.^Angew. Chem., 78, 413 (1966);Angew. Chem. Int. Ed., 5, 385 (1966); IUPAC 1968 Tentative Rules, Section E, / Org. Chem., 35, 2849 (1970). Maquenne, L., Les Sucres et leur Principaux D irivis, Gauthiers-Villars, Paris, 1900; also Georges Carr£ et C. Naud, Paris, 1900. Fletcher, H. G., Jr., Anderson, L., and Lardy, H. A .,/. Org. Chem., 16, 1238 (1951). Angyal, S. J. and Gilham, P. T., J. Chem. Soc., 3691 (1957). Posternak, T., The Cyclitols, Hermann, Paris, 1965. McCasland, G. E.,Adv. Carbohydr. Chefri., 20, 11 (1965). IUPAC Definitive Rules for Nomenclature o f Organic Chemistry, Section C, 2nd ed., Butterworths, London, 1971. IUPAC Definitive Rules for Nomenclature o f Organic Chemistry, Section C, 2nd ed., Butterworths, London, 1971, Rule C-16.3. Hanson, K. R., /. Am. Chem. Soc., 88, 2731 (1966). IUPAC-IUB, IUPAC Information Bulletin No. 7, Carbohydrate Nomenclature-1, IUPAC, Oxford, 1 9 7 0 ;/ Biol. Chem., 247, 613 (1972). IUPAC, J. Am. Chem. Soc., 82, 5575, (1960). IUPAC-IUB, Eur. J. Biochem., 2, 127 (1967); Biochem. J., 105, 897 (1967).

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TENTATIVE RULES FOR CARBOHYDRATE NOMENCLATURE PART 1 (1969)* IUPAC Commission on the Nomenclature of Organic Chemistry (CNOG) and IUPAC-IUB Commission on Biochemical Nomenclature (CBN) PREAMBLE Scope of the Rules These Rules deal with the acyclic and cylic forms of monosaccharides and their simple derivatives; oligasaccharides are also dealt with briefly. Carbohydrate chemistry continues to provide a very fruitful field of research, such that it will be necessary, in the near future, to promulgate further Rules to cover the needs of developing areas, e.g., branched-chain and unsaturated monosaccharides, other carbohydrate acyclic and heterocyclic derivatives, conformational problems, and poly­ saccharides. Use of the Rules These Rules are additional to the Definitive Rules for the Nomenclature of Organic Chemistry1 and are intended to govern those aspects of the nomenclature of carbohydrates not covered by those rules. 1. The Structure Named These Rules are designed to name first a parent monosaccharide represented in the Fischer projection of the acyclic form and then its cyclic forms and derivatives. The numbering system used in monosaccharides is based on the location of the (potential) carbonyl group. Modification of that group or introduction of further similar groups can therefore often destroy the uniqueness of the numbering system and permit a derivative to be named from more than one parent. In order to determine the unique systematic name of a derivative it is important to follow the procedure of establishing the Fischer projection of the appropriate parent monosaccharide, naming that according to the Rules, and thereafter deriving the name of any derivative. 2. Conventional Representations a. The Fischer projection — In this representation of a monosaccharide, the carbon chain is written vertically with carbon atom number 1 at the top. The groups projecting to left and right of the carbon chain are considered as being in front of the plane of the paper. The optical antipode with the hydroxyl group at the highest-numbered asymmetric carbon atom on the right is then regarded as belonging to the D-series. It is now known that this convention represents the absolute configuration. b. The Haworth representation — The Haworth representation of the cyclic forms of monosaccharides can be derived from the Fischer projection, as follows. The monosaccha­ ride is depicted with the carbon-chain horizontal and in the plane of the paper, the potential carbonyl group being to the right. The oxygen bridge is then depicted as being formed behind the plane of the paper. The heterocyclic ring is therefore located in a plane approximately perpendicular to the plane of the paper and the groups attached to the carbon atoms of that ring are above and below the ring. The carbon atoms of the ring are not shown. *l:rom IUPAC Commission on the Nomenclature of Organic Chemistry and IUPAC-IUB Commission on Biochemical Nomenclature, IUPAC Inf. Bull. Append. Tentative Nomencl. Sym. Units Stand., No. 32, August 1973. With permission.

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Groups that appear to the right of the vertical chain in the Fischer projection (A and D below) then appear below the plane of the ring in the Haworth representation (B, C, and E below). However, at the asymmetric carbon atom (C-5 in A; C-4 in D) involved via oxygen in ring formation with the carbon atom of the carbonyl group, a formal double inversion must be envisaged to obtain the correct Haworth representation. In the pyranose forms of D-aldohexoses C-6 will always be above the plane. In the furanose forms of D-aldohexoses the position of C-6 will depend on the configuration at C-4; it will, for example, be above the plane in D-glucofuranoses (e.g., C) but below the plane in D-galactofuranoses (e.g., E): Examples:

3. The Reference Carbon Atom and the A no meric Prefix a. The reference carbon atom - This is defined as the highest-numbered asymmetric carbon atom in the monosaccharide chain. b. The anomeric prefix - In a definitive name, the anomeric prefix (a or β) relates the configuration at the anomeric (or glycosidic) center to that of the reference carbon atom. The anomer having the same orientation, in the Fischer projection, at the anomeric carbon atom and at the reference carbon atom is designated a; the anomer having opposite orientations, in the Fischer projection, is designated β. The anomeric prefix (a or β) can only be used in conjunction with, and having the above-defined relation to, the configurational prefix (D or L) denoting the configuration at the reference carbon atom. Further, it may be used only when the locant of the anomeric center is smaller than that of the reference carbon atom.

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4. Numbering o f Monosaccharides The basic principle for the numbering of monosaccharides gives the (potential) carbonyl group the lower of the possible numbers (cf. Rule Carb-4). This numbering system is usually retained even when a modification introduces a group which, on the basis of general organic chemical nomenclature, would have priority over the (potential) carbonyl group [e.g., in uronic acids the (potential) carbonyl group retains locant one, despite the normal priority of the carboxyl group]. In ketoaldonic acids, the carboxyl group that replaces the original (formal) aldehyde group retains the locant one. 5. New Asymmetric Centers Not infrequently, derivatives of monosaccharides contain asymmetric carbon atoms not present in the parent monosaccharide. Examples include benzylidene derivatives, certain other acetals, ortho ester structures, etc. When the stereochemistry at such a carbon atom is known it will be indicated in the name by use of the appropriate Sequence Rule symbol, R or S? BASIS OF NOMENCLATURE Rule Carb-1 The basis for the naming and numbering of a monosaccharide or monosaccharide derivative is the structure of the parent monosaccharide (CnH2nOn), represented in the Fischer projection of the acyclic form. Choice of Parent Structure Rule Carb-2 If, in naming a derivative, a choice of parent monosaccharide is possible, the selection of parent is made according to the following order of preference, treated in the order given until a decision is reached. (a) The monosaccharide, of which the first letter of the trivial name (Rule Carb-5), or of the configurational prefix, or of the first cited configurational prefix of a systematic name (Rule Carb-8), occurs earliest in the alphabet. If two possible parents have the same initial letter, then the choice will be made according to the letter at the first point of difference in the trivial name, the configurational prefix of the systematic name, etc. Examples: Allose before glucose, glucose before gulose, alio- before gluco-,gluco- before gulo-. (b) The configurational symbol D- before L-. (c) The monosaccharide which gives the point(s) of modification of the CH(OH) chain the lowest locant(s).* (d) The monosaccharide which gives the lowest locants* to the substituents, present in the derivative. (e) The monosaccharide which, when the substituents have been placed in alphabetical order, results in the first-cited substituent having the lowest locant.* Trivial and Systematic Names Rule Carb-3 In naming monosaccharides or monosaccharide derivatives, either trivial or systematic names can be used for the parent monosaccharide. * Lowest locants are defined as follows: When a series of locants containing the same number of terms are compared term by term, that series is “lowest” which contains the lowest number on the occasion of the first difference (see IUPAC, Nomenclature o f Organic Chemistry, Section C, 1965, p. 23, footnote).

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Trivial names are defined in Rule Carb-5. Systematic names are formed by adding one or more configurational prefixes (Rule Carb-8) to the appropriate stem name (Rule Carb-6). Rule Carb-4 The names “aldose” and “ketose” are used in a generic sense to denote monosac­ charides in which the (potential) carbonyl group is terminal (aldehydic) or nonterminal (ketonic), respectively. In an aldose, the carbon atom of the (potential) carbonyl group is atom number one; in a ketose it has the lower number possible. Rule Carb-5 The trivial names of the acyclic aldoses with three, four, five, or six carbon atoms are retained, and are used in preference to their systematic names for the aldoses and for the formation of names of their derivatives. The trivial names of these aldoses are Triose:

Glyceraldehyde (glycerose is not recommend­ ed) Tetroses: Erythrose, threose Pentoses: Arabinose, lyxose, ribose, xylose Hexoses: Allose, altrose, galactose, glucose, gulose, idose, mannose, talose

Rule Carb-6 The “stem names” of the acyclic aldoses having three, four, five, six, seven, eight, nine, ten, etc., carbon atoms in the chain are triose, tetrose, pentose, hexose, heptose, octose, nonose, decose, etc. The “stem names” of the acyclic ketoses having four, five, six, seven, eight, nine, ten, etc., carbon atoms in the chain are tetrulose, pentulose, hexulose, hepulose, actulose, nonulose, deculose, etc. Configurational Symbols and Prefixes Rule Carb-7 Configurational relationships are denoted by the symbols D and L which in print will be small capital roman letters and which are not abbreviations for “dextro” and “laevo.” Racemic forms may be indicated by D L. Such symbols are affixed by a hyphen immediately before the monosaccharide trivial name (Rule Carb-5) or before each configurational prefix (Rule Carb-8) of a systematic name, and are employed only with compounds that have been related definitely to the reference standard glyceraldehyde (see Rule Carb-8). The configurational symbol should not be omitted, if known. If the sign of the optical rotation under specified conditions is to be indicated, this is done by adding (+) or (-). Racemic forms may be indicated by (±). With compounds optically compensated intramolecularly the prefix “meso” is used where appropriate. Examples: D-Glucose or D(+)-glucose, D-fructose or D(-)-fructose, DL-glucose or (±)-glucose. Rule Carb-8 The configuration of a ^>CHOH group or a set of two, three, or four contiguous >CHOH groups (or wholly or partly derivative groups, such as >CHOCH3, >CHOCOCH3 , or ^C H N H 2) is designated by the appropriate one of the following configurational prefixes, which are (except for glycero-) derived from the trivial names of the aldoses mentioned in Rule Carb-5. When used in systematic names these prefixes are to be uncapitalized and are italicized in print. They are affixed by a hyphen to the stem

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name defined in Rule Carb-6. There may be more than one configurational prefix in a name. Each prefix is D or L according to whether the configuration at the reference carbon atom in the Fischer projection is the same as, or the opposite of, that in D(+)-glyceraldehyde. Only the Fischer projections of the D-prefixes are given below; X is the group with the lowest-numbered carbon atom(s). One >CHOH group:

Two ^>CHOH groups:

Three >CHOH groups:

Four >CHOH groups:

The systematic name for a monosaccharide is then formed by using the configurational symbols and prefixes with the appropriate stem name (Rule Carb-6).

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For sets of more than four contiguous >CHOH groups see Rule Carb-9. The trivial names, which are preferred, of the acyclic aldoses with four to six carbon atoms (Rule Carb-5) thus corresponds to the following systematic names. Trivial

Systematic

O-erythro-Tetiose

D -E ry th ro se D -T h re o se

D-r/zra?-Tetrose

D -A ra b in o se D -L y x o s e

D -/yxo-Pentose

O-arabino-?entose

D -R ib o s e

D -n& o-Pentose

D -X y lo s e

D -xy/o-Pentose

D -A llo se

D-tf//oHexose

D -A ltro se D -G alacto se

O-altro-Hexose D-galacto-Hexose

D -G lu co se

D-g/w co-Hexose

D -G u lo se D -Id o se D -M a n n o se

D-^w/o-Hexose D -/do-H exose

D -T alose

D-ta/o-hexose

D-manno-hexosQ

Note: (Anglo-American Usage). Since 1952, usage in the United States and the United Kingdom has been based on a different significance for configurational prefixes in that they have been related to a sequence of consecutive but not necessarily contiguous asymmetric groups. Examples:

N and M are each a single nonasymmetric carbon center or a sequence of nonasymmetric carbon centers. Ketoses and Deoxysaccharides. Prefixes with this significance were used when N is the methylene group of a deoxy compound or the keto group of a ketose containing not more than four asymmetric carbon centers, but not the keto group of higher-sugar ketose. Examples: Names according to this usage are given in notes to the subsequent Rules. Multiple Configurational Prefixes Rule Carb-9 An acyclic monosaccharide containing more than four contiguous asymmetric carbon atoms is named by adding two or more prefixes, together indicating the configurations at all the asymmetric carbon atoms, to the stem name defined in Rule Carb-6. The configurational prefixes employed are given in Rule Carb-8. The sequence of (4n + m\ where n is 1 or more and m is 0, 1, 2, or 3) asymmetric carbon atoms is divided, beginning at the asymmetric carbon atom next to the functional group, into (n) sets of

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four asymmetric carbon atoms, and a final set (m) of less than four. The order of citation of these prefixes commences at the end farthest from carbon number one. The locants corresponding to the configurational prefixes may be inserted in the name, if desired. In such cases, all locants are given and immediately precede the appropriate configurational prefixes. Examples:

Comment. Compounds that require multiple configurational prefixes but which do not necessarily contain more than four contiguous asymmetric carbon atoms are covered by Rule Carb-10 (ketoses) and Carbon-14 (deoxysaccharides). KETOSES

Rule Carb-10 Ketoses are classified as 2-ketoses, 3-ketoses, etc., according to the position of the (potential) carbonyl group (see Rule Carb-4). The systematic name of an individual ketose is obtained by affixing, before the stem name (Rule Carb-6) and by means of a hyphen, the locant of the (potential) carbonyl group. The locant is preceded by the configurational prefix or prefixes (Rule Carb-8) for the groups of asymmetric centers present. If more than one configurational prefix is needed, the order of their citation commences at the end farthest from carbon atom number one. The locant two may be omitted from the name of a 2-ketose when no ambiguity can arise.* When the carbonyl group is at the middle carbon atom of a ketose containing an uneven number of carbon atoms in the chain two names are possible. That name will be selected as accords with the order of precedence given in Rule Carb-2. *In this text, the locant is always retained for the sake of clarity.

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Examples:

The following are examples of nonsystematic names of ketoses that are established by usage and may be retained. D-Ribulose for D-Xylulose for Sedoheptulose for

O-erythro-2-Fentu\ose D-fftra)-2-Pentulose D-fl/iro-2-Heptulose

D-Fructose for D-Psicose for D-Sorbose for D-Tagatose for

Ό-arab ino- 2-Hex ulose D-rz6o-2-Hexulose D-xy/o2-Hexulose D-/yxo-2-Hexulose

DIKETOSES Rule Carb-11 Monosaccharide derivatives containing two (potential) ketonic carbonyl groups have the general name diketose. The systematic name of an individual diketose is derived by the use of the termination “odiulose” in place of the termination “ulose” characteristic of the monoketose (Rule tName according to Anglo-American usage: Ό-arabino-3-Hexulose.

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Carb-6). The locants of the (potential) carbonyl groups are the lowest possible numbers (see Rule Carb-4) and are inserted together with a hyphen before the stem name. They are in turn preceded by configurational prefixes, the latter as prescribed in Rules Carb-8 and Carb-9. The order of citation of these prefixes commences at the end farthest from carbon atom number one. Note. It sometimes happens that, when the carbonyl groups are symmetrically placed along the carbon chain, two systematic names are possible; that name is selected as accords with the order of precedence given in Rule Carb-2. Examples:

ALDOKETOSES Rule Carb-12 Monosaccharide derivatives containing a (potential) aldehyde carbonyl group and a (potential) ketonic carbonyl group have the general name aldoketose. Names of individual aldoketoses are formed in the same way as those of diketoses, but by the use of the termination “osulose” in place of the termination “ose” of the corresponding aldose (Rule Carb-6). The carbon atom of the (potential) aldehydic carbonyl group is numbered one, and this locant is not cited in the name. The locant of the (potential) ketonic carbonyl group is given unless it is two; it may then be omitted.*** Examples:

*Name according to Anglo-American usage: D-r/tm>-2,4-Hexodiulose. f Name according to Anglo-American usage: L-tf/fro-4,5-Octodiulose. **In this text, the locant is always retained for the sake of clarity. ttN am e according to Anglo-American usage: l>0ra6mo-3-Hexulose.

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Comment: 2-Aldoketoses have also been named as “osones” but this practice is not recommended. DIALDOSES Rule Carb-13 Monosaccharide derivatives containing two (potential) aldehydic carbonyl groups have the general name “dialdose.” Names of individual dialdoses are formed in the same way as those of diketoses, but by the use of the termination “odialdose” in place of the termination “odiulose.” Locants are not needed. Examples:

DEOXY-MONOSACCHARIDES AND AMINO-MONOSACCHARIDES Rule Carb-14 (a) The replacement of an alcoholic hydroxyl group of a monosaccharide, or monosaccharide derivative, by a hydrogen atom is expressed by using the prefix “deoxy,” preceded by the appropriate locant and followed by a hyphen together with a systematic or trivial name (Rule Carb-3). The systematic name consists of a stem name with such configurational prefixes as express the configurations at the asymmetric centers present in the deoxy-compound. The order of citation of the configurational prefixes commences at the end farthest from carbon atom number one. A trivial name may be used only if the transformation of the saccharide into the deoxy-compound does not alter the configuration at any asymmetric center.* *The prefix meso- may precede the name of such symmetrical compounds for the sake of the clarity.

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Trivial names of 6-deoxy-hexoses established by usage may be retained and used for the formation of names of derivatives. Examples:

The following is established as a trivial name for biochemical use: Deoxyribose for 2 -deoxy-D -ery thro -pe nt o se. (b) The replacement of an alcoholic hydroxyl group of a monosaccharide, or monosaccharide derivative, by an amino group is envisaged as substitution of the appropriate hydrogen atom of the corresponding deoxy-monosaccharide by the amino group. Substition in the amino group is indicated by use of the prefix TV(Rule Carb-15) unless the substituted amino group has a trivial name (for example: CH3CONH-, acetamido). The stereochemistry at the carbon atom carrying the amino group is expressed according to Rule Carb-8.* *Name according to Anglo-American usage: 3-Deoxy-D-rz6o-hexose.

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Trivial names accepted for biochemical usage: D-Gaiactosamine for D-Glucosamine for D-Mannosame for Neuraminic acid for Muramic acid for

2-Amino-2-deoxy-D-galactopyranose (the name chondrosamine is not recommended) 2-Amino-2-deoxy-D-glucopyranose 2-Amino-2-deoxy-D-mannopyranose 5- Amino-3,5-dideoxy-a-O-glyceroD-gtf/tfCfo-2-nonulopyranosonic acid 2-Amino-3-O-[ l-(S)-carboxyethyl] 2-deoxy-aldehydo-D-glucose

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When the complete name of the derivative includes other prefixes, “deoxy” takes its place in the alphabetical order* of detachable prefixes; in citation the alphabetical order is preferred to numerical order. Examples: 4-Amino-4-deoxy-3-0-methyl-D-e/*yr///O-2-pentulose 4-Deoxy-4-(ethylamino)-D-e/'yr/i/O-2-pentulose

0-SUBSTITUTION Rule Carb-15 Replacement of the hydrogen atom of an alcoholic hydroxyl group of a saccharide or saccharide derivative by another atom or group is denoted by placing the name of this atom or group before the name of the parent compound. The name of the atom or group is preceded by an italic capital letter 0 (for oxygen), followed by a hyphen in order to make clear that substitution is on oxygen. The 0 prefix need not be repeated for multiple replacements by the same atom or group. Replacement of hydrogen attached to nitrogen or sulfur by another atom or group is indicated in a similar way with the use of italic capital letters N or S (for examples see Rules Carb-24 and Carb-36). The italic capital letter C may be used to indicate replacement of hydrogen attached to carbon, to avoid possible ambiguity.* Examples:

Rule Carb-16 (Alternative to Rule Carb-15) 0-Substitution products of saccharides or saccharide derivatives may be named as esters, ethers, etc., following the procedures prescribed for that purpose in IUPAC, Nomenclature o f Organic Chemistry, Section C, 1965. Examples:

See IUPAC, Nomenclature o f Organic Chemistry, Section C, 1965, Rules C-16.1 and C-16.4.

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ACYCLIC FORMS Rule Carb-17 The acyclic nature of a monosaccharide or monosaccharide derivative containing an uncyclized carbonyl group may be stressed by inserting the italicized prefix “aldehydo” or “k e t o respectively, immediately before the configurational prefix(es) or before the trivial name. These prefixes may be abbreviated to “0/” and “fce.” Examples:

Name according to Anglo-American usage: 2,4,5,6-Tetra-(>methyl-fceto-D-tfra&//70-3-hexulose.

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RING SIZE IN CYCLIC FORMS Rule Carb-18 The size of the ring in the cyclic form of a monosaccharide (aldose or ketose) or monosaccharide derivative may be indicated by replacing the terminal letters “se” of the name of the acyclic form by “furanose” for the 5-atom ring, “pyranose” for the 6-atom ring, and “septanose” for the 7-atom ring. Rule Carb-19 (Alternative to Rule Carb-18) The size of the ring in the cyclic form of a monosaccharide (aldose or ketose) or monosaccharide derivative may be indicated by two numerals, placed in parentheses, and joined to the end of the name of the acyclic compound by a hyphen. These numerals denote the two carbon atoms to which the ring oxygen atom is attached, the carbon atom of the potential carbonyl group being cited first. Rule Carb-20 For cyclic forms of ketoses, diketoses, dialdoses, and aldoketoses, the names constructed according to Rule Carb-18 may, when necessary, be followed by a pair of numerals, these numerals having the same significance as in Rule Carb-19. Comment. Examples of the application of Rules Carb-18 to Carb-20 are given in Rules Carb-21 to Carb-23. The system of Rule Carb-18 is preferred, but that of Rule Carb-19 is advantageous in special cases. ANOMERS Rule Carb-21 The free hydroxyl group belonging to the internal hemiacetal grouping of the cyclic form of a monosaccharide or monosaccharide derivative is termed the “anomeric” or “glycosidic” hydroxyl group. The two cyclic forms of an aldose or ketose, or aldose or ketose derivative (termed anomers), are distinguished with the aid of the anomeric prefixes a and ft relating the con­ figuration at the anomeric carbon atom to that at the reference asymmetric carbon atom of the compound; the anomer having the same configuration, in the Fischer projection, at the anomeric and the reference carbon atom is designated a. The anomeric prefix, a or ft followed by a hyphen, is placed immediately in front of the configurational symbol, D or L, of the trivial name or of the configurational prefix denoting the group of asymmetric carbon atoms that includes the reference carbon atom (see Preamble, paragraph 3). Examples:

f (a), (b), and (c), here and subsequently, refer to names coined in terms of Rules Carb-18, Carb-19,

and Carb-20, respectively.

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Rule Carb-22 With ketones that have the (potential) carbonyl group located between two ^>CHOH groups, each separated from the carbonyl group by two, three, or four carbon atoms of the chain, ring-closure may take place towards either end of that chain. Likewise, with dialdoses, diketoses and aldoketoses ring-closure may take place from either (potential) carbonyl group towards the center of the chain. In each case both cyclic forms have the same monosaccharide parent that dictates the basis of the name and numbering of each form (cf. Rule Carb-2). In one form the locant of the anomeric or glycosidic hydroxyl group is lower than that of the reference carbon atom; that cyclic form is named according to Rules Carb-18 and Carb-21. In the other the locant of the anomeric or glycosidic hydroxyl group must be higher than that of the reference carbon atom. This precludes (see Preamble, paragraph 3) the use of a and β to define the two anomers (Rule Carb-21), and the appropriate Sequence Rule sym bol,^ or S (see Preamble, paragraph 5), must be used, in place of a or β, to indicate the configuration at the anomeric carbon atom.* *Name, according to Anglo-American usage: 3-Deoxy-a-D-tfraZ?z>20-hexofuranose.

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Examples:

11)

GLYCOSIDES Rule Carb-23 Mixed acetals, resulting from the replacement of the hydrogen atom of the anomeric or glycosidic hydroxyl group by a group X, derived from an alcohol or phenol (XOH), are named “glycosides.” The term “glycoside” is used in a generic sense only, and may not be applied to specific compounds. Glycosides are named by replacing the terminal “e” of the name of the corresponding cyclic form of the saccharide or saccharide derivative by “ide” and placing before the word thus obtained, as a separate word, the name of the group X.

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Examples:

GLYCOSYL RADICALS AND GLYCOSYLAMINES Rule Carb-24 (a) The radical formed by detaching the anomeric or glycosidic hydroxyl group from the cyclic form of a monosaccharide or monosaccharide derivative is named by replacing the terminal ‘e’ of the name of the monosaccharide or monosaccharide derivative by “yl.” The general name of these radicals if “glycosyl” (glycofuranosyl, glycopyranosyl, glycoseptanosyl) radical.

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Examples: r

(b) The replacement of the glycosidic hydroxyl group of a cyclic form of a monosaccharide derivative by an amino group is indicated by adding the suffix “amine” to the name of the glycosyl radical. Example:

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GLYCOSYLOXY RADICALS Rule Carb-25 The radical formed by removal of the hydrogen atom from the anomeric or glycosidic hydroxyl group of the cyclic form of a monosaccharide or monosaccharide derivative is named by replacing the terminal “e” of the name of the saccharide by “yloxy.” Examples:

ALDITOLS Rule Carb-26 (a) Names for the polyhydric alcohols (alditols) of the saccharide series are derived from the names of the corresponding acyclic aldoses by changing the suffix “ose” to “itol.” If the same alditol can be derived from two different aldoses preference is given to that name which accords with the order of precedence given in Rule Carb-2. Examples:

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Note. Names such as “mannite” for mannitol are deprecated. (b) To the trivial names of alditols optically compensated intramolecularly, which have no D- or L -prefix, the prefix meso- may be added for the sake of clarity. Examples: me so-try thritol, meso-ribitol, meso-xylitol, meso-allitol, raeso-galactitol. The prefixes D and L must however be used (i) in the names of meso-alditols containing more than four contiguous asymmetric carbon atoms in order to define the steric relation of the configurational prefixes cited and (li) in naming derivatives of meso-alditols that have become asymmetric by substitution. Examples:

co-DEOXYALDITOLS Rule Carb-27 The name of an aldose derivative having a terminal CH3 and CH2OH group is derived from that of the appropriate alditol (Rule Carb-2) by use of the prefix “deoxy.”

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Examples:

ALDONIC ACIDS Rule Carb-28 Monocarboxylic acids formally derived from aldoses, having three or more carbon atoms in the chain, by oxidation of the aldehydic group, are named aldonic acids, and are divided into aldotrionic acid, aldotetronic acids, aldopentonic acids, aldohexonic acids, etc., according to the number of carbon atoms in the chain. The names of individual compounds of this type are formed by replacing the ending “oso” of the systematic or trivial name of the aldose by “onic acid.” Derivatives of these acids formed by change in the carboxyl group (salts, esters, lactones, acyl halides, amides, nitriles, etc.,) are named according to the IUPAC Nomenclature of Organic Chemistry, Section C, 1965, Rule C-4. Examples:

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KETOALDONIC ACIDS Rule Carb-29 Keto-carboxylic acids formally derived by oxidation of a secondary alcoholic hydroxyl group of an aldonic acid have the general name ketoaldonic acids. The carbon atom of the carboxyl group is numbered one. Names of individual ketoaldonic acids, or of the glycosides derived from such compounds, are formed by replacing the ending “ose” or “oside” of the appropriate ketose, or of the glycoside derived there from, by 44osonic acid” or 44osidonic acid,” respectively. Derivatives of these acids formed by modifying the carboxyl group (salts, esters, lactones, acyl halides, amides, nitriles, etc.,) are named according to the IUPAC Nomenclature of Organic Chemistry, Section C, 1965, Rule C-4. Examples:

*Name according to Anglo-American usage: Methyl 3-deoxy-LW7zreo-pentonate. ^Name according to Anglo-American usage: 3-Deoxy-D-n^o-hexono-l,5-lactone.

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Comment. Parentheses are suitably inserted where it is necessary to distinguish between an ester alkyl group and the hemiacetal alkyl group of a glycoside of a ketoaldonic acid.

URONIC ACIDS Rule Carb-30 The monocarboxylic acids formally derived by oxidation of the terminal CH2OH group of aldoses having four or more carbon atoms in the chain, or of glycosides derived from these aldoses, to a carboxyl group are named “uronic acids.” The names of the individual compounds of this type are formed by replacing (a) the “ose” of the systematic or trivial name of the aldose by “uronic” acid or (b) the “oside” of the name of the glycoside by “osiduronic acid.” *Name according to Anglo-American usage: D-flrfl6mo-3-Hexulosonic acid.

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The carbon atom of the (potential) aldehydic carbonyl group (not that of the carboxyl group) is numbered one. Derivatives of these acids formed by change in the carboxyl group (salts, esters, lactones, acyl halides, amides, nitriles, etc.,) are named according to IUPAC, Nomen­ clature o f Organic Chemistry, Section C, 1965, Rule C-4. Examples:

*Name according to Anglo-American usage: 2,5-Dideoxy-tfWe/zy 4 )-2

-am ino-2-deoxy-Q !-D -glucopyranose

Trisaccharides and Higher Oligosaccharides Rule Carb-40 (a) Nonreducing. A nonreducing trisaccharide is named as a glycosylglycosyl glycoside, from its component monosaccharide parts. Higher nonreducing oligosaccharides are named similarly. Between the name of one glycosyl radical and the next are placed two locants which indicate the respective positions involved in this glycosidic union; these locants are separated by an arrow (pointing from the locant corresponding to the glycosyl carbon atom to the locant corresponding to the hydroxylic carbon atom involved) and are enclosed in parentheses. Example:

(b) Reducing. A reducing trisaccharide is named as a glycosylglycosylglycose, from its component monosaccharide parts. Higher reducing oligosaccharides are named similarly.

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Examples:

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Handbook o f Biochemistry and Molecular Biology

REFERENCES 1. International Union of Pure and Applied Chemistry, Nomenclature o f Organic Chemistry, Sections A and B, Butterworths, London, 1957 (2nd ed. 1966); Section C, Butterworths, London, 1965. Editorial note: Section A and B are also to be found in J. Am. Chem. Soc., 82, 5545 (1960); Section C in Pure Appl. Chern, 11, Nos. 1 and 2 (1965). 2. Chan, R. S., Ingold, C. K., and Prelong, \.,A g n e w Chem., 78, 413 (1966);Agnew Chem. Int. Ed., 5, 385 (1966); IUPAC Tentative Rules for the Nomenclature of Organic Chemistry, IUPAC Inf. Bull., 35, 71 (1969); [see also/fur. /. Biochem., 18, 151 (1971)].

Carbohydrates

None (meso) None None None None (meso)

2 5 1 -2 5 2 25,34

C3 2h 2 2n 4 o , 6

c 4 h 10o 2

C12H is 0 8 c 8 h 180 4

11 8-120 85

c 4 h 10 o 4

15

9egp

13 13

6rib (2)

5 3rib (2)

5rib (2)

24rib (2)

(F)

ELC

14.1 (3) 13.2(6) 26xyll (7) 28.5 (14)

3.00(11)

4.69 (3) 3.60 (6) 8xyll (7) 5.94 (8)

(G)

GLC

5 5 f (12)

2 3 f (4)

3 5 f (12)

32f (4)

(H)

PPC

Chrom atography, R value, and reference^

5 I f (5)

8 0 f (5)

6 7 f (35t)

62f (5)

(I)

TLC

aIn order of increasing carbon chain length in the parent compounds grouped in the classes - alditols, inositols, inososes, amino alditols, and inosamines. k[a] p for 1—5 g solute, c, per 100 ml aqueous solution at 20—25°C unless otherwise given. References for melting point and specific rotation data. Letter indicates the reference also has chromatographic data according to: c = column, e = electrophoresis, g = gas, p = paper, and t = thin-layer. dR value times 100, given relative to that of the compound indicated by abbreviation: f = solvent front, gal = galactose, glc = glucose, glcl = glucitol, glen = glucosamine, myol= myo-inositol, perl = perseitol, pinl = pinitol, rib = ribose, sorl = sorbitol, sue = sucrose, xyll = xylitol, (as the pentaacetate or the pentamethyl ether, as pertains), and aral = arabinitol (as the pentaacetate). Under gas chromatography (Column GLC or G) numbers without code indication signify retention time in minutes. The conditions of the chromatography are correlated with the reference given in parentheses and are found in Table 5. eSaid to exist as a phosphate ester also.10 fData given are for the enanthiomorphic isomer. gThe author names as 3-dehydroquinic acid, but it is actually 5-dehydroquinic. hThe early given name, /-quercitol, of this compound does not make it the enanthiomorph of d-quercitol; other isomeric relations are involved. lrThis compound is isomeric with the previous one in regard to the TV-methyl group position.

Erythritol Tetraacetate Tetramethyl ether Trimethylsilyl ether Tetrakis-(pnitrobenzoate) 1,4-Dideoxy-ery thritol (2,3-butyleneglycol)

125-126

C j ,H , 4N20 8 9egp

9egp 1,10

None Racemic

c 6 h 14 o 3

c , h 14 o 6

190-192 Oil, bp 188— 189

Alditols

(E)

^•14^1 7N3O1 2 c 3h 8o 3

(D)

Reference0

1 1 1

c 3h 8 o 3

Glycerol (glycerine) Triacetate Trimethyl ether Trimethylsilyl ether 7Ws-(o-nitrobenzoate) l-Deoxyglycerole (1,2propanediol, propylene glycol) Bis-(p- nitr obenzoate)

(C)

M d

Specific rotation

None (meso) None None

(B)

(A)

Melting point °C

20 4 Oil, bp 148

Chemical formula

Substance3 (synonym) derivative

Table 1 NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

139

C18H16N20 8

£w-(p-nitrobenzoate)

Pentaacetate Pentamethyl ether Trimethylsilyl ether Ribitol (adonitol) Pentaacetate 102 51

L l s H22O10 C5H120 5

Cs HJ20 5 C15H22O10

76 101-102

C18H16N20 8 C4H10O2 C8H140 4 C5H120 5

7 2 -7 3

Oil, bp ca 170 141-143 7.6 41—41.5 103

C4H10O2

C15H22O10 Ct 0 H2 2 0 5

219—221f

(0.05 mm) 2 1 8 -2 2 0

C32H22N40 16

C18H180 4

8 8 -8 9 Oil, bp 145

77 19 Oil, bp 1 9 2 194 (745 mm) 142-144

Melting point °C (C)

None (meso) None

+52 (CHC13) Racemic Racemic +7.8 (c 8, borax solution) +37.2 (CHC13) -7.2 (c 9, borax solution) -3 2 (c 0.4, 5% molybdate)

+12.4

acetone)

+87.2 (c 0.4,

-52.7 ± 0.5(c 4 , CHC13) -4.5 -3 2 (C 2H5OH)

-13 +1.4

Alditols (continued)

Specific rotation*3 [a] D (D)

33 34

30

29

27 28p, 30cp

18 24 24 25

18

23

22p

19,22p

18

16 15 17

Reference0 (E)

76rib (2)

124rib (2)

96rib (2) 45xyllf (21)

ELC (F)

44.4 (6) 105xyll (7) 40glcl (32) 39.9(3) 40.0(6)

38.1 (3)

38.1(3)

27.5f (14)

GLC (G)

14f (4)

14f(4)

144glcf (20)

PPC (Η)

37f (26)

7 0 f(3 1 )

32f (26)

TLC (I)

Handbook o f Biochemistry and Molecular Biology

ifcs-(/?-nitr obenzoate) 1.4- Dideox y-DL-threitol Diacetate D-Arabinitol (DaraDitol) Pentaacetate L-Arabinitol

Tetra-(pnitrobenzoate) 1.4- Dideoxy-L-threitol

Trimethylsilyl ether Di-O-benzylidene ether

C4H10O6 C12H18O10

C18H180 4 C4H10O2 C8H140 4

Dibenzoate 1.4- Dideoxy-D-threitol Diacetate

L-Threitol Tetraacetate

Chemical formula (B)

Substancea (synonym) derivative (A)

Chromatography, R value, and reference**

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

140

Tetraacetate D-Mannitol 1-acetate Ό-glycero-D-galacto-

(styra ch ito l)

Hexaacetate Hexamethyl ether Trimethylsilyl ether 1.5- A n h y d r o -D - m a n n it o l

D -M a n n it o l

6 6 -6 7 124-125 183-185,188

157

C6H12Os

C14H20O9 C8H160 7 C7H160 7

126

7 3 -7 4 73.5 121.5 166

C14H20O9 C6 H, 4 0 6 C18H260 12 C6H140 6

C18H260 12 Cj 2 H26 0 6

140-141

78 112 99

167.5-168.5

186-187

6 1,9 2 .5 93.5 6 2 .5 -6 3

Melting point °C (C)

C6H12Os

2H26 0 6

C18H260 12 C12H260 6 C24H620 6Si6 C6H140 6 C18H260 1 2

Hexaacetate Hexamethyl ether Trimethylsilyl ether D-Glucitol (sorbitol) Hexaacetate

Hexamethyl ether Trimethylsilyl ether 1.5- Anhydro-D-glucitol (polygalitol) Tetraacetate L-Iditol Hexaacetate

C6H140 6

C15H22O10 C10H22O5

Cs H120 5

C10H22Os

Chemical formula (B)

Pentaacetate Pentamethyl ether Trim ethylsilyl ether Galactitol (dulcitol)

Pentamethyl ether Trimethylsilyl ether Xylitol

Substancea (synonym) derivative (A)

-20.9 (C2H5OH) +4 -1.1

-49.9

+38.9 (CHC12) -3.5 (c 10) -25.7 (CHC13) -0.21 +16 (5% molybdate) +18.8 (acetic acid)

+42.4

None None None -1.8 (15°) +12.5 (c 0.8, CHC13)

None None None None (meso)

None None None (meso)

Alditols (continued)

Specific rotation^ [a] D (D)

51 52cp 53,54

49

42 43 43,45 46 29 47,48

42

84 39 40,41

37g

37e

36

28,36

Reference0 (E)

140rib (2)

130rib (2)

173rib (2)

161rib(2)

145rib (2)

155rib (2)

ELC (F)

127.2(6) 284xyll (7) 9.46 (8)

153xyllf (21) 38.1(3)

246xyll (7) 27 (32)

144.4(6)

144.4(6) 388xyll (7) 12.47 (38)

52.8 (6) 100xyll(7) 46myol (84)

60xyll (7) 32.8, 38.5 (35g) 30.3(3)

GLC (G)

lOOperl (55a)

8f(4>

92sorl (44)

8f (4)

7f (4)

14f(4)

PPC (Η)

Chrom atography, R value, and reference^

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

"

83f (50a)

2 7 f(5 )

22f (5)

24 f(5 )

92f (351) 26f(26)

TLC (I)

141

Asteritol (an inositol monomethyl ether) Betitol (a dideox y inositol)

Octitol Octaacetate

Ό-ery thro- D-galacto-

D-glycero- D-mannoHeptitol (D-glyceroD-ta/o-heptitol, volemitol) Heptaacetate D-erythro-

Heptaacetate Heptabenzoate L-glycero- D-zrfo-Heptitol Heptaacetate D-glycero-

D -glycero -O -ido -U eptitol

perseitol) Heptaacetate Ό-glycero - D-g/uco-Heptitol (L-glycero - O-taloheptitol, βsedoheptitol) Tri-O-methylene/3-sedoheptitol

Heptitol (L-glyceroD -m an n o -h eptitol,

Substance2 (synonym) derivative (A)

-14 (CHC13) +46 (5% molybdate)

-23.3 (c 0.4, CHCI3)

Sublimes 130, 276-278d

+24.5 (5% molybdate)

4

7h 14o 6

c 6H 12o

c

C24H 34 0 16

Sublimes, melts 164 224

9 9 -1 0 0

+157 (c 0.01)

Inositols

61

60

55

55c

-11 (5% molybdate)

C jH ,, 0 , · H7 0

0Oi 4

+2 (CHCI3)

58,59

+36.1 (CHCI3)

62

^2 1

169-170

58 29

+2.6 +55 (5% molybdate)

4

4

153

^ 2 1^ 3 0 0 ,

C ,H 160 ,

^ ■ 5 6 ^ 4 4 ^ 1

c 7 h 16 o 7

57 57c 57

57c

56

53 55c

29

+24 (CHCI3) None (meso) None

0 .0

Reference0 (E)

Alditols (continued)

W D (D)

Specific rotation”

119-120.5 131-132

Melting point °C (C)

180-181 111- 112 175-176

^"2 1 ^ 3 0 ^ 1 4

c 7h 16 o 7

C ,0HI6 0 7

c , h 16 o 7

C 2 i H 3 0 ° i 4

Chemical formula (B)

140rib (2)

168rib (2)

17lrib (2)

(F)

ELC

719aral (57b)

621aral (57b)

GLC (G)

32f (60)

83perl (55a)

74gal (57a)

7 8 -8 2 gal (57a)

>120suc (55b)

PPC (H)

Chromatography, R value, and reference4*

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

(I)

TLC

142 Handbook o f Biochemistry and Molecular Biology

Dambonitol ( 1,3-di-O methyl-mjO-inositol) Tetraacetate I>Inositol [d-inositol, chiro- (+)-inositol, (+)-inositol, DcfaVo-inositol] Hexaacetate Hexabenzoate L-Inositol [/ inositol, /eyo-inositol, chiro(-)-inositol] Hexaacetate Trimethylsilyl ether D,L-Inositol Hexaacetate Hexabenzoate

Trimethylsilyl ether L-Bornesitol (1-Omethyl L-myo-inositol) Pentaacetate Conduritol (a 2,3dehydro-2,3-dideoxyinositol) Dihydro conduritol Tetraacetate

D-Bomesitol (O-myoinositol monomethyl ether) Pentaacetate

Substance2 (synonym) derivative (A)

62

+11.8 (c 0.8, acetone)

138-139

C i 7H240 h

+64.5 -64.1

21 5-2 2 0 2 52-253 247

96 253 111 213

Ci 8H240 i 2

Cl 8^2 4 D| 2

6h 12o 6

6

c

48h 360 i 2

C i 8H240 i 2

c

C 48R 36D j c 6H 12o 6

c 6H 12o

Racemic None None

77 77 78cp

1

74 74,75 l,76p

23rib (2)

83glc (82)

71c 72c, 73 74

None +60,+65 +68

202 246-247d 230-235

C i 6H24O io

2

Ogle (82)

69,70

8h 16o . None (meso)

c

68 68

204 bp 165 (0.6 mm) 206,210

6h 12o 4 C14H18 D 4 None None

64 67

-11.2 (CHCI3) None (meso)

142-143,157 142-143

Ci 7H240 , , C6HI 0O4

c

63,65cp

-32.1

15glc (82)

20rib (2)

(F)

ELC

2 05-206

c

7h I 4o 6

62

Inositols (continued)

(E )

+31.4

Reference0

201-202

c

d

(D)

H

7h 14o 6

Specific rotation^

Melting point °C (C)

Chemical formula (B)

9.62 (93)

82myol (84)

8.27 (93)

86myol (84)

GLC (G)

49pinl (132)

1 7 f 1 2 f (72, 74)

2 0 f (70)

19glc (66)

PPC (H)

Chrom atography, R value, and reference*1

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

TLC (I)

143

Trimethylsilyl ether «eo-Inositol Hexaacetate Laminitol (6-C-methylmyo inositol) Hexaacetate Leucanthemitol (a dehydro dideoxy inositol) Dihydroleu canthemitol Liniodendritol (1,4-diO-methyl-myoinositol) Tetraacetate Mytilitol (a C-methylscy//oinositol) Hexaacetate d-Ononitol [(+)-ononitol, 4-O-methyl-L-myo inositoll

myo-Inositol (mesoinositol) Hexaacetate

Pentabenzoate

Trimethylsilyl ether l-0-Methyl-(+)-inositol Pentaacetate l-O-Methyl-mueoinositol Pentaacetate

Substancea (synonym) derivative (A>

bp ca 200 (vac) Amorphous 9 5 -1 0 0 22 5 -2 2 7 2 0 6 -2 0 8 221 -2 1 3 118-119 314 251 -2 5 3 2 2 6 -2 6 9 153 13 1-13 2

161 224 139 259 180-181 172

Cl 7H140 6

C18H240 1 2

C24H60O6Si6

C6HI 20 6 C18H240 12 C7H140 6

C19H260 12 C6H10O4

C6H120 4

C8H160 6

C16H24O10 C7H140 6

C19H260 12 C7H140 6

C6H, 20 6

C4 2H34° n

2 0 7 -2 0 8 110.5-111.5 Gum

Melting point °C (C)

C7H140 6 C^H^O^ C7H140 6

Chemical formula (B)

None (meso)

+60.7 +29.1 (CHC13)

None +6.6

-24 None (meso)

-25

-4 0

-19.6 + 1 (CHC13) +101.5

-3

None

Reference0 (E)

92 64

91 92

66,91

90

88 89,90

85,86 86cpt 87c, 88cp

83cp 85 84g

72p

80

80

75 75 80cp,81

Inositols (continued)

Specific rotation*5 [a] D (D)

6Ogle (82)

< lOsorl (94)

83glc (87a)

43rib (2)

16rib (2)

30glc (80)

32glcf (82)

ELC (F)

9.17(93)

10.3,24.3 (8, 79)

13.42 (93)

13.3 (79)

GLC (G)

32f(66)

52glc (66)

27f(87c) 8 5 -8 0 f(8 9 )

10f(87b)

2f (4)

109pinl (81)

PPC (Η)

Chromatography, R value, and reference**

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

79f (50a)

27f (50b;

TLC (I)

144 Handbook o f Biochemistry and Molecular Bioloev

T rim e th v lsilv l e th e r

280d C18H26N2O 10 342-345d

Chemical formula (B) ELC (F)

GLC (G)

PPC (Η)

Chrom atography, R value, and reference^

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

TLC (I)

149

1 50

Handbook o f Biochemistry and Molecular Biology

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES REFERENCES 1.

2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56.

Pollock and Stevens, Dictionary o f Organic Compounds, O x f o r d U n iv e rsity Press, N e w Y o r k , 1965. Frahn and Mills, Aust. /. Chem., 12, 65 (1959). Dooms, Declerck, and Verachtert, J. Chromatogr., 42, 349 (1969). Bourne, Lees, and Weigel, J. Chromatogr., 11, 253 (1963). de Simone and Vicedomini, J. Chromatogr., 37, 538 (1968). Sawardeker, Sloneker, and Jeanes, Anal. Chem., 37, 1602 (1965). Whyte, / Chromatogr., 87, 163 (1973). Roberts, Johnston, and Fuhr,Anal. Biochem., 10, 282 (1965). Dutton and Unrau, Can. J. Chem., 43, 924, 1738 (1965). Lindberg, Ark. Kemi. Mineral. Geol., 23, A 2 (1946-1947). Weatherall,/. Chromatogr., 26, 251 (1967). Boreck^ and Gasparic, Collect. Czech. Chem. Commun., 25, 1287 (1960). Bamberger and Landsiedl, Monatsh. Chem., 21, 571 (1900). Dutton, Gibney, Jensen, and R eid,/. Chromatogr., 36, 152 (1968). Ward, Pettijohn, Lockwood, and Coghill, J. Am. Chem. Soc., 66, 541 (1944). Ciamician and Silber, Ber. Dtsch. Chem. Ges., 44, 1280 (1911). Morell and Auernheimer, /. Am. Chem. Soc., 66, 792 (1944). Rubin, Lardy, and Fischer,/. Am. Chem. Soc., 74, 425 (1952). Bertrand, C. R. Acad. Sci., 130, 1472 (1900). Batt, Dickens, and Williamson, Biochem. J., 77, 272 (1960). Oades, /. Chromatogr., 28, 246 (1967). Hu, McComb, and Rendig, Arch. Biochem. Biophys., 110, 350 (1965). Dutton and Unrau, /. Chromatogr., 20, 78 (1965). Wilson and Lucas, /. Am. Chem. Soc., 58, 2396 (1936). Asahina and Yanagita, Ber. Dtsch. Chem. Ges., 67, 799 (1934). Nemec, Kefurt, and JarΫ,/. Chromatogr., 26, 116 (1967). Frfcrejacque, C. R. Acad. Sci., 208, 1123 (1939). Onishi and Suzuki, Agric. Biol. Chem., 30, 1139 (1966). Richtmyer and Hudson, /. Am. Chem. Soc., 73, 2249 (1951). Touster and Harwell, /. Biol. Chem., 230, 1031 (1958). Grasshof,/. Chromatogr., 14, 513 (1964). Dutton, Reid, Rowe, and R ow e,/. Chromatogr., 47, 195 (1970). Wessely and Wang, Monatsh. Chem., 72, 168 (1938). Binkley and Wolfrom, /. Am. Chem. Soc., 70, 2809 (1948). Gregory, /. Chromatogr., 36, 342 (1968). Wolfrom and Kohn, /. Am. Chem. Soc., 64, 1739 (1942). Wells, Pittman, and Egan, /. Biol. Chem., 239, 3192 (1964). Horowitz and Delman, /. Chromatogr., 21, 302 (1966). Von Lippmann, Ber. Dtsch. Chem. Ges., 60, 161 (1927). Haas and Hill, Biochem. J., 26, 987 (1932). Jeger, Norymberski, Szpilfogel, and Prelog, Helv. Chim. Acta, 29, 684 (1946). Richtmyer, Carr, and Hudson, /. Am. Chem. Soc., 65, 1477 (1943). Bertrand, Bull. Soc. Chim. Fr. Ser. 3, 33, 166 (1905). Britton, Biochem. J., 85, 402 (1962). Perlin, Mazurek, Jaques, and Kavanagh, Carbohydr. Res., 7, 369 (1968). Braham,/ Am. Chem. Soc., 41, 1707 (1919). Patterson and Todd, /. Chem. Soc. (L o n d .), p. 2876 (1929). Iwate, Chem. Zentralbl, 2, 177 (1929). Zervas, Ber. Dtsch. Chem. Ges., 63, 1689 (1930). Hay, Lewis, and Smith, /. Chromatogr., 11, 479 (1963). Asahina, Ber. Dtsch. Chem. Ges., 45, 2363 (1912). Lindberg, Acta Chem. Scand., 7, 1119, 1123 (1953). Jones and Wall, Nature, 189,746 (1961). Maquenne, Ann. Chim. Phys. Ser. 6, 19, 5 (1890). Charlson and Richtmyer, /. Am. Chem. Soc., 82, 3428 (1960). Buck, Foster, Richtmyer, and Zissis, / Chem. Soc. (Lond.), p. 3633 (1961).

151

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES

57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 83. 84. 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100. 101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 111. 112. 113. 114.

Onishi and Perry, Can. J. Microbiol., 11, 929 (1965). Bougault and Aliard, C. R. Acad. Sci., 135, 796 (1902). Maclay, Hann, and Hudson, J. Org. Chem., 9, 293 (1944). Ackerman, Hoppe-Seyler’s Z. Physiol. Chem., 336, 1 (1964). Von Lippmann, Ber. Dtsch. Chem. Ges., 34, 1159 (1901). King and Jurd, /. Chem. Soc. (Lond.), p. 1192 (1953). Bien and Ginsburg,/. Chem. Soc. (Lond.), p. 3189 (1958). Pilouvier, C.R. Acad. Sci., 241, 983 (1955). Post and Anderson, J. Am. Chem. Soc., 84, 478 (1962). Angyal and Bender, J. Chem. Soc. (Lond.), p. 4718 (1961). Kiibler, Arch. Pharm., 246, 620 (1908). Dangschat and Fischer, Naturwissenschaften, 27, 756 (1939). DeJong, Reel. Trav. Chim. Pays-Bas, 27, 257 (1908). Kiang and Loke, J. Chem. Soc. (Lond.), p. 480 (1956). Angyal, Gilham, and MacDonald, J. Chem. Soc. (Lond.), p. 1417 (1957). Ballou and Anderson, J. Am. Chem. Soc., 75, 648 (1953). Umezawa, Okami, Hashimoto, Suhara, Hamada, and Takeuchi, J. Antibiot. Ser. A, 18, 101 (1965). Dzhumyrko and Shinkaxenko, Chem. Nat. Compd. (USSR), 7, 638 (1971). Foxall and Morgan, / Chem. Soc. (Lond.), p. 5573 (1963). Smith, Biochem. J., 57, 140 (1954). Tanret, C. R. Acad. Sci., 145, 1196 (1907). Cosgrove, Nature, 194, 1265 (1962). Lee and Ballou,/. Chromatogr., 18, 147 (1965). Adhikari, Bell, and Harvey, /. Chem. Soc. (Lond.), p. 2829 (1962). Utkin, Chem. Nat. Compd. (USSR), 4, 234 (1968). Angyal and McHugh, /. Chem. Soc. (Lond.), p. 1423 (1957). Lindberg, Acta Chem. Scand., 9, 1093 (1955). Loewus, Carbohydr. Res., 3, 130 (1966). Allen,/. Am. Chem. Soc., 84, 3128 (1962). Cosgrove and Tate, Nature, 200, 568 (1963). Lindberg and Wickberg, Ark. Kemi, 13, 447 (1959). Posternak and Falbriard, Helv. Chim. Acta, 44, 2080 (1961). Kindi, Kremlicka, and Hoffman-Ostenhof, Monatsh. Chem., 97, 1783 (1966). Plouvier, C. R. Acad. Sci., 255, 360 (1962). Plouvier, C. R. Acad. Sci., 241, 765 (1955). Ackermann, Ber. Dtsch. Chem. Ges., 54, 1938 (1921). Krzeminski and Angyal,/. Chem. Soc. (Lond.), p. 3251 (1962). Bourne, Hutson, and Weigel,/. Chem. Soc. (Lond.), p. 4252 (1960). Maquenne, Ann. Chim. Phys. Ser. 6, 22, 264 (1891). Anderson, Fischer, and MacDonald,/. Am. Chem. Soc., 74, 1479 (1952). Pease, Reider, and Elderfield, /. Org. Chem., 5, 198 (1940). Plouvier, C. R. Acad. Sci., 243, 1913 (1956). Anderson, Takeda, Angyal, and McHugh, Arch. Biochem. Biophys., 78, 518 (1958). DeJong, Reel. Trav. Chim. Pays-Bas, 25, 48 (1906). Adams, Pease, and Clark, / Am. Chem. Soc., 62, 2194 (1940). Haustveit and Wold, Carbohydr. Res., 29, 325 (1973). Bourne, Percival, and Smestad, Carbohydr. Res., 22, 75 (1972). Prunier, Ann. Chim. Phys. Ser. 5, 15, 5 (1878). McCasland, Naumann, and Durham, Carbohydr. Res., 4, 516 (1967). Bauer and Moll, Arch. Pharm., 280, 37 (1942). Plouvier, C. R. Acad. Sci., 253, 3047 (1961). Gorter, Annchem, 359, 221 (1908). Haslam, Turner, Sargent, and Thompson,/. Chem. Soc. (Lond.), p. 1493 (1971). Ervigand Koenigs, Ber. Dtsch. Chem. Ges., 22, 1457 (1889). Weiss, Davis, and Mingioli,/. Am. Chem. Soc., 75, 5572 (1953). Adlersberg and Sprinson, Biochemistry, 3, 1855 (1964). Shyluk, Youngs, and Gamborg, /. Chromatogr., 26, 268 (1967). Muller,/. Chem. Soc. (Lond.), p. 1767 (1907).

152

Handbook o f Biochemistry and Molecular Biology

Table 1 (continued) NATURAL ALDITOLS, INOSITOLS, INOSOSES, AND AMINO ALDITOLS AND INOSAMINES 115. Posternak, Helv. Chim. Acta, 25, 746 (1942). 116. Ueno, Hasegawa, and Tsuchiya, Carbohvdr. Res., 29, 520 (1973). 117. Sherrard and Kurth, / Am. Chem. Soc., 51, 3139 (1929). 118. Eijkman, Ber. Dtsch. Chem. Ges., 24, 1278 (1891). 119. Eijkman, Reel. Trav. Chim. Pays-Bas, 4, 32 (1885). 120. McCrindle, Overton, and Raphael, J. Chem. Soc. (Lond.), p. 1560 (1960). 121. Grewe, Buttner, and Burmeister, Angew. Chem., 69, 61 (1957). 122. Salamon and Davis, J. Am. Chem. Soc., 75, 5567 (1953). 123. Horii, Iwasa, Mizuta, and Kameda, J. Antibiot. Ser. A, 24, 59 (1971). 124. Power and Tutin, J. Chem. Soc. (Lond.), p. 624 (1904). 125. Angyal, Gorin, and Pitman, J. Chem. Soc. (Lond.), p. 1807 (1965). 126. Posternak and Schopfer, Helv. Chim. Acta, 33, 343 (1950). 127. Nakajima and Kurihara, Ber. Dtsch. Chem. Ges., 94, 515 (1961). 128. Angyal, Gorin, and Pitman, / Chem. Soc. (Lond.), p. 1807 (1965). 129. Stanacevand Kates, / Org. Chem., 26, 912 (1961). 130. Posternak, Helv. Chim. Acta, 19, 1333 (1936). 131. Magasanik and Chargaff, / Biol. Chem., 175, 929 (1948). 132. Post and Anderson, / Am. Chem. Soc., 84, 471 (1962). 133. Magasanik and Chargaff, / Biol. Chem., 174, 173 (1948). 134. Berman and Magasanik, / Biol. Chem., 241, 800 (1966). 135. Stevens, Gillis, French, and Haskell,/. Am. Chem. Soc., 80, 6088 (1958). 136. Johnson, Gourlay, Tarbell, and Autrey, J. Org. Chem., 28, 300 (1963). 137. Nakajima, Kurihara, Hasegawa, and Kurokawa, Justus Liebigs Ann. Chem., 689, 243 (1965). 138. Bannister and Argoudelis, / Am. Chem. Soc., 85, 119 (1963). 139. Allen, / Am. Chem. Soc., 78, 5691 (1956). 140. Patrick, Williams, Waller, and Hutchings, / Am. Chem. Soc., 78, 2652 (1956). 141. Walker and Walker, Biochim. Biophys. Acta, 170, 219 (1968). 142. Carter, Dark, Lytle, and McCasland, / Biol. Chem., 175, 683 (1948). 143. Peck, Hoffhine, Peel, Graber, Holly, Mozingo, and Folkers, / Am. Chem. Soc., 68, 776 (1946). 144. Nakajima, Hasegawa, and Kurihara, Justus Liebigs Ann. Chem., 689, 235 (1965). 145. Maeda, Murase, Mawatari, and Umezawa, / Antibiot. Ser. A, 11,73 (1958). 146. Neuss, Koch, Malloy, Day, Huckstep, Dorman, and Roberts, Helv. Chim. Acta, 53, 2314 (1970). 147. Kondo, Sezaki, Koika, and Akita,/. Antibiot. Ser. A, 18, 192 (1965). 148. Peck, Graber, Walti, Peel, Hoffhine, and Folkers, / Am. Chem. Soc., 68, 29 (1946). 149. Nakajima, Kurihara, and Hasegawa,/ter. Dtsch. Chem. Ges., 95, 141 (1962). 150. Horii and Kameda,/. Chem. Soc. D Chem. Commun., 746, 747 (1972).

c 3h 6 o 4

Gum

66-68 102

80

(C)

dextro

None None

None

(D)

W d

Specific rotation**

Aldonic Acids

Melting point °C

6

1 1

1,5c

(E)

Reference0

48C1 (2)

(F)

ELC

10.45MU (3)

(G)

GLC

85f (8)

(H )

PPC

55f (4)

75f (4)

(I)

TLC

Chrom atography, R value, and referen ced

Value is in cm/24 h. mValue is in cm /1.5 h. nSome workers relate the formula Cl 2 H21 NOj 0 whose elemental analysis is little different from that of Cx i Hj 9 N 0 9.

k V a lu e is in cm /9 h.

R e fe r e n c e 99 term s this c o m p o u n d 2 -d e o xy-5 -ke to -D -glu c o n ic acid; neither nam e n o r structure seem definite.

!T h e enol fo rm is L -a sc o rb ic acid.

aIn order of increasing carbon chain length in the parent compounds grouped in the classes-aldonic, uronic, aldaric, and amino sugar acids. b [a] D for 1 -5 g solute, c, per 100 ml aqueous solution at 20-25°C , unless otherwise given. References for melting point and specific rotation data. Letter indicates the reference also has chromatographic data according to: c = column, e = electrophoresis, g = gas, p = paper, and t = thin-layer. dR value times 100, given relative to that of the compound indicated by abbreviation: f = solvent front, ala = alanine, ara = arabinose, asa = ascorbic acid, Cl = chloride ion, eic = eicosane,gain = galactono-1,4-lactone, galU = galacturonic acid, glc = glucose, glcN = glucosamine, glcU = glucuronic acid, gNAc = A-acetyl-glucosamine, gNUA = glucosaminuronic acid,kdh= 3-deoxy-erythro-hexulosonic acid, kdo= 3-deoxy-mfl««o-octulosonicacid,kgu = 2-keto-gulonic acid, mal = malonic acid, manU = mannuronic acid, myo = myo-inositol, myot = myo-inositol trimethylsilyl ether, MU = methylene standard hydrocarbon units, nana = A-acetyl-neuraminic acid, pa = picric acid, rha = rhamnose, tmg = 2,3,4,6-tetra-O-methyl glucose, and xyll = xylitol pentamethylether. Under gas chromatography (column Glc or G) numbers without code indications signify retention time in minutes. The conditions of the chromatography are correlated with the reference given in parentheses and are found in Table 5. eValue is in cm/h. ^Equilibrates with the lactone. gData given are for the enanthiomorphic isomer. hThe analytical elemental analysis indicates the compound is an anhydride.

D-Glyceric acid

c 4 h 6o 4

Acetate Ammonium salt Trimethylsilyl ester ether

c„h , n o 3

c 2 h „o 3

(B)

(A)

Glycollic acid (hydroxy-acetic acid)

Chemical formula

Substancea (synonym) derivative

Table 2 NATURAL ACIDS OF CARBOHYDRATE DERIVATION

153

Specific rotation*3 [a ]D

18 5 7 -6 0 75.5 Syrup Oil, bp 142-143

260

C3H60 3 C5H80 4 C3H7N 0 2 C3He0 3

C8H10O3 C3H40 4

C9H9N30 5

ILL-Lactic acid Acetate Amide 3-Hydroxypropionic acid (2-deoxy-glyceric acid) Methyl ester methyl ether Hydroxypyruvic acid (2keto-glyceric acid, 2-triulosonic acid) p-Nitrophenylhydrazone

Oil, bp 45 (22 mm)

C5H10O3

2 5 -2 6

Oil, bp 171-172 4 9 -5 1

2 6 -2 7

Gum 134-135

None

None None

Racemic Racemic Racemic None

+3.8 (15°) -95.5

22.2

[α]

+54.3

-2.3

levo -1 2 (30°)

+

(C) (D) Aldonic Acids (continued) 9 9 .5 -1 0 0 -63.1 (CH3OH) +10.9

Melting point °C

Methyl ester methyl ether Trimethylsilyl ester ether

C3H60 3

C3H7N 0 3

Amide

L-Lacticacid

C5H80 4

C3H60 3

Acetate

D-Lactic acid (2-hydroxypropionic acid, 3-deoxyD-glyceric acid)

Trimethylsilyl ester ether

C3H60 4 CaC6H10O8

CaC6H10O8 C6 Hj 2 0 4

Calcium salt Methyl ester methyl ether

L-Glyceric acid Calcium salt

C3H7N 0 3

(B)

(A)

Amide

Chemical formula

Substance3 (synonym) derivative

1

1 12

1 1 1 1

1

1

1

1

1,5c

1 9

8p

7

(E)

Reference0

Table 2 (continued) NATURAL ACIDS OF CARBOHYDRATE DERIVATION

42C1 @)

(F)

ELC

10.65MU (3)

( 1 0)

16glc

(ID

24xyll

(G)

GLC (Η)

PPC

(I)

TLC

Chromatography, R value, and reference**

154 Handbook o f Biochemistry and Molecular Biology

19

-9 .6 -> -4 1 .7f +37.2 -71.6

118-119 135-136 9 5 -9 8

C5H io 0 6

c 5h ,

Pentulosonic acid, 3deoxy-D-glycero-2(2-keto-3-deoxy-Darabonic acid)

c,

Phenylhydrazide

c , h, o 5

, h 16h 20 5

C,„H20O6

, no5 c 5h 8o 5

No constants known

No constants known

17 18

-1 3 +32.5

20 8 -2 0 9 135-136

C i , H, 6 N j 0 5 Ci 3H ,80 , o

215

5c,13

+ 10.5 (c6)

114-116

C sH10O6

29

24

20 21,22cp

1 1

None None

220 Oil, bp 134-137

3

c , h , n 3o 4

c 3h 60

(14)

8 .6 e

(2 )

50C1

(ID

97 glc ( 10) 295xyll

55glc ( 10)

10.91MU (3)

6 If (29)

73f (28)

16f (28)

2 Ogle (15)

62f (32)

40fS (16) 75fS (23)

35f (32)

16f (16)

(I)

(H)

(G)

(F)

(E) 1

TLC

PPC

GLC

ELC

Chrom atography, R value, and reference*^

Reference0

13.6

Methyl ester methyl ether

Lactone trimethylsilyl ether

Amide 1.4-Lactone (7-lactone)

L-Arbinonic acid

Phenylhydrazide Tetraacetate Trimethylsilyl ester ether

D-Arabinonic acid (arabonic acid)

p-Nitrophenylhydrazone Methyl ester Trimethylsilyl ester

W d

°c

(D) (C) Aldonic Acids (continued) None

Specific rotation**

Melting point

c , h 4o 3

(B)

(A)

Pyruvic acid (2-keto-3 deoxy-glyceric acid)

Chemical formula

Substance3 (synonym) derivative

Table 2 (continued) NATURAL ACIDS OF CARBOHYDRATE DERIVATION

155

C5H ,,N 0 5

C28H36N ,O 10 C5H80 5

Brucine salt 1.4- Lactone

C5H10O6

Cx0 H2 0 0 6

Amide

D-Xylonic acid

Methyl ester methyl ether

C5H80 5

1.4-

Lactone

Ο ,Η ,,Ν Ο ;

C5H80 5 C11H16N20 5 C5H100 6

1.4- Lactone Phenylhydrazide D-Ribonic acid

Amide

C5H10O6

Dinitrophenyl-hydrazone C11H10N4O7^1 * Lactone Cs H60 4

1 7 0 -172 9 8 -1 0 1

8 1 -8 2

Syrup

77

1 3 6 -137

108-1108 163 112-113

1148

220-223d

-2 .9 -> +20. l f + 4 4 .5 ^ +23.8 -37.4 +91.8 -* +86.7

+ 17-*+ 8 (13 days)

+17

+70& +13.7 -1 7 f

+82.7&

-22.7 (c 0.3, dioxane)

-29.4 No constants known

154-155 No constants known

C28H34N2O10 C5H80 5

Aldonic Acids (continued)

(D)

Specific rotation** M d

-10.3

163

(C)

Melting point °C

C5H80 6

L-Lyxonic acid

1.4-

2.4-

Pentulosonic acid, O-threo-4(4-fceto-D-arabonic acid) Brucine salt Pentulosonic acid, 3deoxy-L-glycero-2(2-keto-3-deoxy-Larabonic acid)

C11H12N40 8

(B)

(A)

2.4-Dinitrophenyl-hydrazone

Chemical formula

Substance3 (synonym) derivative

38 21

37

5c,36

34,35p

33

5c,25,36^ 458 46p 26cp 5c,31

30

27 28

27

29

(E)

Reference0

Table 2 (continued) NATURAL ACIDS OF CARBOHYDRATE DERIVATION

9.1e (14)

(F)

ELC

(ID

142xyll

(G)

GLC

82f (28)

29f (28)

14f (29)

(Η)

PPC

79f (23)

38f (32) 73f (23) 61f (32)

(I)

TLC

Chromatography, R value, and reference**

156 Handbook o f Biochemistry and Molecular Biology

. . Lactone . . 1.4-

C 6 H 13N 0 6

rC6H10O6 u n

Γ n n C6H12U7

, . . ., D-Galactomc acid

A m i**6

(^6^ 10^5

Cj j H 22 0 6

Hexulosonic acid, 3,6dideoxy-O-threo-2- (2keto-3-deoxy-D-fuconic acid)

C6H10Os

1.4-Lactone

C12H18N20 6 20 6

Phenylhydrazide D-Fuconic acid

M e t h y l ester m e th y l ether

C6H120 , C6H10O6

C28H36N2O10 C5H80 5 C13H18O10

C 5 H , 00 6

D-Altronic acid 1.4-Lactone

Brucine salt 1.4- Lactone Tetraacetate

L - X y lo n ic acid

Trimethylsilyl ester ether

M e t h y l ester m e th yl ether

C l 0H 20 0 6

(B)

(A)

Lactone trimethylsilyl ether

Chemical formula

Substance* (synonym) derivative

N o co n sta n ts know n

175

+ 3 1 .5

-7 3 ;-* -63.7

-15.6-> -17

148

1liU 1 0 -1n1 2z , 1 32-133

-11.2-► 57 6f

No constants known

+18.4^ No constants known

+24.3 -82.2 -4.5 (c 2, C2H5OH) +8 +35

N o co nsta nts know n

122 AZZ

No constants known

104g

150—152 No constants known

V&

1 7 7 -178 97 8 6 -8 8

(D)

Specific rotation1* [+l 16.9

167 7 1 -7 3

C6H i 20 6 C i 0H2o0 6

+153 (CH3OH) -12 (CH3OH) -16.1±2 -17.2±2 (c 0.9)

+133±2 +14.8±2 (15°) (CHC13 ) -96.5±2 (15°) (CHCI3 ) +29 (c 0.45)

+118 (CH3OH)(16°) +8.6^+22.3 (c 0.6) (18°)

C6H10O5 c 12 h 19 n 2 o 5

Gum 1 06-110

Syrup

79

112-113

Syrup 111-113

155, 177

d

(D)

W

Specific rotation*5

112—113s, 122- 123 -12± 1 (CHCI3) Syrup levo Syrup -30 143-145

Hi 2Os

Ci 3 h 20 o 8

c

, h 160 5 c 6 h 12 o 5 c 7 h 14 o 5

C8 H, 6 Os

c

3

c, H2 08

c,

C »H 16O s

c

c

C, e H2 4 O j o

C 6H 14O s

BrC, 2 H , , N 20 4

(C)

(B)

(A)

p-Bromophenylhydrazone 6-Deoxy-D-altritol (1-deoxy-D-talitol) 6-Deoxy-D-altritol pentaacetate Methyl a-pyranoside D-Altrose, 6-deoxy-30-methyl- (D-vallarose) Methyl a-pyranoside α-Pyranoside triace­ tate |3-Pyranoside triace­ tate D-Altrose, 6-deoxy-4Omethyl- (sordarose) Methyl a-pyranoside Methyl /3-pyranoside L-Altrose, 6-deoxyL-Altrose, 6-deoxy-3O-methyl- (L-vallarose) α-Pyranoside triacetate Antiarose Antiaronolactone Antiaronic acid phenylhydrazide a-D-Galactose Pyranose tetramethyl ether α-Pyranoside penta­ acetate Trimethylsilyl ether

°c

Melting point

Chemical formula

Substance3 (synonym) derivative

Table 3 (continued) NATURAL ALDOSES

188

D-Galactose, 6-deoxy2-0-m ethyl-

Methyl α-pyranoside D-Galactose, 4 ,6-CM1carboxyethylidene)Ammonium salt Ethanolate 4,6-0-(l-carboxyethylidene methyl ester)-D-galactitol Methyl α-pyranoside methyl ester α-D-Galactose, 6-deoxy(D-fucose, rhodeose) Benzylphenylhydrazone 6-Deoxy-D-galactitol Fucitol pentaacetate α-Pyranoside tetraacetate Trimethylsilyl ether 140-145 178-179

9 2 -9 3

C6H12Os

C19H24N20 4

C6H14Os C16H24O10 C14H20O9

155-161

Syrup

Cn Hl 80 8

C7H14Os

104-105

1 0 9 ,1 3 9 -1 4 0 No constants known

153-155

C9H17N 0 8 C9H140 8*C2H5OH C10H18O8

C7H12Os C9H140 8

C6H10O5 C8H160 6 C18H20N2O4

143-145 192

C6H120 6 C12H17N30 7 142

143

(C)

M elting p oin t °C

C8H160 6

(B)

(A)

α-D-Galactopyranoside, ethyl/3-D-Galactose p-Nitrophenylhydrazone /3-Pyranoside pentaacetate Dimethyl acetal D-Galactose, 3,6-anhydroTrime thy lsilyl ether Diphenylhydrazone

Chem ical form ula

Substancea (sy n on y m ) derivative

+73-H-87

+129 (CHC13)

-14.9 (c 0.4, CH3OH)

+120-^+76.3 (c 10)

+133(CHC13)

+ 5 1 (c0 .4 3 ) +49 -18 (c 0.6, CH3OH)

+12,+21.3(10°) +29 (17°) +34.5-»+23.6 (CH3OH) (14°) +80,+175 (10°) No constants known

+52.8^+80.2 +70 (c 0.3, C5Hs NC2Hs OH) +25 (CHC13)

+185

(D)

Sp ecific rotation'5 [a ]D

134

133

129

129,412c

128

127 126 126

123,124 126

123-125 125 124

122

119,411c 31

121

(E)

R eference0

Table 3 (continued) NATURAL ALDOSES

lOOsor (132)

(F)

ELC

6.2,7.1 (59b)

7.7(131)

108glct (9)

(G)

GLC

180fuc(135)

I9 f(4 9 )

20gal (127)

170rha(124)

35f (150)

(Η)

PPC

Chromatography, R value, and reference**

61,69f (59a)

25f (130)

54f (59)

81 f (69)

(I)

TLC

189

144-145 134 7 5 -7 6 Syrup Syrup 9 9 -1 0 3 129

96

9 3 -9 8

C8H160 5 C14H22N20 6S

C8H ,6Os

C9H i8Os C9H180 5 C14H22N20 5

C8H160 5

C8H18O s

C9H18Os

C9H18Os

C12H240 5

C12H240 5

Methyl α-pyranoside

Methyl/3-pyranoside

Methyl α-D-fucopyranoside trimethyl ether Methyl/3-D-fucopyranoside trimethyl ether

111

85

137—138 9 8 .5 -1 0 0 1 0 8 -1 1 0 1 31 -132

C7H140 6 C8H16Os C8H160 5 C7H14Os

Digitalonolactone Methyl α-pyranoside Methyl 0-pyranoside D-Galactose, 6-deoxy-4O-methyl- (curacose) Methyl/3-pyranoside p-Tolylsulfonylhydrazone D-Galactose, 6-deoxy-2,3di-O-methylMethyl α-pyranoside Methyl/3-pyranoside Onic acid phenylhydrazide D-Galactose, 6-deoxy2,4-di-O-methyl(labilose) Labilitol

Syrup 98.5-99.5 106,119

(C)

C8H16Os Cs H160 5 C7H140 5

(B)

(A)

Melting point °C

Methyl α-pyranoside Methyl/3-pyranoside D-Galactose, 6-deoxy-3O-methyl- (digitalose)

Chemical formula

Substance3 (synonym) derivative

+11.2

+213 (c0.3)

-20.9 (CHC13 )(30°)

+37.4 (c 0.5, CHC13) (30°) +176 (CHC13 )(30°)

+190 (acetone) +0.7 (acetone) +21.5± 3 (c 0.7, CH3OH) +82 (c 0.5)(27°)

+73,+105

-14.6 (c 0.9, CH3OH) -1 6 — ► —3 (C5Hs N)

-83 +198 (c 0.7, CH3 OH) +9.9 (c 0.3, CH3OH) +102.6-+80.6 (c 0.9)

+173.6 +3.5 (CH3OH) +106

(D)

Specific rotation** [a jp

173

140

140

140

140

140cp

135,136 135,136 135

136,139

138 138

137 136 136 38,138

136 136 137

(E)

Reference0

Table 3 (continued) NATURAL ALDOSES

12.5j (94a)

(F)

----- — ELC

4.6 (140c)

(G)

275fuc(135)

85tem g(136) 97tem g(136)

267fuc(135)

217mfuc(136) 163mfuc(136) 142mfuc (136) 52f (38)

30aco (94b)

180mfuc (136)

(Η)

28f (140b)

18f (140b)

17f (140a) 13f (140b)

104rha (96b, ep)

(I)

Chromatography, R value, and reference** --------------------------------------------------------------------GLC PPC TLC

190 Handbook o f Biochemistry and Molecular Biology

Referencec

146

147-149

148

141

151

+31.9

+62-->+92

-84-->-39 (CH, OH)

+76 (17°)

+165

Syrup

207,218

167-168

119-120

137-138 181.5-182.5

C 8 H 16 0 6

C,H, • 0 6

C,,H, 9 NO,

C 7 H, 4 0 6

C,H, 6 0 6 C 12 H 22 0 0

C 1 ,H 20 N2 0, c.H, 2 0.s C6 H 1 2 0 9 S

155

152 153 154

145,146

+15Q-++108

144-147

C,H, 4 0 6

+5 2 (as Ba salt) +64 (c 0.5 )(as NH 4 salt) +58.4 (16°)(as Na salt)

141 142 142,143 141

+84.9 (c 0.5)(16°) +180 (CH,OH) +1.69

(E)

-85 (18°)

-39 (CHC13)

-113 (CHC13)

(D)

Specific rotationb [a] D

C6H120 8S

7 6 -7 8 ,1 3 0 -1 3 2 178-179d 3 6 -3 7

Syrup 98—99

C8H16Os C8H16Os

C8H16Os C19H24N40 3 C9H18Os

149-150

C7H140 5

110

172

C14H20O9

C7HM Os

92—93

(C)

Melting point °C

C14H20O9

(B)

(A)

a-Pyranoside tetraacetate 0-Pyranoside tetraacetate Trimethylsilyl ether L-Galactose, 6-deoxy2-0 -me thy 1Methyl α-pyranoside Methyl (3-pyranoside

Chemical formula

Substance4 (synonym) derivative

141gp 176

159p

153ep 153

174g

172

164,172

169,170pt 169 172

164,170gpt

136 136

164,168

166

165

(E)

Reference0

Table 3 (continued) NATURAL ALDOSES

74xyl(159c)

lOOgals (175a)

~~

(F)

ELC

7.2(34)

(G)

GLC

81glc (175b)

720temg (80)

92temg (164)

45glc (169)

180mfuc(136) 217mfuc (136)

60tem g(164)

(Η)

PPC

Chromatography, R value, and reference**

(I)

TLC

193

101-108 2 1 5 -2 1 6

1 02-104 104-105 4 0 -4 1

146 166 Syrup 83 114

C16H24O10 C36H28N40 18

C7H140 6

C15H22O10 C11H220 6

C6H120 6 C7H140 6 C, , H2 2 0 6

C6H120 6 *H20 C16H! 20 , ,

Cl 0H20O6

9 8 -1 0 0

C8H160 6

methyl-D-glucopyranose Trimethylsilyl ether

110-115

C36H28N40 18

96

+92-+84

+101.6 (CHC13)

+112^+52.7 +158.9 +144 (acetone)

-18.7 (CHC13 ) -17.3

-32

+16.2(CHC13) +28 (18°)(acetone)

-37.9

1 1 3 -114

C8H160 6

193

186 182,187

186,411c 186 194,195

182,183 185

181

1 1

1,180c

1

1,180c

177

127

α-D-Glucopyranoside, ethylTetra-p-nitrobenzoate Trifluoroacetate /3-D-Glucopyranoside, ethylTetraacetate Tetra-p-nitrobenzoate Trifluoroacetate Trimethylsilyl ether 0-D-Glucopyranoside, me thy 1Tetraacetate 2,3,4,6-Tetramethyl etherk Trimethylsilyl ether a-D-Glucose Methyl α-pyranoside Methyl α-pyranoside tetramethyl ether Monohydrate Pentaacetate

Syrup

C6 H, 20 9 S

L-Galactose 6-sulfate

-32 (c 0.56)(as NH4 salt) -43 (c 0.56)(as NH4 salt) -47 (c 0.2)(as Na salt) +150.3

127

Syrup

(E)

C6H120 9S

(D)

Reference0

159

(C)

Specific rotation** [a ]D

C7H140 6

(B)

(A)

Melting point °C

L-Galactose, 6-0methyl-1 L-Galactose 3-sulfate

Chemical formula

Substance3 (synonym) derivative

Table 3 (continued) NATURAL ALDOSES

0 (5 ,2 8 )

16rib (28) 9rib (28)

6rib (28)

92xyl (159c)

(F)

lOOglct (9)

6.9 (189)

358damg (184) 100, 143/ltemg (80) 49, 107glct (9)

10.1 (180b) 195mmt (192)

6.2 (180b)

(G)

82f(150)

27f (188a)

8f (49) 20f (49)

24f(150)

60f(180a)

56gal (127)

75gal (127)

(Η)

6 6 f(5 9 )

86f (30b)

68f

25f (30a) 29f(130) 29f (40)

76f (69) 46f (40)

61f(30c)

78f(69]

(I)

Chromatography, R value, and reference** ------------------------------------------------------------------------- - — ELC GLC PPC TLC

194 Handbook o f Biochemistry and Molecular Biology

C27H30O17

203

203

+56

203

202

202m

No constants known

-25.6 (18°)

178 200 178 201

No constants known

2 1 1- 212

C13H16O10

+32.9 (CHC13)

+48 (C2H5OH)

178p, 179

196,197 197 198 199c

182,190

31

186 65,191

(E)

R eferencec

-24.3 (acetylene tetrachloride) +64

140-141 Amorphous 104—106 132

C13H160 7 Cl 3H160 7 *H20 C21H240 11

-26.8

+30.2 (CHC13)

+48 -13

+3.8 (c 7, CHC13)

+18.7—+52.7 +21.5 (CSH5N, C2H5OH) -88 (c 0.5)

(D)

S p ecific rotationb [°*] d

125-126

193

C13H160 7

C26H44O10

133-135 136 183-184 104-106

135

148-150 189

(C)

M elting p o in t °C

C8H140 7 C14H20N2O6

D-Glucose 1-7 -hydroxyCn H180 8 a-methylene-butyrate (1-tuliposide A) D-Glucose 6^y-hydroxyCn H180 8 α-methylene-butyrate (6-tuliposide A) D-Glucose l-0,7-di C ,, Hl 8 0 9 hydr oxy-a-me thy lenebutyrate (1-tuliposide B)

Heptaacetate

Pentaacetate Trimethylsilyl ether D-Glucose 6-acetate Phenylhydrazone Tetrabenzoate D-Glucose 6-acetate, 2,3,4-tri-O- [ (+)-3methyl-valeryl] D-Glucose 1-benzoate (periplanetin) Tetraacetate D-Glucose 6-benzoate Monohydrate 0-Pyranoside tetraacetate D-Glucose 4-gallatem

C6H120 6 C12H17N30 7

(B)

(A)

0-D-Glucose p-Nitrophenylhydrazone

Chem ical form ula

Substance* (sy n o n y m ) derivative

Table 3 (continued) NATURAL ALDOSES C hrom atography, R value, and reference**

(F)

157glct (9)

(G)

149glc (203)

312glc (203)

28temg(197)

21f(188a)

(Η)

8 l f (69) 56f (59)

(I)

----------------------------------------------------------------------------------------------ELC GLC PPC TLC

195

No constants known 139-140

C9H14Os

C14H20O9

C7H14Os

C6H10O5

C6H14Os

145

151-152

125.5-126.5 103 125-126.5 150-152.5 104-105.5

C17H23N30 16 C19H25N30 17 C15H21N30 1S C15H21N30 15 C ,8H24N40 18

C6H12Os

145-146 1 3 2 -1 3 4 ,1 3 8 120-122

No constants known No constants known

(C)

Melting point °C

C12H18N20 12 C12H18N20 12 CI 5H21N30 1S

C9H140 9

?

(B)

(A)

D-Glucose ? (tuliposide C) D-Glucose 3-malonate D-Glucose di-/3-nitropropionate (endecaphyllin D) (endecaphyllin E) D-Glucose tri-/3-nitropropionate (endecaphyllin A, karakin) Monoacetate Diacetate (endecaphyllin B) (endecaphyllin C) D-Glucose tetra-0-nitropropionate (endeca­ phyllin X, hiptagin) D-Glucose, 4,6-0-(Γcarboxyethylidene α-D-Glucose, 6-deoxy(chinovose, epirhamnose, quinovose) 6-Deoxy-D-glucitol ( 1-deoxy-L-gulitol) D-Glucomethylonic acid lactone Methyl a-pyranoside trimethylsilyl ether Methyl |3-pyranoside trimethylsilyl ether Methyl a-or/3-pyranoside Pyranoside tetraacetate

Chemical formula

Substance4 (synonym) derivative

+23 (CHC13)

+66.9-++5.4

+73.3-H-29.7 (c 8)

No constants known

+4.5

No constants known

No constants known

(D)

Specific rotation*5 [a ]D

211

209

208,411c

207

204 205 204 204 204,206

204t 204,205 204,205p

212p

203

(E)

Reference0

Table 3 (continued) NATURAL ALDOSES

94glcl (312)

148rha (96a)

(F)

ELC

3.6 (210a)

3.4 (210a)

(G)

GLC

lOOglc(203)

96rha (96c)

27temg (205)

(Η)

PPC

Chromatography, R value, and reference**

48f (210b)

99rha (96b)

(I)

TLC

196 Handbook o f Biochemistry and Molecular Biology’

/3-Pyranoside tetraacetate

-methyl-D-glucitol

Methyl α-pyranoside Methyl α-pyranoside triacetate Trimethylsilyl ether /3-D-Glucose, 3-O-methyl3-O-Methyl-A-phenylD-glucopyranoside Methyl/3-pyranoside Methyl/3-pyranoside triacetate Penta-O-acetyl-3-O-

Methyl α-pyranoside Methyl α-pyranoside triacetate Methyl/3-pyranoside Methyl/3-pyranoside triacetate D-Glucose, 6-deoxy-2,3di-O-methylMethyl /3-pyranoside D-Glucose, 6-deoxy-6sulfonic acid (6sulfoquinovose) Allyl α-pyranoside cyclohexylamine salt Methyl α-pyranoside cyclohexylamine salt α-D-Glucose, 3-O-methyl-

O-methyl- (D-thevetose)

162-167

C7H140 6

Cl s H22O10

C, 7 H2 6 O, , 9 5 -9 6

Syrup

173-174

C13H27N 0 8S

C8H160 6 C14H220 9

151.5-153

C15H29N 0 8S

130-132 152-153

7 6 -7 8 No constants known

C9H180 5 C6H120 8S

C7H140 6 C13H19NOs

Syrup

C8H16Os

80 -8 1

116-117 121

C8H16Os C13H20O8

C8 6 0 6 · ViH2 O C14H220 9

8 6 -8 7 105

116,126

(C)

M elting p o in t °C

C8H16Os C ,3H20O8

C7H140 5

(B)

(A)

Q!-D-Glucose, 6-deoxy-3-

Chem ical form u la

Substance3 (syn on y m ) derivative

-5.2 (CHC13)

+31.9^+55.1 -108-+-46±2 (c 0.5, CH3OH) -26 (c 5.5)

+ 164± 2(c0.9)

+98->+59.5 (c 0.4)

+87

[a]N a5 8 9 +86

-49 (CHC13) No constants known

+40.4±2

-44±2 +6 (acetone)

+148±2 +122 (acetone)

+84-*+33

(D)

S p ecific rotation** [^ Id

224

222

221 223

220

218c

217

217

216 217

216ep

215 213

215 213

213,214 cp

(E)

R eference0

Table 3 (continued) NATURAL ALDOSES

90glc (223)

13rib (28)

15.5^ (94a)

(F)

ELC

18lamgl (184)

266damg(184)

3.46 (219b)

180damg(184)

(G)

184glc (219a)

39f (217)

50aco (94b)

(Η)

Chrom atography, R value, and reference^ " GLC PPC

4f (30b)

22f (219c)

(I)

TLC

197

134

6 2 -6 4

141-143 143-145 9 7 -9 8 126 -1 29

C7H ,80 6 CM H22 0 8

C6H120 6 C6Hl 2Os

C10H22O4S2 C7H14Os

C, 6 H26 0 , 0

C, 4 H2, NOs

8 0 -8 2

C7H180 6 C, j H2 2 0 8

+47.1 -36.9±2

-9 5 .5 --5 1 .4 -8 4 .7 --3 0 .1

-36.6

+5.9-H-50.9 (acetone) -83 (CHC13)

+8l.9->+48.3 (acetone) +142.6

+20.9 (CHC13)

+111.8 (CHC13)

233 234

231 232,233

222

230

221,229

221

135,221

228

228

227

99rha (96a)

20.6glc (19c)

8 5 -8 7

C8H160 6

10 8 -1 1 0 ,1 2 1

29 (184)

9 1 -9 3

C15H22O10

C8H160 6

15 (184)

119-120

Cl s H22O10

-27

72.5damg (184)

3.76 (219b)

139damg (184)

133-135

226

C8H160 6 Cj 4 H2 2 0 9

(G)

110damg(184)

+127.9

87glc(2l9d)

(F)

Syrup

225

(E)

C8H i60 6 C14H2 20 9

+57.5

(D)

Reference0

(19a)

247rha (96c)

97rha (95)

57temg

211fuc(135)

176glc(219a)

(Η)

Chromatography, R value, and reference** ■ 1 ■■■■....... ■ ■ ■ ' ■ ■ ■■..... ELC GLC PPC

Methyl α-pyranoside Methyl α-pyranoside triacetate Methyl β-pyranoside Methyl 0-pyranoside triacetate α-Pyranoside tetraacetate 0-Pyranoside tetraacetate Trimethylsilyl ether +46.2 (6h)

+30.4 (CHC13)

+29.4±2 (16°) (CH3OH) +47^+64 (c 0.5)

394 394

394cp

390

389ep, 392 cp 389

387,388pt

351,387

360 360

20y sor (5)

40sor (5)

103rha (96a)

39glc (360b)

427xglct (9)

6 3 -6 5 9 1 -9 2

C7H14Os C13H20O8

386 386

134-135 136-137

C6H10O5 C13H20N2O4

-10-*+4 (16°)(c 0.8, C2Hs OH) +33±2 (18°) -12 (17°)(c 0.8, C2 Hs OH) -104 -73.3 (c 1.2, CH3OH) -19.4

145-147

BrC12H17N20 4

385cp 360ep 386

113rha (96a)

-20.5±1.4

(G)

126-127

106rha (82b)

(F)

ELC

80glc (393)

15f (391)

385rha (96c)

81f(360a)

189rha (96c)

163xyl (82a)

(Η)

Chrom atography, R value, and reference** ■■ ------- ■■■'■" 1 GLC PPC

C6H12Os



(E)

R eference0

+53 (C5Hs N:C2 Hs OH, 347 2:3) +16.5 82

(D)

Sp ecific rotation ” [a]D

31xyll (82c)

Syrup

176-178

(C)

M elting p o in t °C

Ct s H24 0 9

C7H140 5

Cl8 H24N40 3

(B)

(A)

Phenylosazone

Chem ical form ula

Substance3 (syn o n ym ) derivative

Table 3 (continued) NATURAL ALDOSES

94rha (96b)

49rha (96b)

(I)

TLC

215

116 2 0 1 -2 0 2 100 No constants known

C21H30O14

CMH240 6 S2

C49H380 13

C7H140 6

C8H160 6 C16H24O10

C l 9 H2sO l2

7 7 -7 8

179-181

C7H140 7 -H 20

C7H140 6

1 3 9 -140 Syrup 176-177

C19H260 13 C8H160 7 C13H19N30 8

See Table 1 for this compound C21H30O14 Syrup

+80 (c 0.5) +62 (c 0.4, CHC13)

+30±5

No constants known

-32 (CHC13)

+9.9 (C5H5N)

-11 (CHC13)

+ 1 4 (c 0 .9 )

+65 (CHC13) +47 (CH3OH)

+34 (c 0.4, CHC13)

+48 (c 0.2)

164-165

C7H120 7

(D)

Specific rotation** [a ]D

+21 (CH3OH)

(C)

Melting point °C

C7H140 7

(B)

(A)

Heptose, D-glyceroD-mannoHeptonolactone, Dglycero-D-mannoHeptitol, D-glyceroΌ-mannoO-glycero-Ό-mannoheptitol heptaacetate α-Hexaacetate Methyl pyranoside p-Nitrophenylhydrazone Trimethylsilyl ether Heptose, L-glycero-DmannoL-glycero-D-mannoheptitol heptaacetate Heptose diethyl dithioacetal Hexabenzoate Trimethylsilyl ether Heptose, 7-deoxy-Lglycero-O-mannoHeptononitrile acetate Potassmm heptonate trimethylsilyl ether Heptose, 6-deoxy-Dmanno6-Deoxy-D-mannoheptitol hexaacetate Methyl α-pyranoside Methyl α-pyranoside tetraacetate

Chemical formula

Substance4 (synonym) derivative

403 egp 403

402,403

401

397

400

397g

3 9 7 -399

396cp 396 396

397g

395-397 egpt 395cp

(E)

Reference0

Table 3 (continued) NATURAL ALDOSES

80glc (397)

80y sor (5)

(F)

125glca (402b)

16 9 (401a) 14 2 (401b)

461mant (398b)

229glca (398b)

338mant (398b)

198glca (398b)

(G)

ca. 10 (402a)

64glc (398a)

lOOhep (395)

85glc (398a)

(Η)

(I)

Chromatography, R value, and reference** ---------------------------------------------------------------------------------ELC GLC PPC TLC

216 Handbook o f Biochemistry and Molecular Biology

C 19H29NO jj

Compiled by George G. Maher.

Octose, 6-amino-6,8dideoxy-7-O-methyl-Dery thro-D-galac to(celestose) Pentaacetate

C9H19N 0 6

(B)

(A)

Heptose, unidentified

Chem ical form ula

Substance4 (sy n o n y m ) derivative

215 —216t, 2 3 4 234.5

No constants known No constants known

(C)

M elting p oin t °C

No constants known

No constants known

(D)

Sp ecific rotation** [a]D

409

408

4 0 4 -4 0 7 z

(E)

R eference0

Table 3 (continued) NATURAL ALDOSES

(F)

— ELC

(G)

68glc (406a) 99glc (406b)

(Η)

Chrom atography, R value, and reference** ■■■ ----- ■ ....................... — ----------- ---GLC PPC

(I)

TLC

217

218

Handbook o f Biochemistry and Molecular Biology

Table 3 (continued) NATURAL ALDOSES REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56.

Pollock and Stevens, Dictionary o f Organic Compounds, O x fo rd U niversity Press, New Y o rk , 1965. Williams and Tucknott,/. Sci. Food Agric., 22, 264 (1971). Bloem,/. Chromatogr., 35, 108 (1968). Wohl and Momber, Ber. Dtsch. Chem. Ges., 50, 456 (1917). Bourne, Hutson, and Weigel, J. Chem. Soc. (L o n d .), p. 4252 (1960). Bourne, Hutson, and Weigel, J. Chem. Soc. (Lond.), p. 5153 (1960). Bancher, Scherz, and Kaindl, Mikrochim. Acta, p. 1043 (1964). Fischer and Baer, Helv. Chim. Acta, 17, 622 (1934). Sweeley, Bentley, Makita, and Wells, J. Am. Chem. Soc., 85, 2497 (1963). Williams and Jones, Can. J. Chem., 42, 69 (1964). Vongerichten, Justus Liebigs Ann. Chem., 321,71 (1902). Schmidt, Justus Liebigs Ann. Chem. 483, 115 (1930). Duff, Biochem. J., 94, 768 (1965). Hulyalkar, Jones, and Perry, Can J. Chem., 43, 2085 (1965). Bentley, Cunningham, and Spring,/. Chem. Soc. (Lond.), p. 2301 (1951). Hockett and Hudson,/. Am. Chem. Soc., 56, 1632 (1934). Nemec, Kefurt, and Jar^, /. Chromatogr., 26, 116 (1967). Fischer, Bergmann, and Schotts, Ber. Dtsch. Chem. Ges., 53, 522 (1920). Misaki and Yukawa, J. Biochem. (Tokyo), 59, 511 (1966). Haworth, Peat, and Whetstone,/. Chem. Soc. (Lond.) p. 1975 (1938). Halliburton and M cllroy,/. Chem. Soc. (Lond.), p. 299 (1949). Lynch, Olney, and Wright, /. Sci. Food Agric., 9, 56 (1958). Williams and Jones, Can. J. Chem., 45, 275 (1967). Sowden, Oftedahl, and Kirkland,/. Org. Chem., 27, 1791 (1962). Jones, Kent, and Stacey,/. Chem. Soc. (L o n d .), p. 1341 (1947). Vogel, Helv. Chem. Acta, 11, 1210 (1928). Montgomery and Hudson,/. Am. Chem. Soc., 56, 2074 (1934). Frahn and Mills, Aust. J. Chem., 12, 65 (1959). Phillips and Criddle, /. Chem. Soc. (Lond.), p. 3404 (1960). Wolfrom, Patin, and de Lederkremer, /. Chromatogr., 17, 488 (1965). Whistler and Kirby, /. Am. Chem. Soc., 78, 1755 (1956). Hudson and Dale, J. Am. Chem. Soc., 40, 995 (1918). Jones,/. Chem. Soc. (Lond.), p. 1055 (1947). Roberts, Johnston, and Fuhr, Anal. Biochem., 10, 282 (1965). Mackie and Percival, Biochem. J., 91, 5P (1964). Alberda van Ekenstein, Chem. Weekbl., 11, 189(1914). Adachi,/. Chromatogr., 17, 295 (1965). Galmarini and Deulofeu, Tetrahedron, 15, 76 (1961). Levene and Wolfrom,/. Biol. Chem., 78, 525 (1928). Gee, Anal. Chem., 35, 354 (1963). Dyer, McGonigal, and Rice, J. Am. Chem. Soc., 87, 654 (1965). Kuehl, Jr., Flynn, Brink, and Folkers, /. Am. Chem. Soc., 68, 2679 (1946). Tatsuoka, Kusaka, Miyake, Inone, Hitomi, Shiraishi, Iwasaki, and Imanishi, Pharm. Bull, 5, 343 (1957). Stodola, Shotwell, Borud, Benedict, and Riley, Jr., /. Am. Chem. Soc., 73, 2290, 5912 (1951). Brimacombe and Mofti, /. Chem. Soc. D Chem. Commun, p. 241 (1971). Ganguly, Sarre, and Morton,/. Chem. Soc. D Chem. Commun, p. 1488 (1969). Hogenkamp and Barker,/. Biol. Chem., 236, 3097 (1961). Deriaz, Overend, Stacey, Teece, and Wiggins, /. Chem. Soc. (L o n d .), p. 1879 (1949). Bourne, Lees, and Weigel,/. Chromatogr., 11, 253 (1963). Lombard,/. Chromatogr., 26, 283 (1967). Allerton and Overend,/. Chem. Soc. (Lond.), p. 1480 (1951). Oades,/. Chromatogr., 28, 246 (1967). Phelps, Isbell, and Pigman,/. Am. Chem. Soc., 56, 747 (1934). Levene and Tipson,/. Biol. Chem., 115,731 (1936). Zinner, Ber. Dtsch. Chem. Ges., 86, 817 (1953). Barker and Smith,/. Chem. Soc. (Lond.), p. 1323 (1955).

219

Table 3 (continued) NATURAL ALDOSES 57. Burton, Overend, and Williams, /. Chem. Soc. (Lond.), pp. 3433, 3446 (1965). 58. Ezekial, Overend, and Williams, Carbohydr. Res., 11, 233 (1969). 59. Karkkainen, Haohti, and Lehtonen, Anal. Chem., 38,1316 (1966). 60. Schroeder, Barnes, Bohinski, Mumma and Mallette, Biochim. Biophys. Acta, 273, 254 (1972). 61. Levene and Sobotka, J. Biol. Chem., 65, 55 (1925). 62. Hudson and Yanovsky,/. Am. Chem. Soc., 39, 1013 (1917). 63. Isbell and Pigman, /. Res. Natl. Bur. Stand., 18, 141 (1937). 64. Alberda van Ekenstein and Blanksma, Reel. Trav. Chim. Pays-Bas, 22, 434 (1903). 65. Reclaire, Ber. Dtsch. Chem. Ges., 41, 3665 (1908). 66. Hudson and Johnson,/. Am.Chem. Soc., 37, 2748 (1915). 67. Stephen, Kaplan, Taylor, and Leisegang, Tetrahedron, Suppl. 7, 233 (1966). 68. Tyler,/. Chem. Soc. (Lond.), pp. 5288, 5300 (1965). 69. Hay, Lewis, and Sm ith,/. Chromatogr., 11, 479 (1963). 70. Gorin, Hough, and Jones, /. Chem. Soc. (Lond.), p. 2140 (1953). 71. Levene and Compton,/. Biol. Chem., I l l , 325 (1935). 72. Ryan, Arzoumanian, Acton, and Goodman, /. Am. Chem. Soc., 86, 2497 (1964). 73. Andrews and Hough, Chem. Ind, p. 1278 (1956). 74. Alam and Mcllroy,/. Chem. Soc. Sect. C Org. Chem., p. 1579 (1967). 75. Robertson and Speedie, J. Chem. Soc. (Lond.), p. 824 (1934). 76. Lance and Jones, Can. J. Chem., 45, 1995 (1967). 77. Laidlaw, / Chem. Soc. (Lond.), p. 752 (1954). 78. Aspinall and McKay, J. Chem. Soc. (Lond.), p. 1059 (1958). 79. Laidlaw and Percival, /. Chem. Soc. (Lond.), p. 528 (1950). 80. Aspinall,/. Chem. Soc. (Lond.), p. 1676 (1963). 81. Hough and Jones, / Chem. Soc. (Lond.), p. 4349 (1952). 82. Weckesser, Mayer, and Fromme, Biochem. J., 135, 293 (1973). 83. Percival and Willox, J. Chem. Soc. (Lond.), p. 1608 (1949). 84. Wintersteiner and Klingsberg,/. Am. Chem. Soc., 71, 939 (1949). 85. Weckesser, Rosenfelder, Mayer, and Liideritz, Eur. J. Biochem., 24, 112 (1971). 86. Anderle, Koviic and Anderlovd, /. Chromatogr., 64, 368 (1972). 87. Kunstmann, Mitscher, and Bohonos, Tetrahedron Lett., p. 839 (1966). 88. Paulsen and Redlich, Angew. Chem. Int. Ed., 11, 1021 (1972). 89. Beylis, Howard, and Perold, J. Chem. Soc. DChem. Commun., p. 597 (1971). 90. Steiger and Reichstein, Helv. Chim. Acta, 19, 184 (1936). 91. Scher and Ginsburg, /. Biol. Chem., 243, 2385 (1968). 92. Levene and Jacobs, Ber. Dtsch. Chem. Ges., 43, 3141 (1910). 93. Lerner and Kohn,/. Med. Chem., 7, 655 (1964). 94. Muhlradt, Weiss, and Reichstein, Justus Liebigs Ann. Chem., 685, 253 (1965). 95. MacLennan and Randall, Anal. Chem., 31, 2020 (1959). 96. Kaufmann, Muhlradt, and Reichstein, Helv. Chim. Acta, 50, 2287 (1967). 97. Keller and Reichstein, Helv. Chim. Acta, 32, 1607 (1949). 98. Perry and Daoust, Carbohydr. Res., 31, 131 (1973). 99. Levene and Compton,/. Biol. Chem., 117, 37 (1937). 100. Iselin and Reichstein, Helv. Chim. Acta, 27, 1203 (1944). 101. Brimacombe and Husain, Chem. Commun., 630 (1966). 102. Hoffman, Weiss, and Reichstein, Helv. Chim. Acta, 49, 2209 (1966). 103. Brimacombe and Portsmouth,/. Chem. Soc. Sect. COrg. Chem., p. 499 (1966). 104. Krasso and Weiss, Helv. Chim. Acta, 49, 1113 (1966). 105. Dion, Woo, and Bartz,/ . Am. Chem. Soc., 84, 880 (1962). 106. Brimacombe, Ching, and Stacey,/. Chem. Soc. Sect. C Org. Chem., p. 197 (1969). 107. Brimacombe, Stacey, and Tucker, /. Chem. Soc. (Lond.), p. 5391 (1964). 108. Jager, Dissertation (Basel) (1959). 109. Gut and Prins, Helv. Chim. Acta, 29, 1555 (1946). 110. Iwadare, Bull. Chem. Soc. Jap., 17, 296 (1942). 111. Krauss,Dissertation (Basel) (1959). 112. Grob and Prins, Helv. Chim. Acta, 28, 840 (1945). 113. Hauser and Sigg, Helv. Chim. Acta, 54, 1178 (1971). 114. Ellwood and Kirk, Biochem. J., 122, 14P (1971).

220

Handbook o f Biochemistry and Molecular Biology

Table 3 (continued) NATURAL ALDOSES 115. 116. 117. 118. 119. 120. 121. 122. 123. 124. 125. 126. 127. 128. 129. 130. 131. 132. 133. 134. 135. 136. 137. 138. 139. 140. 141. 142. 143. 144. 145. 146. 147. 148. 149. 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 160. 161. 162. 163. 164. 165. 166. 167. 168. 169. 170. 171. 172.

Kaufmann, Helv. Chim. Acta, 48, 83 (1965). Brim acorn be, Da’aboul, and Tucker,/. Chem. Soc. Sec. C Org. Chem., p. 3762 (1971). Kiliani, Ber. Dtsch. Chem. Ges., 46,667 (1913). Kiliani, Arch. Pharm., 234, 449 (1896); Chem. Zentralbl., 67, II, 591 (1896). Ruber, Minsaas, and Lyche,/. Chem. Soc. (Lond.), p. 2173 (1929). Charlton, Haworth, and Hickinbottom, J. Chem. Soc. (Lond.), p. 1527 (1927). Nottbohm and Mayer, Vorratspflege Lebensmittelforsch., 1, 243 (1938). Hudson and Parker,/. Am. Chem. Soc., 37, 1589 (1915). O’Neill, J. Am. Chem. Soc., 77, 2837 (1955). Araki and Hirase, Bull. Chem. Soc. Jap., 29, 770 (1956). Clingman and Nunn, / Chem. Soc. (Lond.), p. 493 (1959). Gorin and Spencer, Can. J. Chem., 42, 1230 (1964). Nunn, Parolis, and Russell, Carbohydr. Res., 29, 281 (1973). Gorin and Ishikawa, Can. J. Chem., 45, 521 (1967). Votocekand Valentin, Collect. Czech. Chem. Commun., 2, 36 (1930). Lato, Brunelli, Ciuffini, and Mezzetti, /. Chromatogr., 34, 26 (1968). Shaw and Moss, /. Chromatogr., 41, 350 (1969). Bourne, Hutson, and Weigel,/. Chem. Soc. (Lond.), p. 35 (1961). Lewy and McAllan, Biochem. J., 80, 433 (1961). MacPhillamy and Elderfield,/. Org. Chem., 4, 150 (1939). Khare, Schindler, and Reich stein, Helv. Chim. Acta, 45, 1534 (1962). Springer, Desai, and Kolechi, Biochemistry, 3, 1076 (1964). Lamb and Sm ith,/. Chem. Soc. (Lond.), p. 422 (1936). Gros, Carbohydr. Res., 2, 56 (1966). Schmidt and Wernicke, Justus Liebigs Ann. Chem., 556, 179 (1944). Akita, Maeda, and Umezawa, J. Antibiot. {Tokyo) Ser. A, 71, 200 (1964). Nunn and Parolis, Carbohydr. Res., 6, 1 (1968); 8, 361 (1968). Bell and Williamson, /. Chem. Soc. (Lond.), p. 1196 (1938). Oldham and Bell, /. Am. Chem. Soc., 60, 323 (1938). Freeman, Stephan, and Van der Bijl, /. Chromatogr., 73, 29 (1972). Lechevalier and Gerber, Carbohydr. Res., 13, 451 (1970). Reber and Reich stein, Helv. Chim. Acta, 28, 1164 (1945). Hirst and Jones, /. Chem. Soc. (Lond.), p. 506 (1946). Jeanloz, /. Am. Chem. Soc., 76, 5684 (1954). Itasaka, /. Biochem. {Tokyo), 60, 52 (1966). Kocourek, Ticha, and Kostiv,/. Chromatogr., 24, 117 (1966). Goldstein, Hamilton, and Smith,/. Am. Chem. Soc., 79, 1190 (1957). Hassid and Su, Biochemistry, 1, 468 (1962). Bowker and Turvey, /. Chem. Soc. (Lond.), p. 983, 989 (1968). Love and Percival,/. Chem. Soc. (Lond.), p. 3338 (1964). Turvey and Williams,/. Chem. Soc. (Lond.), p. 2119 (1962); p. 2242 (1963). Anderson, / Biol. Chem., 100, 249 (1933). Fischer and Hertz, Ber. Dtsch. Chem. Ges., 25, 1247 (1892). Araki and Hirase, Bull. Chem. Soc. Jap., 26, 463 (1953); 33, 291 (1960). Kochetkov, Usov, and Miroshnikova,/. Gen. Chem. USSR Engl. Ed., 40, 2457, 2461 (1970). Usov, Lotov, and Kochetkov,/. Gen Chem. USSR Engl. Ed., 41, 1156 (1971). Nunn and von Holdt,/. Chem. Soc. (Lond.), p. 1094 (1957). Duff and Percival,/. Chem. Soc. (Lond.), p. 830 (1941). Minsaas, Reel. Trav. Chim. Pays-Bas, 50, 424 (1933). Gardiner and Percival,/. Chem. Soc. (Lond.), p. 1414 (1958). Lewy and McAllan, Biochem. J., 80, 433 (1961). Westphal and Feier, Ber. Dtsch. Chem. Ges., 89, 582 (1956). Horowitz and Delman,/. Chromatogr., 21, 302 (1966). Anderson, Andrews, and Hough, Chem. Ind., p. 1453 (1957). Conchie and Percival,/. Chem. Soc. (Lond.), p. 827 (1950). Percival and Young, Carbohydr. Res., 32, 195 (1974). Dejter-Juszynski and Flowers, Carbohydr. Res., 28, 61 (1973). Schmidt, Mayer, and Distelmaier, Justus Liebigs Ann. Chem., 555, 26 (1943).

221

Table 3 (continued) NATURAL ALDOSES 173. 174. 175. 176. 177. 178. 179. 180. 181. 182. 183. 184. 185. 186.

James and Smith, / Chem. Soc. (Lond.), p. 739, 746 (1945). Katzman and Jeanloz, /. Biol. Chem., 248, 50 (1973). Anno, Seno, and Ota, Carhohydr. Res., 13, 167 (1970). Araki, Arai, and Hirasi, Bull. Chem. Soc. Jap., 40, 959 (1967). Turvey and Rees, Nature, 189, 831 (1961). Quilico, Piozzi, Pavan, and Mantia, Tetrahedron, 5, 10 (1959). Zervas, Ber. Dtsch. Chem. Ges., 64, 2289 (1931). Imanari and Tamura, Agric. Biol. Chem., 35, 321 (1971). Plouvier, C.R. Acad. Sci., 256, 1397 (1963). Hudson and Dale, J. Am. Chem. Soc., 37, 1264, 1280 (1915). Harris, Hirst, and Wood, / Chem. Soc. (Lond.), p. 2108 (1932). Jones and Jones, Can. J. Chem., 47, 3269 (1969). Purdie and Irvine, / Chem. Soc. (Lond.), p. 1049 (1904). Bates, Polarimetry, Saccharimetry and the Sugars: National Bureau o f Standards Circular C440, U.S. Gov. Print. Off., Washington, D.C., 1942. 187. Georg, Helv. Chim. Acta, 12, 261 (1929). 188. Micheel and Berendes, Mikrochim. Acta, 519 (1963). 189. Brennan,/. Chromatogr., 59, 231 (1971). 190. Brigl and Scheyer, Hoppe-Seyler's Z. Physiol. Chem., 160, 214 (1926). 191. Alberda van Ekenstein and Blanksma, Reel. Trav. Chim. Pays-Bas, 24, 33 (1905). 192. Yoshida, Honda, lino, and Kato, Carbohydr. Res., 10, 333 (1969). 193. Irvine and Oldham, J. Chem. Soc. (Lond.), p. 1744 (1921). 194. Purdie and Irvine,/. Chem. Soc. (Lond.), p. 1049 (1904). 195. Irvine and Moodie, /. Chem. Soc. (Lond.), p. 1578 (1906). 196. Duff, /. Chem. Soc. (Lond.), p. 4730 (1957). 197. Duff, Webley, and Farmer, Biochem. J., 65, 21P (1957). 198. Joseph son, Ber. Dtsch. Chem. Ges., 62, 317 (1929). 199. Schumacher, Carbohydr. Res., 13, 1 (1970). 200. Ohle, Biochem. Z., 131, 611 (1922). 201. Brigl and Griiner, Justus Liebigs Ann. Chem., 495, 60 (1932). 202. Fischer and Bergmann, Ber. Dtsch. Chem. Ges., 51, 1760, 1804 (1918). 203. Tschesche, Kammerer, and Wulff, Tetrahedron Lett., p. 701 (1968). 204. Finnegan, Mueller, and Morris, Proc. Chem. Soc. London, p. 182 (1963). 205. Carter, / Sci. Food Agric., 2, 54 (1951). 206. Finnegan and Stephani, J. Pharm. Sci., 57, 353 (1968). 207. Sloneker and Orentas, Can. J. Chem., 40, 2188 (1962). 208. Fischer and Lieberman, Ber. Dtsch. Chem. Ges., 26, 2415 (1893). 209. Fischer and Zach, Ber. Dtsch. Chem. Ges., 45, 3761 (1902). 210. Evans, Long, Jr., and Parrish,/. Chromatogr., 32, 602 (1968). 211. Stan'ek and Tajmr, Chem. Listy, 52, 551 (1958). 212. Ebert and Zenk, Arch. Mikrobiol., 54, 276 (1966). 213. Fr£rejacque, C.R. Acad. Sci., 230, 127 (1950). 214. Korte, Ber. Dtsch. Chem. Ges., 88, 1527 (1955). 215. Reyle and Reich stein, Helv. Chim. Acta, 35, 195 (1956). 216. Allgeier, Weiss, and Reichstein, Helv. Chim. Acta, 50, 456 (1967). 217. Miyano and Benson, /. Am. Chem. Soc., 84, 59 (1962). 218. Chanley, Ledeen, Wax, Nigrelli, and Sobotka,/. Am. Chem. Soc., 81, 5180 (1959). 219. Saier, Jr. and Ballou,/. Biol. Chem., 243, 992 (1968). 220. Jeanloz and G ut,/. Am. Chem. Soc., 76, 5793 (1954). 221. Irvine and Scott,/. Chem. Soc. (Lond.), p. 571, 575, 582 (1913). 222. Oldham,/. Am. Chem. Soc., 56, 1360 (1934). 223. Jeanloz, Rapin, and Hakomori,/. Org. Chem., 26, 3939 (1961). 224. Levene and Raymond,/. Biol. Chem., 88, 513 (1930). 225. Lee and Ballou,/. Biol. Chem., 239, 3602 (1964). 226. Helferich, Klein, and Schafer, Ber. Dtsch. Chem. Ges., 59, 79 (1926). 227. Helferich and Himmen, Ber. Dtsch. Chem. Ges., 62, 2136, 2141 (1929). 228. Helferich and Gunther, Ber. Dtsch. Chem. Ges., 64, 1276 (1931). 229. White and R ao,/. Am. Chem. Soc., 75, 2617 (1953).

22 2

Handbook o f Biochemistry and Molecular Biology

Table 3 (continued) NATURAL ALDOSES 230. 231. 232. 233. 234. 235. 236. 237. 238. 239. 240. 241. 242. 243. 244. 245. 246. 247. 248. 249. 250. 251. 252. 253. 254. 255. 256. 257. 258. 259. 260. 261. 262. 263. 264. 265. 266. 267. 268. 269. 270. 271. 272. 273. 274. 275. 276. 277. 278. 279. 280. 281. 282. 283. 284. 285. 286.

Christensen and Sm ith,/. Am. Chem. Soc., 79, 4492 (1957). Fischer, iter. Dtsch. Chem. Ges., 23, 2618 (1890). Makarevich and Kolesnikov, Chem. Nat. Compd., (USSR), 5, 164 (1969). Zissis, Richtmyer, and Hudson, J. Am. Chem. Soc., 73, 4714 (1951). Blindenbacher and Reichstein, Helv. Chim. Acta, 31, 1669 (1948). Frdrejacque and Hasenfratz, C.R. Acad. Sci., 222, 815 (1946). Fr^rejacque and Durgeat, C.R. Acad. Sci., 228, 1310 (1949). Doebel, Schlittler, and Reichstein, Helv. Chim. Acta, 31, 688 (1948). Perry and Daoust, Can. J. Chem., 51, 3039 (1973). Capek, Tikal, Jary, and Masojidkovd, Collect. Czech. Chem. Commun., 36, 1973 (1971). Takita, Maeda, Umezawa, Omoto, and Umezawa, J. Antibiot. (Tokyo) Ser. A, 22, 237 (1969). Evans and Parrish, Carbohydr. Res., 28, 359 (1973). Wolfrom and A nno,/. Am. Chem. Soc., 74, 5583 (1952). Cooke and Percival, Carbohydr. Res., 32, 383 (1974). Ohashi, Kawabe, Kono, and Ito, Agric. Biol. Chem., 37, 2379 (1973). Avigad, Amaral, Asensio, and Horecker,/. Biol. Chem., 237, 2736 (1962). Maradufer and Perlin, Carbohydr. Res., 32, 127 (1974). Wolfrom and Usdin, /. Am. Chem. Soc., 75, 4318 (1953). Perlin, Mackie, and Dietrich, Carbohydr. Res., 18, 185 (1971). Webb, Broschard, Cosulich, Mowat, and Lancaster,/. Am. Chem. Soc., 84, 3183 (1962). Overend, Stacey, andStandk, /. Chem. Soc. (Lond.), p. 2841 (1949). Bonner,/. Org. Chem., 26, 908 (1961). Wirz and Hardegger, Helv. Chim. Acta, 54, 2017 (1971). Keleti, Mayer, Fromme, and LUderitz, Eur. J. Biochem., 16, 284 (1970). terny, Pacrfk, and Stan^k, Chem. Ind., p. 945 (1961). Herzog, Meseck, Delorenzo, Murawski, Charney, and Rosselet, Appl. Microbiol., 13, 515 (1965). Zorbach and Ciaudelli, / Org. Chem., 30,451 (1965). Studer, Panavaram, Gavilanes, Linde, and Meyer, Helv. Chim. Acta, 46, 23 (1963). Berlin, Esipov, Kiseleva, and Kolosov, Chem. Nat. Compd., (USSR), 3, 280 (1967). Brufani, Keller-Schierlein, Loffler, Mansperger, and Zahner, Helv. Chim. Acta, 51, 1293 (1968). Ganguly and Sarre, /. Chem. Soc. D Chem. Commun., p. 1149 (1969). Vischer and Reichstein, Helv. Chim. Acta, 27, 1332 (1944). Tschesche and Buschauer, Justus Liebigs Ann. Chem., 603, 59 (1957). Allgeier*Helv. Chim. Acta, 51, 311,668 (1968). Westphal, LUderitz, Fromme, and Joseph, Angew. Chem., 65, 555 (1953). Fouquey, Lederer, LUderitz, Polonsky, Staub, Stirm, Tirelli, and Westphal, C.R. Acad. Sci., 246, 2417 (1958). Williams, Szarek, and Jones, Can. J. Chem., 49, 796 (1971). Stirm, LUderitz, and Westphal, Justus Liebigs Ann. Chem., 696, 180 (1966). Berlin, Esipov, Kolosov, Shemyakin, and Brazhnikova, Tetrahedron Lett., p. 1323 (1964). Miyamoto, Kawamatsu, Shinohara, Nakadaira, and Nakanishi, Tetrahedron, 22, 2785 (1966). Blindenbacher and Reichstein, Helv. Chim. Acta, 31, 2061 (1948). Hesse, Ber. Dtsch. Chem. Ges., 70, 2264 (1937). Celmer and Hobbs, Carbohydr. Res., 1, 137 (1965). Davies, Nature, 191,43 (1961). Ganguly, Sarre, and Reimann, /. Am. Chem. Soc., 90, 7129 (1968). Stevens, Nagarajan, and Haskell,/. Org. Chem., 27, 2991 (1962). Stevens, Cross, and Toda,/. Org. Chem., 28, 1283 (1963). Albano and Horton,/. Org. Chem., 34, 3519 (1969). Williams, Szarek, and Jones, Carbohydr. Res., 20, 49 (1971). Berlin, Esipov, Kolosov, and Shemyakin, Tetrahedron Lett., p. 1431 (1966). Berlin, Borisova, Esipov, Kolosov, and Kirvoruchko, Chem. Nat. Compd., (USSR), 5, 89, 94 (1969). Brimacombe and Portsmouth, Carbohydr. Res., 1, 128 (1965); Chem. Ind., p. 468 (1965). Howarth, Szarek, and Jones, Can. J. Chem., 46, 3375 (1968). Shoppe and Reichstein, Helv. Chim. Acta, 25, 1611 (1942). Tamm and Reichstein, Helv. Chim. Acta, 31, 1630 (1948). Brimacombe, Portsmouth, and Stacey,/. Chem. Soc. (Lond.), p. 5614 (1965). Miyamoto, Kawamatsu, Shinohara, Asahi, Nakedaira, Kakisawa, Nakanishi, and Bhacca, Tetrahedron Lett., p. 693 (1963).

223

Table 3 (continued) NATURAL ALDOSES 287. 288. 289. 290. 291. 292. 293. 294. 295. 296. 297. 298. 299. 300. 301. 302. 303. 304. 305. 306. 307. 308. 309. 310. 311. 312. 313. 314. 315. 316. 317. 318. 319. 320. 321. 322. 323. 324. 325. 326. 327. 328. 329. 330. 331. 332. 333. 334. 335. 336. 337. 338. 339. 340. 341. 342. 343.

Iselin and Reichstein, Helv. Chim. Acta, 27, 1200 (1944). Brockmann and Waehneldt, Naturwissenschaften, 48, 717 (1961). Wyss, J&ger, and Schindler, Helv. Chim. Acta, 43, 664 (1960). Renkonen, Schindler, and Reichstein, Helv. Chim. Acta, 42, 182 (1959); 39, 1490 (1956). Kilani, Arch. Pharm., 234, 486 (1896). Stahl and Kaltenbach, / Chromatogr., 5, 351 (1961). Haga, Chonan, and Tejima, Carbohydr. Res., 16, 486 (1971). El-Dash and Hodge, Carbohydr. Res., 18, 259 (1971). Krasso, Weiss, and Reichstein, Helv. Chim. Acta, 46, 1691 (1963). Jacobs,/. Biol. Chem., 88, 519 (1930). Bolliger and Ulrich, Helv. Chim. Acta, 35, 93 (1952). Prins, Helv. Chim. Acta, 29, 378 (1949). Fouquey, Polonsky, Lederer, Westphal, and Luderitz, Nature, 182, 944 (1958). Davies, Staub, Fromme, Luderitz, and Westphal, Nature, 181, 822 (1958). Ekborgand Svensson, Acta Chem. Scand., 27, 1437 (1973). Woo, Dion, and Bartz, / Am. Chem. Soc., 83, 3352 (1961). Keller-Schierlein and Roncari, Helv. Chim. Acta, 45, 138 (1962); 49, 705 (1966). Westphal and Luderitz, Angew. Chem., 72, 881 (1960). Kochetkov and Usov, Bull Acad. Sci. USSR Engl. Ed., p. 471 (1965). Stevens, Blumbergs, and Wood, / Am. Chem. Soc., 86, 3592 (1964). Brockmann and Waehneldt, Naturwissenschaften, 50, 43 (1963). Rinehart, Jr. and Borders, / Am. Chem. Soc., 85, 4037 (1963). Haines, Carbohydr. Res., 21, 99 (1972). Kowalewski, Schindler, Jager, and Reichstein, Helv. Chim. Acta, 43, 1214, 1280 (1960). Golab and Reichstein, Helv. Chim. Acta, 44, 616 (1961). Angus, Bourne, and Weigel, / Chem. Soc. (Lond.), p. 22 (1965). Bolliger and Reichstein, Helv. Chim. Acta, 36, 302 (1953). Jacobs and Bigelow, / Biol. Chem., 96, 355 (1932). Abisch, Tamm, and Reichstein, Helv. Chim. Acta, 42, 1014 (1959). Hauenstein and Reichstein, Helv. Chim. Acta, 33, 446 (1950). Matern, Grisebach, Karl, and Achenbach, Eur. J. Biochem., 29, 1,5 (1972). Arcamone, Barbieri, Franceschi, Penco, and Vigevani, / Am. Chem. Soc., 95, 2008 (1973). Regna, Hochstein, Wagner, and Woodward, / Am. Chem. Soc., 75, 4625 (1953). Hofheinz, Grisebach, and Friebolin, Tetrahedron, 18, 1265 (1962). Lemal, Pacht, and Woodward, Tetrahedron, 18, 1275 (1962). Flaherty, Overend, and Williams,/. Chem. Soc., Sect. C, Org. Chem., p. 398 (1966). Foster, Inch, Lehmann, Thomas, Webber, and Wyer, Proc. Chem. Soc. London, p. 254 (1962); Chem. Ind., p. 1619 (1962). Paul and Tchelitcheff, Bull. Soc. Chim. Fr., p. 443 (1957). Jaret, Mallams, and Reimann, J. Chem. Soc. (Lond.) Perk. I, p. 1374 (1973). Omura, Katagiri, and Hata, / Antibiot. (Tokyo), 21, 272 (1968). Watanabe, Fujii, and Satake, / Biochem. (Tokyo), 50, 197 (1961). Flynn, Sigal, Wiley, and Gerzon, / Am. Chem. Soc., 76, 3121 (1954). Corcoran, / Biol. Chem., 236, PC27 (1961). Wiley and Weaver, / Am. Chem. Soc., 77, 3422 (1955); 78, 808 (1956). Luderitz, Staub, Stirm, and Westphal, Biochem. Z., 330, 193 (1958). Wiley, Mackellar, Carron, and Kelly, Tetrahedron Lett., p. 663 (1968). Zhdanovich, Lokshin, Kuzovkov, and Rudaya, Chem. Nat. Com pd, (USSR), 7, 625 (1971). Okuda, Suzuki, and Suzuki, J. Biol. Chem., 242, 958 (1967); 243, 6353 (1968). Haworth, Raistrick, and Stacey, Biochem. / , 29, 2668 (1935). Sorkin and Reichstein, Helv. Chim. Acta, 28, 1, 662 (1945). Stoffyn and Jeanloz, / Biol. Chem., 235, 2507 (1960). Baggett, Stoffyn, and Jeanloz, / Org. Chem., 28, 1041 (1963). Vargha, Ber. Dtsch. Chem. Ges., 87, 1351 (1954). Levene,/. Biol. Chem., 57, 329 (1923); 59, 129 (1924). Bishop, Perry, Blank, and Cooper, Can. J. Chem., 43, 30 (1965). Hamilton, Partlow, and Thompson, /. Am. Chem. Soc., 82, 451 (1960). Levine, Hansen, and Sell, Carbohydr. Res., 6, 382 (1968).

224

Handbook o f Biochemistry and Molecular Biology

Table 3 (continued) NATURAL ALDOSES 344. 345. 346. 347. 348. 349. 350. 351. 352. 353. 354. 355. 356. 357. 358. 359. 360. 361. 362. 363. 364. 365. 366. 367. 368. 369. 370. 371. 372. 373. 374. 375. 376. 377. 378. 379. 380. 381. 382. 383. 384. 385. 386. 387. 388. 389. 390. 391. 392. 393. 394. 395. 396. 397. 398. 399. 400. 401.

Butler and Cretcher, J. Am. Chem. Soc., 53, 4358, 4363 (1931). Omoto, Takita, Maeda, and Umezawa, Carbohydr. Res., 30, 239 (1973). Dutton and Yang, Can. J. Chem., 50, 2382 (1972). Markovitz,/. Biol. Chem., 237, 1767 (1962). Ganguly and Saksena, J. Chim. Soc. D Chem. Commun., p. 531 (1973). Wiley, Duchamp, Hsiung, and Chidester, J. Org. Chem., 36, 2670 (1971). Morrison, Young, Perry, and Adams, Can. J. Chem., 45, 1987 (1967). MacLennan, Biochem. J., 82, 394 (1962). MacLennan, Smith, and Randell, Biochem. J., 74, 3P (1960); 80, 309 (1961). Ovodov and Evtushenko, J. Chromatogr., 31, 527 (1967). Caudy and Baddiley, Biochem. J., 98, 15 (1966). Aspinalland Zweifel, J. Chem. Soc. (Lond.), p. 2271 (1957). Scheer, Terai, Kulkami, Conant, Wheat, and Plowe, J. Bacteriol., 103, 525 (1970). Perry and Webb, Can. J. Chem., 47, 31 (1969). Gros, Deulofeu, Galmarini, and Frydman, Experientia, 24, 323 (1968). Behrend, Ber. Dtsch. Chem. Ges., 11, 1353 (1878). Collins and Overend, J. Chem. Soc. (Lond.), p. 1912 (1965). Purdie and Young, J. Chem. Soc. (Lond.), p. 89, 1194 (1906). Fischer, Ber. Dtsch. Chem. Ges., 28, 1158 (1895). Fischer, Ber. Dtsch. Chem. Ges., 29, 324 (1896). Fischer, Bergmann, and Rabe, Ber. Dtsch. Chem. Ges., 53, 2362 (1920). Vaterlaus, Kiss, and Spieglberg, Helv. Chim. Acta, 47, 381 (1964). Barker, Homer, Keith, and Thomas,/. Chem. Soc. (Lond.), p. 1538 (1963). Hinman, Caron, and Hoeksema, / . Am. Chem. Soc., 79, 3789 (1957). Walton, Rodin, Stammer, Holly, and Folkers,/. Am. Chem. Soc., 80, 5168 (1958). Young and Elderfield,/ Org. Chem., 7, 241 (1942). Andrews, Hough, and Jones,/. Am. Chem. Soc., 77, 125 (1955). Hirst, Percival, and Williams,/. Chem. Soc. (Lond.), p. 1942 (1958). Schmidt, Plankenhorn, and Kubler, Ber. Dtsch. Chem. Ges., 75, 579 (1942). Brown, Hough, and Jones,/. Chem. Soc. (Lond.), p. 1125 (1950). Percival and Percival,/. Chem. Soc. (Lond.), p. 690 (1950). Butler, Lloyd, and Stacey,/. Chem. Soc. (Lond.), pp. 1531, 1537 (1955). Charalambous and Percival,/. Chem. Soc. (Lond.), p. 2443 (1954). Geerdes and Smith, /. Am. Chem. Soc., 77, 3572 (1955). Chaput, Michel, and Lederer, Experientia, 17, 107 (1961). Hirst, Hough, and Jones,/. Chem. Soc. (Lond.), pp. 928, 3145 (1949). Wiley and Sigal, /. Am. Chem. Soc., 80, 1010 (1958). Pigman and Isbell,/. Res. Natl. Bur. Stand., 19, 189 (1937). Britton, Biochem. J., 85, 402 (1962). Hickman and Ashwell,/. Biol. Chem., 241, 1424 (1966). Stevens, Glinski, and Taylor,/. Org. Chem., 33, 1586 (1968). MacLennon, Biochim. Biophys. Acta, 48, 600 (1961). Schmutz, Helv. Chim. Acta, 31, 1719 (1948). Von Euw and Reichstein, Helv. Chim. Acta, 33, 485 (1950). Kapur and Allgeier, Helv. Chim. Acta, 51, 89 (1968). Sephton and Richtmyer, / . Org. Chem., 28, 1691 (1963). Strobach and Szabo, /. Chem. Soc. (Lond.), p. 3970 (1963). Isherwood and Jermyn, Biochem. /., 48, 515 (1951). MacLennon and Davies, Biochem. J., 66, 562 (1957). Davies, Biochem. J., 67, 253 (1957). Begbie and Richtmyer, Carbohydr. Res., 2, 272 (1966). Richtmyer and Charlson, J. Am. Chem. Soc., 82, 3428 (1960). Hulyalkar, Jones, and Perry, Can. J. Chem., 41, 1490 (1963). Young and Adams, Can. J. Chem., 43, 2929 (1965). Adams, Quadling,and Perry, Can. J. Microbiol, 13, 1605 (1967). Teuber, Bevill, and Osborn, Biochemistry, 7, 3303 (1969). Weidell, Hoppe-Seyler’s Z. Physiol. Chem., 299, 253 (1955). Varma, Varma, Allen, and Wardi, Carbohydr. Res., 32, 386 (1974).

225

Table 3 (continued) NATURAL ALDOSES

402. 403. 404. 405. 406. 407. 408. 409. 410. 411. 412.

Hellerqvist, Lindberg, Samuelson, and Brubaker, A eta Chem. Scand, 26, 1389 (1972). Boren, Eklind, Garegg, Lindberg, and Pilotti, Acta Chem. Scand., 26, 4143 (1972). Davies, Nature, 180, 1129 (1957). Missale, Colajacomo, and Bologna, Boll. Soc. Ital. Biol. Sper., 36, 1885 (1960); Chem. Abstr., 55, 24869 (1961). Kuriki and Kurahashi,/. Biochem. (Tokyo), 58, 308 (1965). Fraenkel, Osborn, Horecker, and Smith, Biochem. Biophys. Res. Commun., 11,423 (1963). Hoeksema,./. Am. Chem. Soc., 90, 755 (1968). Hoeksema and Hinman, J. Am. Chem. Soc., 86, 4979 (1964). Tschesche and Kohl, Tetrahedron, 24, 4359 (1968). Martinsson and Samuelson, J. Chromatogr., 50, 429 (1970). Walborg, Jr. and Kondo, Anal. Biochem., 37, 323 (1970).

3 0 8 -3 0 9 217 80 (dimer)

46—47

C15H12N80 8

C9H9N30 3

C3H80 3

C7H10O6

None

None

None

None

None

(D)

Specific rotation*3 [a] D

1

1

1

1

1

(E)

Reference0 (F) 6.3,26.6 (3)

(G)

Of (8)

55f(4)

88f(7)

(Η)

(I)

TLC

4 0 f(2 )

113 for (17)

75f (2)

Chromatography, R value, and referenced ■■ '■ .............. ......... ELC GLC PPC

Handbook o f Biochemistry and Molecular Biology

aIn alphabetical order by parent sugar names within groups of increasing carbon chain length in the parent compounds. b [a ]D for 1 -5 g solute, c, per 100 ml aqueous solution at 20-25°C , unless otherwise given. References for m.p. and specific rotation data. Letter indicates that the reference also has chromatographic data as follows: c = column, e = electrophoresis, g = gas, p = paper, and t = thin-layer. dR value times 100, given relative to that of the compound indicated by abbreviation: f = solvent front, for = formaldehyde 2,4-dinitrophenyIhydrazone, fru = fructose, glc = glucose, glcl = glucitol, glct = glucose trimethylsilyl ether, manh = manno-heptulose, rha = rhamnose, rib = ribose, sed = sedoheptulose, sor = sorbitol, van = vanillin, xyl = xylose. Under gas chromatography (column GLC or G), numbers without code indication signify retention time in minutes. The conditions of the chromatography are correlated with the reference given in parentheses and are found in Table 5. eA possible finding of glyoxal as a component in ethanol distillery streams exists, retention time of 29.9 min, but the identification needs other evidence.3 fThere is no clear evidence that the configuration is D- or L. ^Value is in cm/3 hr. ^Data are for the enanthiomorphic isomer. *The 1/2H2 O and 2H2 O forms also exist. Rrom cured tobacco and animal products fructose and amino acid combinations, which are probably rearranged glycoside compounds and hence not included here, have been isolated; see References 71 and 72. *This is an early structural name. The modern, preferred one is 3-hydroxy-2-furyl methyl ketone.98 While perhaps not carbohydrates in a strict sense, this group of pyranose compounds is included because of their intimate relationship. lA hemihydrate of lower melting point forms from the anhydrous anhydro sugar upon aging.

Oil, bp 72

(C)

Melting point °C

C3H40 2

(B)

(A)

Triosulose, 3-deoxy-(3deoxy-2-keto-glyceraldehyde, methyl glyoxal, pyruvic aldehyde)e fcw-2,4-Dimtrophenylhydrazone p-Nitrophenylhydrazone Triulose (2-ketoglyceritol, dihydroxyacetone) Diacetate

Chemical formula

Substance3 (synonym) derivative

Table 4 NATURAL KETOSES

226

160

Cj H j j N j C^

None None None

75 Liquid, bp 56 128 149 Liquid, bp 88

2 5 2 -2 5 4 23.4 7.6 Syrup

152-153

C3H7NO · HC1 C3H60

C9H10N4O4

C4H60 2

C16H14N80 8

C4H10O2

C4H10O2

C4H80 4

C10H13N3Os

+48 (C2H5OH) (18°)

+12

None (racemic)

None(meso)

None

None None

No constants known

No constants known

None

None

(D)

Sp ecific rotation*5 M d

C3H7NO

Dimer

277—278

(C)

M elting p o in t °C

C15H12N80 9

(B)

(A)

Ws-2,4-Dinitrophenylhydrazone p-Nitrophenylhydrazone Trimethylsilyl ether Triulose, l-amino-1,3dideoxy- (aminoacetone) Hydrochloride Triulose, dideoxy(acetone) 2,4-Dinitrophenylhydrazone p-NitrophenylhydraTetradiulose, 1,4dideoxy- (2,3-butanedione, diacetyl, dimethylglyoxal) bw-2,4-Dinitrophenylhydrazone eryi/iro-Butane-2,3diol D,L-f/j/*eoButane2,3-diol Tetrulose, L-glycero(L-erythrulose, ketoerythritol, Ltreulose) o-Nitrophenylhydrazone

Chem ical form ula

Substance3 (sy n o n y m ) derivative

15

11,12

1

1

1

1 None

1

1 1

1

1

1

(E)

R eference0

Table 4 (continued) NATURAL KETOSES

33rib(10)

6rib (10)

1 ,6

(F)

ELC

See also Table I

See also Table I

1.6(6)

82glct (5)

(G)

GLC

225glc(13)

Of (8)

4.1 (3)

93f (7)

(H)

PPC

Chrom atography, R value, and reference**

8 2 f(9 )

7 3 f(1 4 )

G)

TLC

227

Pentulose, 4-C-methyl 1,3,5-trideoxy- (diacetone alcohol, 4hydroxy-4-methyl-2pentanone)

b«-2,4-Dinitropheny lhydrazone 3-Deoxy-pentitol acetates Pentosulose, O-threo-f (xylosone, xylosulose) bis-2,4-Dinitrophenylhydrazone Methyl/3-pyranoside

sone)

D -( 3-d e o xy-D -p e n to -

3-hydroxybutan-2-one) 2.4- Dinitropheny 1hydrazone Fentodiulose, 1,3,5trideoxy-2,4-(acetylacetone, 2,4-pentanedione) 2.4- Dinitrophenylhydrazone o-Nitrophenylhydrazone eryi/iroPentane-2,4diol threo-Pentane-2,4diol Pentosulose, 3-deoxy-

D -£ /yce ro(a ce to in ,

C6H120 2

C8H10O5

0 17Η17Ν80 31

C5H80 5

Ci 3Hi 6° e

C17H16N8O10

No constants known Liquid, bp 164

No constants known 231

259

No constants known +187 (c 0.36, dioxane) No constants known None

+294 (dioxane)

+7

1

17

17

18, 19ct

1 7 -1 0

100van(20a)

250van(10a)

Oil

23

C5H80 4

None

22

Orib (10)

100s, 135 m

Cn H13N303

None

1

(F)

" ELC

C5H x2 0 2

122

Cn Hn N4Os

None

1

1,6,16

(E)

Reference0

Orib (10)

Liquid bp 139 (746 mm)

C5H80 2

-12(CHC13)

(H 2O)

-1 .4 (neat),-105

(D)

Specific rotation11 [a ]D

37.8(3)

16.5, 18.5 (19c)

17.3(3)

2 4 (3 )

(G)

GLC

162glc (20b)

430glc(19b)

91f(9)

(Η)

PPC

Chromatography, R value, and reference1*

C5Hl 2 0 2

114-116

Liquid, bp 143

(C)

Melting point °C

C10H15N ,O s

C .H .O ,

(B)

(A)

Tetrulose, 1,4-dideoxy-

Chemical formula

Substance3 (synonym) derivative

Table 4 (continued) NATURAL KETOSES

66 for (17)

(I)

TLC

228

Handbook o f Biochemistry and Molecular Biology

Pentulose, l^threo- (Lxylulose, L-xylulose, xyloketose) p-B rom ophenylhy drazone

-5 ± 1 (CH3OH) 34c

174-175

C5H10O4

C5H120 4 C5Hj 2 0 4 C17H20N4O2

128-129

175—176

CMH14N4Oe

BrC11H15N20 4

1 26-128

BrC11H15N20 4

Syrup

Syrup

C5H10Os

C5H10O5

126-127

C6H10O5 Ct j C^H j 4N20 4

-26-*+31.9 (C5H5N)

+74->+7 (C5H5NC2H5OH) +33.3

+ 2 4 .1 -» -31 (C5H5N) 7d

-3 3

+47.4 (c 0.3, CH3OH) None (meso) None

162-163

C11H15N30 6

+16.6

Syrup

-5 2 ± 5 (CH3OH)

-1 5

None

(D)

S p ecific rotation** [a]D

C5H10O5

165-166.5

Syrup

C5H10Os

AHx s N30 6

1 9 8 -199

(C)

M elting p o in t °C

C12Hi e N4Os

(B)

(A)

2.4- Dinitrophenylhydrazone Pentulose, Ώ-erythro(adonose, D-ribulose) o-Nitrophenylhydrazone Trimethylsilyl ether Pentulose, L-erythro(L-ribulose) 0- Nitrophenylhydrazone Pentulose, erythro-32.5- Dichlorophenylhydrazone Pentulose, Ώ-threo- (Dxylulose) p-Bromophenylhydrazone 2,4-Dinitrophenylhydrazone Pentulose, 5-deoxy-Dthreo- (5-deoxy-Dxylulose) 1-Deoxy-D-arabinitol 1-Deoxy-L-xylitol Phenylosazone

Chem ical form ula

Substancea (syn o n ym ) derivative

35

25p,35,36

34

32

24,3 3

24p

31cp 32cp

30

27p, 29

27

24,25cp

1

(E)

R eference0

Table 4 (continued) NATURAL KETOSES

103glcl (43) 96glcl (43)h

194rib(10)

9 .l g (31)

209rib(10)

(F)

ELC

153rha(34)

43f (26)

25, 33, 35glct (28)

(G)

GLC

65f(30c)

45f(44)

68f (30c)

38f (26)

(Η)

PPC

Chrom atography, R value, and reference**

( 36)

117 xyl

(I)

TLC

229

See also l-Deoxy-D-galactitol and -D-talitol under Hexodiulose, 6-deoxy-D-ery//ira-2,5above Hexosulose, 3-deoxy-Deryth ro- (3-deoxy-2-

Hexos-5-ulose, 6-deoxyD-arabinoiw-(p-Nitrophenyl-

Tetraacetate ·Η 20

1-Deoxy-D-talitol Hexodiulose, Ό-threo2,5-(5-keto-fructose) 6/s-Phenylhydrazone Hexos-2,3-diulose, 4,6dideoxy- (actinospectose) Hexosulose, Ό-arabino(D-glucosone) 2,4-Dinitrophenylosazone Phenylosazone 253d 20 6-20 8

C18Hi e N80 12

C18H22N40 4

C6H10O5

Cj e H2(1N60 ,

Ce H10O8 211d

112

Syrup

C8H10O6

C ,4Η χ80 , 0 · H20

No constants known

157-159, 172-174 1 3 3 -1 3 5 ,1 4 1

162-164 No constants known 106-108

(C)

Melting point °C

C6H80 4

C18H22N40 4

C ,H 14Os C„H1(,Oe

C6H14Os Ce H140 5

C17H20N4O3 C6 9 0 5

(B)

(A)

Phenylosazone Hexodiulose, 6-deoxy-Derythro- 2,51-Deox y-L-altritol l-Deoxy-D-galactitol

Chemical formula

Substance3 (synonym) derivative

-2 .5 -+ 1 .5 (c 6) (27°)

+1.1 (c 0 .6 ,C 5H5N) (15°)

17,46,50

49

4 8 ,4 9

47

45

46

41,42

40

38,39

38,39p

58

25 37

(E)

Reference0

-Ί5-+-41 (c 0.7, C5Hs N-C2H5OH, 2:3) +14.7->+53.7 (20% C2H5OH) 96h -4 .3 (CH,OH) (12°)

- 1 0 . 6 + 7 . 9 (c 8.5) (15°)

No constants known

-1 6 4 (C 5H5N)

-85

No constants known -2.6 (18°)

(D)

Specific rotation** [a] j)

Table 4 (continued) NATURAL KETOSES

98glcl (43)h lOOglcl (43)" 104glcl (43)

(F)

ELC (G)

GLC

20 0 -2 7 0 137 106gle(51)

38f(49)

25glc (45)

70fru (38)

36f(44) 31f(44)

(Η)

PPC

Chromatography, R value, and reference^

(17)°*

(I)

TLC

230 Handbook o f Biochemistry and Molecular Biology

6-Deoxy-L-talitol (1-deoxy-Laltritol) Hexos-3-ulose, Ό-ribo(3-keto-D-glucose) Methylα-pyranoside trimethyl ether

Hexosulose, 6-deoxy-Llyxo- (angustose, 2keto-fucose) Methyl pyranoside dimethyl acetal Methyl pyranoside

No constants known Oil, bp 4 7 -4 9 (0.3 mm) No constants known

C6HJ0O4

106-108

5 8 -6 0 82.5-83.5

C6Hi e 0 6 «5H20

C10H180 6

7 7 -7 8

115-116

C6H140 5

C9H180 6

C6H10O5

123-124

C18H22N40 4

[a] s78 +164 (c 0.9, CHCl^)

+14.8 (26°)

-53.3 (C2H5OH) (18°) -2.6 (18°)

-19.3(C H 3OH)

-138.5 (c 0.25, C5H5N) +18(C 2H5OH)

60t

59

58

58

58

58c

57

57p 57

157-158 173-174

Cu H20N6 O9

- 86.6

56 56

+310±2 (CHCI3)11 + 347± 2(c0.6, CHC13)h

158-159

C7H120 3 C13H17N30 4

54

53

53t

46,51,52

(E)

R eference6

55

No constants known

No constants known +166.3 (27°)

+86 (c 0.09, DMSO)

(D)

Sp ecific rotation** [a]D

C6H10O3

C6H10O4

C9H140 4

2 5 Id, 265d

(C)

M elting p o in t °C

Ο ,,,Η ,,Ν ,Ο ,,

(B)

(A)

2,4-Dinitrophenylosazone Hexos-4-ulose, 3,6dideoxy-D-erythrowo-Propylidene ether Hexos-4-ulose, 3,6dideoxy-L-erythroHexos-4-ulose, 2,3,6trideoxy-L-g/ycero(cinerulose A) M ethylα-pyranoside Methyl α-pyranoside p-nitrophenylhydrazone Hexos-5-ulose, D-lyxobis- (p-N itr ophenylhy drazone) Ms-Phenylhydrazone

Chem ical form ula

Substance2 (sy n o n y m ) derivative

Table 4 (continued) NATURAL KETOSES

98glcl (43)h

(F)

' ' ELC

(G)

GLC

116fru(59)

36f(44)h

36f(58)

(Η)

PPC

Chrom atography, R value, and reference4* ’

7 0 f(5 6 )h

37 for ( 17)

(I)

TLC

231

o-Nitrophenylhydrazone Hexulose, D-lyxo- (Dtagatose) Phenylosazone Pyranose pentaacetate

136-137 131-132 186-187 132

C12H17N30 6

C4H120 6

C18H22N40 4 C16H220 11

C6H140 5 C6H140 5

[0 5

Ce H80 4

C6H60 4

C10H10O6 C18H14N8O10

CJ8H18N40 2 C6H60 3

CJ3H10O4 C7H80 3

C13H1JN 0 4

115.5-117

C8Hi e Os

Phenylurethane

187

C6H60 5

Pyran-4-one, 3,5-dihydroxy-2-hydroxymethyl(wo-kojic acid, hydroxy-kojic acid, oxy-kojic acid) 3,5-Di-(9-methyl ether 2.4- Dinitrophenylhydrazone Pyran-4-one, 3,5-dihydroxy-2-methyl-(5hydroxy-maltol, oxymaltol) 3.5- Di-O-methyl ether Pyran-4-one, 2,3-dihydro-3,5-dihydroxy6-methyl- (dihydrohydroxy-maltol) Pyran-4-one, 5-hydroxy2-hydroxy m ethy 1(kojic acid) Diacetate 2,4-Dinitrophenyl hydrazone Phenylosazone Pyran-4-one, 3-hydroxy2-methyl- (maltol) Benzoate Methyl ether

(C)

(B)

(A)

Melting point °C

Chemical formula

Substance3 (synonym) derivative

None

None

None None

None None

None

None

None

None

None

None

None

(D)

Specific rotation** [a ]D

95

95

92 95,96,98p

93 94

91

92

90

90,92

90

90

90

(E)

Reference0

Table 4 (continued) NATURAL KETOSES

(F)

ELC

44 (92a)

65 (92a)

67.5 (92a)

(G)

GLC

6 If (91)

72f (91)

46f (91)

(Η)

PPC

Chromatography, R value, and reference**

45f (92b)

38f (92b)

43f(92b )

(I)

TLC

234 Handbook o f Biochemistry and Molecular Biology

100-101 216 101.5-103 128-130 144.5-146 125-128 164-167 Amorphous

155-156

9 8 -99.5 101-102(91s)

C13H10O4 C12H19N40 6

C7H80 3 C7H140 7 C7H160 7

C7H160 7

C19H28N4Oe C7H140 7

C7H120 6

C19H260 13

C7H120 6 *H20

C25H620 7Si6

101±2

(C)

M elting p o in t °C

C6H60 3

(B)

(A)

Trimethylsilyl ether Pyran-4-one, 3-hydroxy5-methyl-k (isomaltol) Benzoate 2,4-Dinitrophenylhydrazone Methyl ether Heptulose, D-alioD-glycero-Ό-alloHeptitol Ό-glycero-O-altroHeptitol Phenylosazone Heptulose, Ώ-altro(sedoheptose, sedoheptulose) See D-glycero-D-glucoand D-glycero-O-taloHeptitols in Table 1 2,7-Anhydro-0pyranose (sedoheptulosan Pyranose hexaacetate Sedoheptulosan hydrate Sedoheptulosan trimethylsilyl ether Trimethylsilyl ether

Chem ical form ula

Substance3 (sy n o n y m ) derivative

+18 (hexane)

-132

+59 (CHC13)

-145

+2.5 (c 10)

-0.3±0.4

None +52.8 (c 0.2) None (meso)

None None

None

(D)

Sp ecific rotation** [a]D

106

104

105

101

101 101,102

107,122

92,97 101c,122 122

97 97

97

(E)

R eference0

Table 4 (continued) NATURAL KETOSES

lOOrib(10) 144rib (10)

(F)

ELC

166glct(106)

112glct(28)

21 (92a)

4.6 (100)

(G)

GLC

73f(103)

41f(103)

99fru(101)

(Η)

PPC

Chrom atography, R value, and reference** '

50f(92b )

75f(92b )

(I)

TLC

235

Trimethylsilyl ether Heptulose, L-guloSee L-glycero-D-gluco-Ueptitol above and O-glycero-D-glucoHep titol in Table 1

L-glycero-L-guloHep titol L-glycero-L-idoHep titol Phenylosazone

100-102 100-115

C4 2H340 12 C7H140 7 · O

C7H140 7

C25H620 7Si6 Syrup

181—182d

C19H26N40 5

-2 8

+6->-35.3 (C5H5NC2H s OH,2:3) 96h +36 (hexane)h

-0 .8

129-130

C7H160 7

-68 None (meso)

171-172

C7H140 7

-90->-45 -113 (CHC13)

- 8 0 ,- 9 0

+20

(D)

Specific rotation** [—13.4 (c 0.6)

Syrup 178-180

C l 4C12 H2 0N2 0 7

+47.4->+12.9 (6h)

C8H160 8

135-137

C7H140 7

+74-H-35 +39 (CHC13) +30.4 (hexane)

None (meso)

200 110

C19H26N40 5 CI9H260 13 C25H620 7Si6

C7H160 7

152

178-179

C19H26N40 5

C7H140 7

-34±8 (c 0.3)

172

C7H120 6

+11.6-+-43.4 (C5H5N) 72h +29.4

None (meso)

+111-H-65 (C5HSN) 47h -2 0

-39.7

(D)

Sp ecific rotation** [a]D

C7H160 7

C7H140 7

197-200d

C19H26N40 5

Heptulose, D-idoSee O-glycero-Oido-Heptitol in Table 1 Ό-glycero-L-idoHeptitol Anhydro-D-wfo-heptulose (idoheptulosan) Phenylosazone

11 3 -1 1 5 1

C7H120 6

2,7-Anhydro-L -guloheptulose (guloheptulosan) Phenylosazone

(C)

(B)

(A)

M elting p oin t °C

Chem ical form ula

Substancea (syn o n ym ) derivative

123cp, 124cp 123

3

121,122

110,119 120 106

101c,115

104

113

104

112

112

(E)

R eference0

Table 4 (continued) NATURAL KETOSES

40sor(116)

182rib (10)

(F)

ELC

194glct(106)

(G)

GLC

42sed (101)

138manh(110)

102glc(117)

86rib (113)

50f (118)

65f (118)

(Η)

PPC

Chrom atography, R value, and reference**

(I)

TLC

237

Heptulose, Ό-mannoSee D-glycero-O-galactoand O-glycero-O-taloHeptitols in Table 1 Phenylosazone Pyranose hexaacetate Trimethylsilyl ether Heptulose, Ό-taloSee O-glycero-Dfl/iro-Heptitol above D-glycero-L-altroHeptitol Octulose, D-glycero-Lgalacto 2.5-Dichlorophenylhydrazone - 5 7 , -43.4->—13.4 (c 0.6)

Syrup 1 78-180

C8H160 8

C, 4C12H20 N20 7

+47.4->+12.9 (6h) None (meso)

135-137

C7Hl4 0 7

+74-H-35 +39 (CHC13) +30.4 (hexane)

C7H160 7

200 110

C19H26N40 5

C19H26N4Os C19H260 13 C2 5H6 20 7 Si6

178-179

C7H120 6

152

-34±8 (c 0.3)

172

C7H160 7

C7H 140 7

None (meso)

188-189d

C20H26N4O6 C7H140 7

+11.6->-43.4 (CSHSN) 72h +29.4

-20

169-170

Cl 4CLjH2 0 N2 0 7

+20,+25 (CH3OH)

(D)

Specific rotation** [a] D

Syrup

(C)

Melting point °C

C8H160 8

(B)

(A)

Octulose, D-glycero-Όmanno2.5-Dichlorophenylhydrazone Phenylosazone Heptulose, Ό-idoSee D-glycero-D/