Isobenzopyrylium Salts

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u m m zm m & zm m m

Walter Behert Kmx

A d iss e rta tio n submitted In p a rtia l fu lfillm e n t of the requirements fo r the degree of Doctor of Philosophy in the Department of Chemistry in %he Graduate College of the State University of Iowa August I 950

ProQuest Number: 10666175

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v ^ o W A r 0 - 0 0 . &-

I wish t© express Ey appreciation i© Professor MLph I*. Sbriner fo r M s en th u siastic guidance throughout th is study.

I als© wish to express ®y appreciation to the

facu lty o f the organic chemistry d iv isio n o f the S tate U niversity ©f Iowa* for ®a©y helpfnl suggestions*

r

os X

U ii

C harter

i ii H i

£m>

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♦ * *

mmowmh jm

3

mnmmtm vwssaam

9

* * . . . . . . . . . . . . .

A, Btc&ies «a- 1,3~3iph6isyl~2~heE£opyryIi^ S a lts . . . . B. S t a l e s ©a 1,3* 4V£riph©isyl^2-ben2Gpyrylim S a lts . C* Jgesevtega* S iraetn res o f S^Bengopyrylim S a lts . 15, Absorption Spectra o f 2~Benz©pyryliPm S a lts

and Helatsd Gomponnds. . . . . . . . . I?

Mwmmmm

%

9

. 14 *

. . . . . . . 29

.............................................................................. 4 i

a cid . . . . . i &I H©©©phihaXie amfc^&rl&e . . . . . . . . . . . . . . . . 42 3 -P h a i^ llseco m a rla . . i * 42 1 #3-B lphenyl-2~beasopyryl lam p erch lo ra te. . . . . . . . 43 1#3-Blph©Byl-2-Mns©pyrylitiEi ch lo rid e . . . . . . . . . 44 1 #3 ~M pM nyl~ 2-b en 2©pyrylinm bromide . . . . . . . . * 44 1* 3 *Slph©nyl^2^'b©nzGpjr3rlinffi ferrieh lorid © . . . . . ( . 45 1 ,3~£iphesyl~2~bensGpyryXinm fe r r i’broml&e . * . . . r'. . 4 5 O zonolysis o f 1 $3~d iphenyl-*2~'ben zopyry1 in® p erch lorate . . . . 4 6 B ensalphthallde . . . . . . 46 2 ,3^BiphenyIiEd©ne ........................ 4f 2Jfc3*B tphei^ liad^ © . . . . . . . 4 * * * . . . . . . . . . . 48 - ( Q-Beiixoylphjenyl 5-a c ©topfcenone and conversion to 1* 3^Iph®nyi~2~hen£opprylisaa perch lorate. . . . . . . 49 2* 3-'%Gsy-2#3-diphenylinda»on© * . . . 5© 3* 4^Biphes^liscconcJarlR . . . . . . . . . . . . . . . . 5© 3f ^Trlp3seajrl-2*-heiis:op7r^lli2Ei perch lorate . . . . . . 5© OiKWJolysts o f 1 .3*4~triphenyl~2~)^n£opyrylinja perch lorate . . . . . . . . . . . . . . . . . . . . . 5 1 l~Phenyl~3* A-dti-t p *~ni tr©phenyl )-*2-henKop^rylinan perch lorate • • . • . • . . * • . . . . . • • . . • • 5 2 O sonolysis ©f l-p h en yl~3. p*- n i trophenyl )~2~ beazopyrylicm perch lorate * . 4 . . . . . . . . . . . 53 Phenylphthalide . . ..................................... 54

ill

,*2j

Chanter

£a23. .................... 5 ^ o -aiieM oyi benzene. (p ' -AiBlnobenzoyl )-e-benzojrl benzene. ............. 55 (p*-Hitrobenzoyl)*o*-benzeyl benzene. . . . . . . . . 56 Measurement of absorption speotra . . . . . . . . . 56

V

n m

SQNNAST

....................

ttsuomtsm, aiosa«?sr ,

62

. 63 .................................................................65

iv

X

Gh&pter I

Most organic! compounds are characterized By the fa c t th a t the carbon atoms are covalently linked to other atoms*

R elatively few types

o f compounds possess physical m d chemical p ro p erties in d ic atin g Ionic stru c tu re s in which the earhoa atom lo present as a p o sitiv e earbenlum ion or a negative Cartmnlon*

£w© eltu etu ree possessing carbonim lone

are the trlarylm ethyl d eriv ativ es (1) and hemsopyryllnai s a lts (II)* fhese formulas represent only one of several co n trib u tin g resonance alruc~ tu ree.

0

I

IE

A survey o f the lite r a tu r e revealed th a t only two d e fin ite examples of leobemaopyyyltum s a lts ( I I I ) have been prepared.

Structure

(111) i s isomeric w ith ( I I ) and again the formula drawn is only one of several resonance co n trib u to rs.

Because i t represents an unusual and

In te re stin g type of carbonic® salt* I t was of in te re s t to devise methods fo r the synthesis of isobenzopyry 1ium s a lts and to study th e ir p ro p erties.

C l On.

3 Ofe&pter II n m & itiC A i m

wmmmwM *

In 1909 Etcher end I’e lse r (I) prepared th© dibonsopyxyllum s e ll (?) f t m dibease~Oh pyroae (I?)*

Ft Uv

3Z

32

Inspection o f the structure of formula ? shows that i t may be regarded as a bemaepyyyliuja s a il (rings A and B) or as an isobeasopyryl lum sa lt ( rings € and ®). Only two examples of m fuestioaable isobensopyryllm sa lt struc­ ture have been described. the parent tsobeazopyryUu® sa lt (VII) was obtained V HttJttt and Eobinsoa ( 2 ) as the resu lt of the action o f lead tetraacetate on tr^as-l T2-hydriadanedlol (VI)*

^he intermediates were

not Isolated hut the solution containing them yielded the ferrichloride after addition of ferrio ohlorlde and hydrogen chloride.

CHO \ f* CH -C H

i

H ‘Eh© structure shown was based m the fa et that m am .&a converted It to ieoquinoliae. Shriner and Johnstea ( 3) also prepared a sa lt o f d efin ite ise~ benzopyrjrllum nature hjr the action o f phenylm&gneslum bromide on iso** couei&ria*

ONfyoh

Ct H$flAg8>-ym

NH+O

5 $he additio n compound was decomposed hy am ammonium chloride solution, and the carhimol ( I I ) yielded the perchlorate (X) upon treatment with p e rc h lo ric a d d .

I t may he seen th a t these two preparations outline two d istin c ­ tiv e ly d iffe re n t method© fo r the preparation of Isoheaisopyryliu® s a lts . Both methods however* precede through the same type of heml^aeetal, or homi-ketal, which may also he considered as a oarhl&ol. Im the ease of j|& or $ r | substituted phenyli aohenjsopyrylium s a lts i t would he e s p e e te d th at they might he prepared from e ith e r the corresponding lactone* w ith phonyImagneslw hremi&e, or the diketone hgr the simple addition o f strong ac id .

wi t h i* 3^diphonyi*2^hens#p2rxylium

perchlorate (XII) these two procedures may he outlined a s follows?

6 •r,

$0*1 U

/>« CH-c-Ctrif

$

{/c, a n

c /< V ^ H C f& UHf

The lacto ae, 3~pheay:ilsooetuaaria (XI)f was prepared by the method a f ©raebe aad freaky (b) froa homaphbhaMe anhydride ( 5),

K >6>^

/V c ftH CH1 CO1 H

AjCb r e flv *

fYcT

The desired ketoae,tX~(o~benaoylph©i^l Wcebepheaon© (X III), was obtained by oaonolysis of 2 ,3~diphe»yli»dea© which was prepared by the

7 raarraasan eat of i,2«dlph«ayiia4oad (6 ).

Z * /, H

hoH

HC/ Ct,Hs

a le .

CcC

M other lactone, 3,^-cLipheaylieooonsiariii (X?), which susy he used fo r the p rcttw tio a o f i sohensopyryli'm s a lts has heea previously prepared hy Xeelsch and he C laire {?)♦

^hie was prepared frost 2,3*

dlphenylindoae (XIT) (B) la the mmmr indicated.

Jk S 2 >

X Z

337

Shriner, Johnston end Kaslow (3 ) devised an easy method o f stru ctu re proof o f isohensopyry 1 ium s a lt s hy means o f s e le c tiv e osouc ly e t s .

With l-phenyl»2*heasopyrylium s a lt s th is procedure may he seen

to g iv e o-'heasoyl’bensclc a c id .

8

I. O i

/V fc tH r t c Ox

X. HxOt H>ojl

With li^ ip h e j& y l* , aad Xf 3»^trlpheayl-2~heaaepyrylim s a lts the degrada­ tio n $>ro&uets would he expected to he heasolc aeld, and e-heaaoylteasoic aold or eMihe&seylfcease&e resp ectiv ely .

9 Chapter I I I

m scm m m A.

of

mm&n

Studies on 1 ,3~liphe»yl~£~b©nsopyryllu« 8<s fh# oxidation of laden® to homophth&lie acid was ca rrie d out

using the d ire c tio n s of Whitmore end Cooney (9) and also those of Omm* m itt (5)*

^h© l a t t e r 1® procedure which involved a controlled oxidation

gave h o tte r yield® (63.?$) and a purer product* Homophthalic anhydride was mad# s a tis f a c to rily by dehydration of homophthalic acid w ith a c e tic anhydride.

Homephthalle anhydride may

he p u rifie d by c r y s ta llis a tio n from e ith e r g la c ia l acetic acid (10) or treason# (11).

However, a product o f reasonable p u rity was obtained di­

r e c tly without re c ry s ta llis a tio n , i f pur# homophthalic acid was employed, th e Frle&el and Graft reactio n of homophthalic anhydride and benzene (A) does not proceed too s a tis f a c to rily ,

fhe o rig in al work of

Graebe and frumpy reported th a t the reaction produced ch iefly o-carboxydeaoxybenaoia.

However, i t has been found th at i f the o rig in a l crude

p re c ip ita te was washed w ith cold sodium carbonate solution instead of a hot solution, th a t the ma^or product of the reactio n Is a lk a li Insol­ uble 3-pbenyXlsoeeumarla.

When 3-pheaylisocoumarin i s heated w ith sodium

carbonate solution i t i® hydrolysed to the acid ,

fhe o-carboxydesoxybea-

zoln produced l a the reaction m y be converted to 3-phenyl1 socoumarin l a b e tte r y ie ld by reflu x ln g in bensene with excess aluminum chloride than w ith phosphorous peataehloride as used by Gy&ebe and frumpy.

It

10 i s asstmed th a t the acid Is f i r s t prodneed la the Frie&el sad Craft reac tio n , hy aaeisgjr to the ease with phthaltc anhydride to produce e-henzoylheaaoic acid, and th is l a t e a condenses with I t s e l f to tom the lactone*

(A®* 0 “; ^ c6 ~ When 3**phes$ileeecw&ria was reacted w ith as excess (1 %e 3) of phenylmgne sin© hrosti&e in a reverse manner,, addition took place to give the corresponding

addition compound*

11

Sthis magnesium complex m s hydrolysed by the action of amaftninw ch lo rid e solution to give tb s c s rb is e l.

ffce e th ers! carbincl eolation

v a t tre a te d d ire c tly w ith p erch lo ric acid to give the perchlorate s a lt, 1, 3^ipb©nyl-2-benz©pyryiitna p erch lo rate.

Cuttf

f h ls s a l t m s re e ry s ta llis e d from e ith e r ethylene dichloride or g la c ia l a c e tic acid w ith a small amount o f perchloric acid .

In re c ry sts lliz in g

fv m the acid m ixture, wMcb was found to be sore sa tisfa c to ry , cere must he taken sines i t i s necessary to heat to the h e llin g point in order to a f f e c t solu tio n .

I f th e hot so lu tio n m s allowed to become very concen­

tra te d i t may oxidise w ith explosive violence. fhe diketone C{~(2-benzeylphenyl) -acetoplienone m s prepared as an a lte rn a te method of synthesis o f the interm ediate k e ta l.

In order to

prepare 2 ,3~diphenylindene; 2 ,3-diphenylindone (8) was reduced by the Clem®pnson reduction w ith sine amalgam and hydrochloric acid.

However,

in the reactio n m a lly lio type s h if t produced 1 ,2-diphenylindene.

12

Z vJsL tfc/ CcHf

t h i s was Id e n tifie d % it® almost q u an titativ e conversion to 2 , 3dlphenylin&eae by warming w ith alcoholic potassium hydroxide (6 ).

This

diphesylladeae was ozonixed and ezoai&e decomposed re&nctiveiy using a low pressure i^&rogen&tor and a c a ta ly s t of palladium on calcium carbonate, fb e e zonulysis o f 2 ,3~&iphen5rlin&eae has been reported by Banus and Calveb

(12 )

to produce beasoylphengrl Co-benzoyl) c&rbinol.

However, a f te r

ezoaolysia the decomposition o f the osonide was achieved merely by lo t­ tin g I t atand,

I t seems lik e ly th a t the hydrogen peroxide lib e ra ted In

the slow decomposition oxidised th is su b stitu ted desoxybenzoin to the corresponding bens©in.

However* when the ozonolysis was followed by a

reductive decomposition, the diketone formed did not resemble the sub­ s titu te d benzoin described % Bonus and C&lvet.

Since no su itab le means

e f purifyin g the th ic k o ily o H 2~bmzoylphenyl )-acetophBnone was read ily available* I t was converted directly to the perchlorate s a lt by the addi­ tio n of perch lo ric acid ,

fb ls yellow orange so lid was found to be

id e n tic a l w ith th a t previously prepared.

13

CHiCCuHr

fh® stru ctu re ©f th is diphenylieobensopyryliua percfcolate was determined by se lec tiv e ©sonolysis* followed “by oxidative decomposition of the ozonide.

Beasjci® acid end heasoylfceasole acid ( 13) were separated

and Id en tifie d “by th e ir melting points and mixed melting points with known samples*

+ CIO*. W>

-t C c H f C d t t \J-C O xH

Although the perchlorate anion was perhaps the most convenient for us© In is o la tio n of isohenzopyryllua salts* other anions may he used. In the case ©f 1* 3*^iph©nyliS0henz0pyrylium s a lts the ferrich lo rid e, ferrihrooide* chloride and “bromide were also prepared.

The ferrichlorid©

and ferrihromlde were prepared from the perchlorate by dissolving the

14 s a lt In hydrochloric or hy&robromie acid and adding a solution of the corresponding f e r r ic chloride or f e r ric bromide dissolved in hydrochloric or hydrobremte acid respectively. The chloride and bromide, which were found to he very hygro­ scopic, were prepared by bubbling anhydrous hydrogen chloride or hydrogen bromide through the e th e r solution of the diphenyli sobenssopyrylium carbln o l. B,

Studies ©a l,3t^lHphenyl~2~bensopyryiium S alts The I n s ta b ility of the diphenyl isobonzopyrylirn s a lt prepared,

in attempted n itr a tio n reactions, l e t to the preparation of a triphenyl s a lt, In the hope® th a t the 4-pheayl group would siabali&e the system. This salt* 1* 3 ,4-triphejiyl-2-bensopyryliu£} perchlorate, was prepared la a manner sim ilar to the f i r s t described fo r the diphenyl s a lt, with the corresponding lactone as m interm ediate.

The preparation of 3. ^-diphenyl-

isoceumariu may be outlined by the following reactions!

+ Q H yC H z^W

$h© preparation ©fheazalphthaXide by the Parkin coadenaalloa of phonylacet!© acid and phtfc<e anhydride with subsequent decarbonyla*' U oa, as described by W eiss (1A}# proceeded r e r y s a tis fa c to rily .

An

excess of the ©rig&ard reagent phenylffl&gaeaium bromide was reacted with benz&lphth&lide followed by hydrolysis and rearrangement with the lees ©f water in the manner of Allen, Sates and f m Allen (B), t© produce 2# 3-diphenylindon© in good y ie ld ,

fhe re a c tire 2t 3-double bond of th le

diphenylIn&on© was then oxidised to produce the corresponding 2t 3-epoay-* 2f 3-diphenylindono in good y ie ld , % alk alin e hydrogen peroxide (7). fh® rearrangement o f th is ©poxyla&on© to the lactone 3 ,^d ip h en y liso eoumorin (?) has been postulated to proceed through an qf~oxaaol type of interm ediate by Allen and Sates ( 15).

As evidence ter the mmhmim they have f0uM th a t when the epcry composed i s tre a te d with dry hydrogm chloride in g la c ia l ac etic a d d the interm ediate G&rhtnol which i s la equilibrium with the O[~oxanol compoxmd may he isolated*

S o w s r , when the epoay ocaspomd was warmed

w ith mineral acid only the lactone was isolated*

fh& ad d itio n of ph&aylmg&esits® bromide to 3 *^-diphenyl i socetim&rin followed by hydrolysis and p re c ip ita tio n o f l t 3,h~iriphe«yl~ 2-benzopyrylium p erch lo rate, by the addition of perchloric acid to the carb ln o l, proceeded in only a ra th e r poor y ie ld .

H increase in the mole

r a tio o f pheeylmagbeeim bromide to the lactone does not appear to increase the y ie ld of isebenzepyrylinm s a lt obtained; generally however, some of the u&re&eted 3 ,b-diphenyHsocom&rla was recovered from the reactio n m ixture.

17

$he proof o f stru ctu re of X,3. h-lriphemyl-^hensopyrylium per* ch lo rate was ca rrie d out in a manner sim ilar to th a t used fo r the diphenyl Halt h r deeselyei* followed hy mild oxidative decomposition of the ojsonide*

o

I.03

+

J L .W >

C(,Hr COx H

c C js o

Bensoto acid and c-dlheaaoylheiisseie acid were separated and Id en tified h r m elting point and mined melting point of the corresponding known com­ pound.

fo r th is procedure a sample of e-dihensoylhenzene was prepared

hy the method of Ouyoh and Oatel (16).

2 .H ,p > N H « a

I h OAc

Q

f c

^

o

+

IB Although such a procedure has not been trie d , i t seems lik e ly th a t 1 ,3#^triphei^I-2-beneopyrylium perchlorate might he prepared by the oxonolysia o f 1,2* 3~trlphenylindeae (17); followed by reductive decompo­ s itio n of the ©sseai&e using a low pressure by&rogenator and a palladium calcium carbonate c a ta ly s t to produce t|-phenyl-*fA^ 1.58 1.65 1.68 1.71 1.69 1.67 1.59 1.54 1.51 1.46 1.39 1.28 1.16 1.00 .93 .91 .945 .938 .923 .522 .792 .666 ,443 .227 .095 .031 .008 .000

dP 2.13 1.32 1.62 1.53 1.46 1.42 1.41 1.43 1.50 1.56 1.61 1.64 1.60 1.57 1.53 1.48 1.43 1.37 1.27 1.18 .96 .71 .53 .37 .29 .23 .18 .12 .06 .03 .02 .02

te r f OTSMAHY two mw examples o f isobensepyryliua s a lts W o boon sy n th esised f it.f a) 1#3~diphe*tyl~2~heasopyryllm milte %) 1*3,^iriphe»yl^2*henzopyryltm salts* Their ttr a ta v * * torn* %eem established by degradation by- osonolysria and ch aracterisatio n o f the products o f th is reac tio n . The n itra tio n o f 1* 3f ^ t r f ph©»yl~2~be»aopyryIipn perchlorate was found to prodnee l**phenyl~3'#**~(p*~»1trophenyl ^ H m s o p y r y l tun p erch lo rate, th e stru ctu re of th is d ta itro compound was established by ozonolysis and id e n tific a tio n o f the degradation products. The ah sorption spectra of these s a lts ta re been determined and the curves in te rp reted in to m s o f possible resonance stru c tu re s.

63 B iB U o m k m l.

D e c k e r a n d T e ls o r * B e n J£L 3 7 5 5 (1 9 0 8 )

2*

B l o t r n t a n d B o M a s o a * J . Ofeesu 8 ©©* ( 1 9 3 3 ) * 5 5 5

3.

Shrl*Wfl% Johnston end Kaelmr* J . Org. Ghea. j ^ f 204 (1949)

4,

Sraehe and 7rampy# Bar, .JJ* 375 (1898)

5#

Orwisaiti, Kagan and Buekt Org. Syn. Jg* 49 (1 ^ 9 )

6#

Bng®Hf Aim.

7.

Koelseh and M in i* * , J , Am. Ohem. Soc. £& 754

8.

Allen* Gate® and Tan Allan, Org. Sym. gg* 30 (1947)

9*

Whitmore and Goeney* J . As, Chen. See.

10 *

125 (1917)

7239

(1943)

(1944)

BiecSsBaan, Bey* !£* 1432 (I 914 )

11* Wisllceatt®, Ann*

102*109 (188$)

12.

B a n n s a n d C a l r e t * A nal.# S e e . Begum # P i s .

Jg*

13.

Ennelcell and Knigge* Bar. gj* 194 (190$)

14.

Wales, Org. Syn. Cel. T el. £* & (1943)

15.

Allen and Oates* J . Am. Ohea. See. |& t 1230 (1943)

16.

Geyot and C atel, Coapt. Bend. 3^ 9* 1348 (1905)

17.

Kohler* Am. Che®. Jo n r. |fi» 217 (1908)

IS.

Be T erre1* J . Chem. Sec., (1929)* 2??1|Terr© and h® Terr©1 ih id (1932), 1988s Terre1 and Pearson, Ibid, (1934)* 37

19.

Shriner and Moffett* 1 . Am. Cfcea. See. M* 301 £» 54 (1901)

22.

Btgiart* A ttl. Aooad. lin e a l % 58? (192?), 8. A.

4 9 ( 1929)

2466 (1927)

6k 23* Pauling, «$h© Hature of the Ohoaical Bond*, 2nd M , Cornell University Press# Ithaca, lew fo rk (1^10)

$k* WMUiaA, **fhe theory o f Hesonemse#11 John Wiley end Sens, In c ., Sew fo rk , (1944)

25,

lorolok, °®l©e iro n ic In terp re tatio n s of Organic Ch^»lstry,*J, John Wiley * end Sons* In n ,, lew fork# (1903).

26.

fhelen, Ph.©. Shesie, State U, of Iowa (191*9)

2?,

Saekola# Angew* Ohoa. Jfc ??? (1934)

28.

Horton end dow cla,