Attempts to synthesize vinyl thiazoles

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Authors Ciko, Geraldine Ann, 1941-

Publisher The University of Arizona.

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ATTEM PTS TO SYNTHESIZE VINYL THIAZOLES

by

G erald ine Ann Ciko

A T hesis Subm itted to the F acu lty of the

DEPARTM ENT OF CHEMISTRY

In P a r t ia l F u lfillm en t of the R equ irem en ts F o r the D egree of

MASTER OF SCIENCE

In the G raduate College

THE UNIVERSITY O F ARIZONA

19 66

STATEMENT BY AUTHOR

T his th e s is has been subm itted in p a rtia l fu lfillm ent of req u ire m e n ts fo r an advanced degree at The U n iversity of A rizona and is deposited in the U n iversity L ib ra ry to be m ade availab le to b o rro w e rs under ru le s of the L ib ra ry .

B rie f quotations from th is th e s is a re allow able without spec ia l p e rm iss io n , provided that accu ra te acknowledgm ent of sou rce is m ade. R equests fo r p e rm iss io n for extended quotation from o r rep roduction of th is m an u scrip t in whole o r in p a rt m ay be g ran ted by the head of the m a jo r departm en t o r the Dean of the G raduate C ollege when in his judgm ent the p roposed u se of the m a te r ia l is in the in te re s ts of sch o larsh ip . In a ll o ther in stan ces , how ever, p e rm iss io n m ust be obtained from the author.

SIGNED

APPROVAL BY THESIS DIRECTOR

This th e s is has been approved on the date shown below:

A ssocia te P ro fe s s o r of C h em istryJAMES E. MULVANEY

s t i

ACKNOWLEDGMENT

I would like to thank D r. Jam es M ulvaney fo r d irec tin g th is

w ork and for the in te re s t and patience he has shown throughout my

two y e a rs of g raduate study.

I would also like to thank m y p a re n ts , w ithout whose love,

devotion, and encouragem ent m y attainm ent of th is degree would

not have been p oss ib le .

TABLE OF CONTENTS

Page

LIST OF TABLES . vi

ABSTRACT * * * • * * ♦ * ♦ ♦ * ♦ ♦ • * ♦ * ♦ * « ♦ « » ♦ • » ♦ » ♦ ♦ ♦ • ♦ * • # » * y ii

INTRODUCTION 1

DISCUSSION OF RESULTS , . , , ................................... 7

EXPERIM ENTAL 19

F r ie d e l-C ra f ts R eaction of C hloroacety l C hlorideand E thylene 19

M ethyl Vinyl Ketone and T hioacetam ide with SulfurylC hloride ............... 20

M ethyl Vinyl Ketone and T hioacetam ide with Iodine . . . . . 21 M ethyl Vinyl Ketone and T h ioacetam ide with Thionyl

C h lo rid e ...................................................... 21A cry lo n itr ile and Hydrogen Sulfide ........................ 21A cry lam ide and P hosphorus P en tasu lfide in Xylene . . . . . 22 A cry lam ide and Phosphorus P en tasu lfide in C hloroform . . 23 M ethacrylam ide and Phosphorus P en tasu lfide in

C hloroform ....................................... 24T hioacry lam ide and C hloroacetaldehyde . .................. 24T hioacry lam ide and C h lo roacetal in E thanol . . . . . . . . . . 25A cry lam ide , P hosphorus P en tasu lfide , and

C h lo ro a c e to n e ................................................ . . . . . . . . 25T h ioacry lam ide and C h lo roaceta l in H ydrochloric

A cid ...................... 26T hioacry lam ide and C h lo roacetal w ith A nhydrous

O xalic Acid ........................... 26T hioacry lam ide and (phloroacetal in E thanol

(Acid Catalyzed) . . . . . . . . . . . . . . . . . . . . . . . . . 27T hiom ethacry lam ide and C h lo roacetal with A nhydrous

O xalic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27T hiom ethacry lam ide and C h lo roaceta l in

D im ethy lfo rm am ide , ...................28T h ioacry lam ide and C yclopentadiene ........................ . 28T hiom ethacry lam ide and Cyclopentadiene . . . . . . . . . . . 28

iv

V

TABLE OF CONTENTS - - (Continued)

Page

T hiom ethacry 1-amide with H ydrochloric Acid inE t h a n o l ............................................. 29

B ase-C ata ly zed P o ly m eriza tio n of T h io a c ry la m id e ................. 29B ase -C ata ly zed P o ly m eriza tio n of T h iom ethacry lam ide . . . 30

REFERENCES .......................................................................................31

LIST OF TABLES

Table Page

1. Sum m ary of A ttem pts to Synthesize Vinyl and2-Isopropeny l T h iazo les . . . . . . . . . . . . . . . . . . . . . . 11

v i

ABSTRACT

Reaction of acry lam ide with phosphorus pentasu lfide in ch lo ro ­

form y ields th ioacry lam ide (I, 45. 9%). U nder the sam e conditions

m ethacry lam ide y ields th iom ethacry lam ide (II, 44%). When reac ted

with chloroacetaldehyde o r ch loroacetaldehyde diethyl ace ta l, both

th ioam ides failed to yield th iazo les .

P o ly m eriza tio n of (II) with po tassium t-bu tox ide yielded p r i ­

m a rily sim ple vinyl po lym er. P o ly m eriza tio n of (I) under the sam e

conditions yielded a po lym er of undeterm ined s tru c tu re .

CH =NH

I II

INTRODUCTION

Until recen tly , the m ost w idely studied vinyl m onom ers and

po lym ers w ere those of s ty ren e and its d e riv a tiv es . T hese studies

have yielded m uch in form ation concerning the effect of substituen ts on

the double bond on m onom er rea c tiv ity . The m ost d ire c t m eans of

de term in ing m onom er rea c tiv ity is through copolym erization e x p e ri­

m en ts, w hereby the tendency of the active chain end, w hether it be

rad ic a l, carbonium ion, o r carbanion , to add to its own m onom er o r

the second m onom er can be m easu red .

A ssum ing the following reac tio n s to take p lace during a

copolym erization

-M • + M 11

+ M2

-M.

-Mg' + M 2T-m 2-

-M -

-m 2-+ m 2 -M2-

and defining M and M9 as m onom er 1 and m onom er 2, resp ec tiv e ly ,

ku k22r i aS ” k------' and Tg as — ----- , the copolym er com position equation

12 21

dMt M l r 1[M1] + [M2]"

dM2 M2 r 2 [M2 J + Im J

1

provides fo r the de te rm ina tion of the d e s ire d re la tiv e re a c tiv itie s .

Much in te re s t has been shown in m onom ers re la te d to s ty ren e ,

that is , in m onom ers containing ring s tru c tu re s which can exhibit

a ro m a tic c h a ra c te r s im ila r to benzene. In an ex tensive study of such

com pounds, Koton* found that the in troduction of a h e te ro a to m into the

ring usually causes a m arked in c re a se in m onom er re a c tiv ity . R e­

activ ity is fu rth e r enhanced if a condensed rin g s tru c tu re is p resen t.

Co po lym eriz ing 2 -vinyl pyrid ine (I), 2 -vinylthiophene (II), 2 -v iny l-

fu ran (III), 2 -vinyl quinoline (IV), 2 -vinyl benzofuran (V),

2 -vinyldibenzothiophene (VI), and 2 -v inyld ibenzofuran (VII) with s ty ren e

as Mg, he found the h e te ro cy c lic m onom er to be m ore rea c tiv e than

s ty ren e its e lf in a ll cases except 2 -v iny lfuran , as ind icated by r^

values g re a te r than one, and r^ values le s s than one.

I

CH = CH,SII

-CH = CHrO '

III

CH = CHr

IV

CH = CHr CH = CH

CH = CH CH = CH,

In addition, Koton found th a t m onom ers containing condensed ring

s tru c tu re s w ere m ore rea c tiv e than those containing only one ring .

2K oton 's re s u lts su b stan tia te those rep o rte d e a r l ie r by W alling on

vinyl pyrid ine and v inyl thiophene.

While the tren d tow ard in c re a se d re a c tiv ity of h e te ro cy c lic

m onom ers is not confined to copo lym erization with s ty re n e , the use

of o ther m onom ers as y ie lds re s u l ts not quite as consisten t.

3 4F ran k ’ showed that while 2 -, 3 -, and 4 -vinyl pyrid ine and se v e ra l

a lky lated d e riv a tiv es of th ese copolym erize fa s te r with butadiene than

does s ty ren e , 2 -v inylfuran , and 2 -vinylthiophene copolym erize slow er5

than s ty ren e with the sam e com onom er, and K am enar found.that the

copo lym erization of 2 -v iny lfu ran with vinylidene ch lo ride p roceeded at

a slow er ra te than did the ho mo po lym eriza tion of e ith e r m onom er. In

the case of the 2 -v inylth iophene-bu tad iene sy stem , how ever, Meehan^

showed that, while the copo lym erization p roceeded at a slow er ra te

than did the s ty ren e -butadiene system ,. 2 - v inyl thiophene e n te rs the

chain at a fa s te r ra te than , does s ty ren e , since butadiene - s ty ren e

(75:25) copolym ers a t 70-80% conversion have s ty ren e constan ts of

20 .3 -21 .2% , while 2 -vinyl thiophene e n te rs the copolym er a t a ra te

approxim .ately p ro p o rtio n a l to i ts concentration, in the m onom er m ix ­

tu re (25%).

The fu ran rin g apparen tly deac tiva tes the vinyl group in7

copo lym erization re a c tio n s . B orrow s stud ied the effect of fu ran

analogs of e innam onitrile on the po lym eriza tion of s ty re n e , and found

that th ese compounds inhib it the po lym eriza tion in the p resen c e of a ir

and re ta rd in the absence of a i r . Koton* also found th a t the p ro p e rtie s

of vinyl fu ran hom opolym ers a re dependent on the ava ilab ility of

m o lecu la r oxygen. In the p resen c e of oxygen, a soft, low m elting

po lym er was obtained, while in the absence of oxygen, f re e ra d ic a l

in itia tion .y ie lded a h a rd , infusib le po lym er., Koton p roposed that, in

th is case , the double bonds in the fu ran also po lym erize , form ing a

th ree -d im en s io n a l, highly c ro ss - lin k e d po lym er.

The addition of a second o r th ird h e te ro a to m fu r th e r enhances

activ ity , as has been shown by the copo lym erization of s ty re n e with

2, 4 -d im e th y l- 6 -v in y l-s - tr ia z in e and 2 - dim ethyl am ino- 4 -vinylpy r im i -

8dine .

A nother a re a of in te re s t in the study of vinyl he te rocyc les, is

th a t of b io log ical ac tiv ity . A lthough th e re a re a g re a t m any n a tu ra lly -

o ccu rrin g po lym ers which exhibit b io log ical activ ity , notably the

p ro te in s and nucleic ac id s, th ese a re c la ss if ied as condensation poly­

m e rs , and vinyl po lym ers exhibiting s im ila r activ ity a re r a r e , if

indeed, ex isten t a t a ll.

Some syn thetic vinyl p o lym ers, how ever, do show bio logical

ac tiv ity . Polyvinyl py rro lidone (VIII) has been used in the p rep a ra tio ng

. of syn thetic blood p lasm a , although the rea so n s fo r i ts e ffectiveness

5

a re incom pletely understood .

VIII

T here ex is ts the p o ssib ility , how ever, that if vinyl po lym ers

could be p rep a red containing substituen t groups s im ila r to those co n si­

dered to be the active s ite in b io logically active com pounds, the

po lym ers them se lves m ight show b io log ical ac tiv ity . But it has been

shown that s im ila r ity in s tru c tu re does not in i ts e lf guaran tee the

d e s ired activ ity . F o r exam ple, Overberger"*- ̂ studied the p o ly m eriza ­

tion of 4 -v inylpyrim id ine (IX) and 2-N , N, - d im ethy lam ino-4 - v iny l-

pyrim id ine (X). The pyrim id ine b ases a re p rim a ry constituen ts of

ribonucleic acid (RNA) and deoxyribonucleic acid (DNA), and it was

hoped tha t the po lym ers under investigation would exhibit antib iotic

ac tiv ity . Although the m onom ers po lym erized read ily , the resu ltin g

po lym ers showed no outstanding b io logical activ ity .

CH—CH,

X

i CH=CH,

rx

The in te re s t in th iazo les a ro se from the fact that the th iazole

ring sy stem is p a rt of the basic nucleus of th iam ine (V itam in B^) (XI).

H3C"TNK + _

y-NHgCl

N. -CH2

XI

+.N

CT

.CH2 CH2 OH

- CH3

11Buchman , in a study of the effect of a ttached group -R on

th e rap eu tic activ ity , syn thesized a s e r ie s of 4 -m ethy lth iazo le analogs

(XII), and found that none of these

H3C-

R-

‘N

- S -

XII

R = -H, -C 2 H5 , -C H =C H 2 ,

- c h o h c h 3 , - c h 2 c h 2c h 2o h ,

-C H 2 CHOHCH3, -CHgOH

compounds exhibited v itam in B^ potency. F ro m th is he concluded that

even a sm a ll change in the sub stitu en ts on the ring re s u lts in lo ss of

activ ity .

DISCUSSION

Although the syn thesis of vinyl th iazo les and 2 -isopropeny l

th iazo les is rep o rte d in the l i te ra tu re , * * * ̂ these m ethods involve as

the final step the dehydration of a lcohols, the dehydrohalogenation of

halogenated d e riv a tiv e s , o r the p y ro ly sis of e s te r s . This work deals

with a ttem pts to p re p a re vinyl th iazo les and 2 -isop ropeny l th iazo le

from compounds a lread y containing the v inylic bond, and, finally , the

po lym eriza tion of these com pounds.

p ro p er th ioam ides and carbonyl com pounds, it is possib le to obtain

an un lim ited num ber of substitu ted o r unsubstitu ted th iazo le s .

The m ost gen era lly applicable m ethod of th iazo le syn thesis is

14the reac tio n of th ioam ides with u-halo carbonyl com pounds. The

m echan ism appears to be as follows:

w here -R , -R , and -R m ay be H, alkyl, a ry l, e tc . By the use of the

7

T hioform am ide is rep o rte d in the l i t e r a t u r e ^ , and y ie lds

th iazo les unsubstitu ted in the 2 -position . It was hoped that trea tm en t

of th ioform am ide with chlorom ethyl vinyl ketone would y ie ld 4 -vinyl

th iazo le (XIII).

N CH=CH2

XIII

McMahon re p o r ts the sy n th esis of ethyl vinyl ketone by a

F r ie d e l-C ra f ts reac tio n of propionyl ch lo ride and ethylene, followed by

16the dehydrochlorination of the obtained ethyl /3-chloroethyl ketone

A pplication of th is m ethod using ch lo roace ty l ch lo ride to the p rep a ra tio n

of chlorom ethylyvinyl ketone, how ever, re su lte d in a black infusib le,

inso luble m a te r ia l, p resum ab ly som e s o r t of c ro s s - lin k e d polym er

(see ex p erim en ta l). Since m ethyl vinyl ketone is one of the m ost reac tiv e

17m onom ers known , it is possib le that po lym eriza tion o c c u rre d under

the reac tio n conditions em ployed.

Dodson and King developed a m ethod w hereby a th ioam ide and a

ketone a re heated with a halogen, th ereb y avoiding the n ecess ity of

18iso la ting the a -ha lo carbonyl , o r , a lte rn a te ly , d ispensing with the

halogen en tire ly , and substitu ting a s tro n g oxidizing agent, such as

19thionyl ch lo ride , su lfu ric acid , su lfu ry l ch lo ride , e tc . Both these

m ethods w ere a ttem pted with m ethyl vinyl ketone and th ioace tam ide ,

using iodine, thionyl ch lo ride , and su lfu ry l ch lo ride . A ll th re e reac tio n s

9

re su lte d only in unw orkable t a r s . P resu m ab ly , the rea c tiv ity of m ethyl

vinyl ketone m akes it unsu itab le fo r such rea c tio n s .

A ttem pts to syn thesize th ioacry lam ide by the p ro ced u res

rep o rted in the l i te ra tu re failed to y ield the d esired product. The

m ethod of F a irf ie ld , involving the addition of hydrogen su lfide to

20n itr i le s , when applied to a c ry lo n itr ile , y ielded a sa tu ra te d compound

which m ay be NC-CHgCH^SCHgCHg-CN. This compound contained

n itrogen and su lfu r, but the n. m . r . sp ec tru m showed a com plex m u lti­

p le! at 7. 1‘T', and the in fra re d sp ec tru m showed strong n itr ile

-1 -1 absorp tion at 2250 cm and peaks in the reg ion 730-780 cm , strongly

21suggestive of the -C H g-S-C H g- linkage . P resu m ab ly , cyanoethylation

of hydrogen sulfide took p recedence

over th ioam ide fo rm ation . An a ttem pt to p re p a re th ioacry lam ide by

15E rle n m e y e r 's p ro ced u re fo r th ioform am ide re su lte d in an a lm ost

quantitative reco v ery of s ta r tin g m a te r ia l.

The d e s ired th ioacry lam ide and th iom ethacry lam ide w ere finally

acqu ired by a m odification of th is p ro ced u re (see experim en ta l).

CH2 = CH-CN + H2S ---- ^ NCCHgCHgSCHgCHgCN

50-60

CHC1

CH

CH2 = C - C - NH2

50-60°

10

The n .m . r . sp ec tru m of th ioacry lam ide showed vinyl abso rp tion at

4. 25 T and 3. TS'tf, as w ell as a sh a rp sing le t at 7. 84 'C', which was

assigned to the -SH proton on the b asis of com parison with the sp e c ­

tru m of th ioace tam ide . The n .m . r . sp ec tru m of th iom ethacry lam ide

showed vinyl abso rp tion at 4. 5 2 and 4 . 157f, the -SH sing le t at 7. 84

nf, and a m ethyl peak, sp lit into a doublet, at 8. 0 1 T . The in fra red

sp e c tra of both compounds showed the d isappearance of the carbonyl

bands. Both compounds had c o rre c t e lem en ta l an a ly ses . T h io ac ry la ­

m ide y ielded a D ie ls -A ld er adduct when tre a te d with cyclopentadiene

in refluxing ethanol, but th iom ethacry lam ide failed to r e a c t with

cyclopentadiene in anhydrous ethyl e th e r at room te m p e ra tu re o r in

refluxing ch lo ro fo rm o r ethanol (see experim en tal).

In o rd e r to obtain a vinyl th iazo le unsubstitu ted in both the

4- and 5- positions, it would be n e c e ssa ry to use a haloacetaldehyde.

W iley and England s ta te that it is p re fe ra b le to u se som e m ore stab le

22deriva tive of th ese . T here a re num erous accounts in the l i te ra tu re

of the use of a ce ta ls . ^ ^ In th is w ork, ch loroacetaldehyde d iethy la-

ce ta l as w ell as ch loroacetaldehyde was used .

T hioacry lam ide and ch lo roace ta l w ere heated with ethanol

until the ethanol evaporated . D issolving the res id u e in w a te r, t r e a t ­

m ent with sodium hydroxide, ex trac tio n w ith e th e r, and d is tilla tio n

re su lte d in a n early quantitative rec o v e ry of ch lo ro ace ta l. Since it

is n e c e ssa ry fo r the ace ta l to b reak down to the aldehyde before reac tio n

11

TABLE I

Thioam ide

SUMMARY OF ATTEM PTS TO SYNTHESIZE VINYL AND 2-ISOPROPENYL THIAZOLES

C arbonyl o r D erivative Solvent C ata lyst R esult

Thioacet-am ide

M ethyl vinyl ketone

None T ar

• M SOCL

T hioacry l-am ide

it

C h lo roaceta l E thanol

S02C12

None

D im ethyl- "fo rm am ide

99% rec o v e re d ch lo roace ta l

U nidenti­fied solid

None Anhyd,oxalic

acid

U nidenti­fied sludge

6N HC1 U ndistil- able am ount oil

E thanol

T hiom ethacryl-am ide

C hloroacet-aldehyde

Ethanol

C h lo roace ta l , None

" D im ettiyl-fo rm am ide

HC1 75% c h lo ro ­aceta l + ch lo ro ace t- aldehyde

None ■ U nidenti­fied carbonyl compound

Anhyd.oxalic

acidNone

U ndistil- able amount oil T ar

12

can occu r, it is p robable that such decom position did not occu r under

under the reac tio n conditions. The fa ilu re to re c o v e r any th io a c ry la -

m ide can. be explained by the fac t th a t th is compound, is rea d ily soluble

in w a ter and. is , th e re fo re , lo s t in the w orkup.

An attem pted rea c tio n of the sam e two compounds, in refluxing

d im ethyIform am ide y ielded a white c ry s ta llin e so lid m elting a t 179-

180°. This compound contained ch lo rine , but n e ith e r n itro g en nor

su lfu r. The n. m . r . sp e c tru m failed to ind icate any v iny lic p ro tons,

and th is compound was not c h a ra c te r iz e d fu r th e r .

23The m ethod of H antzsch u tiliz e s anhydrous oxalic acid , p r e ­

sum ably to fac ilita te the decom position of ch lo ro ace ta l to ch lo ro ace ta l-

dehyde. The product obtained in th is case was a brow n sludge, which

could not be re c ry s ta l l iz e d o r iden tified .

When 6N hydroch lo ric acid w as em ployed as so lvent, the

re s id u a l o il a fte r rem ova l of the e th e r w as p re se n t in such sm all

am ounts that d is tilla tio n was not p o ss ib le . It is po ss ib le , but not

proven, tha t such a high acid concen tra tion did com pletely decom pose

the ace ta l, but that the aldehyde was lo s t in the w orkup. The fa ilu re of

th iazo le fo rm ation to occu r could not be explained a t th is point.

A. s im ila r rea c tio n of the th ioam ide and ch lo ro ace ta l in refluxing

ethanol with a tra c e of acid re su lte d in 75% rec o v e ry of u n reac ted

ch lo ro ace ta l, However, a sm a ll am ount of ch loroacetaldehyde was

obtained, indicating that som e h yd ro ly sis did o ccu r. The fac t that no

13

vinyl th iazo le was obtained seem ed .to suggest the p o ss ib ility of a

com petitive rea c tio n o ccu rrin g which would e ssen tia lly rem ove thp

th ioam ide from the rea c tio n . The obvious con jec tu re , of c o u rse , was

tha t the th ioam ide was reac tin g with, i ts e lf in som e way, A. study of

th iom ethacry lam ide showed what the n a tu re of th is rea c tio n was (see

below).

A m odification of the reac tio n , in troduced by H ro m a tk a ^ ^ ' ^/

avoids iso la tion of the th ioam ide, and co n sis ts of heating a m ix tu re of

the am ide, phosphorus pen tasu lfide , and the a -h a lo ca rb o n y l compound.

27A rea c tio n following the m ethod d esc rib ed by Schwarz fo r 2 ,4 -d i ­

m ethyl th iazo le , using aery lam id e , phosphorus pen tasu lfide , and

ch lo roacetone , fa iled to y ie ld the d e s ired product (2 - vinyl - 4 - m ethyl -

th iazo le). However, th is re fe re n c e m entions the p o ss ib ility of

obtaining a substitu ted oxazole in th is rea c tio n . T his e lim in a tes

hydro lysis of the th ioam ide as a rea so n fo r the fa ilu re of the p rev iously

d esc rib ed re a c tio n s , s ince , even w ere hyd ro ly sis to o ccu r, som e

2 -vinyl oxazole should be iso la ted , which w as not the case .

R eactions of th iom ethacry lam ide and ch lo ro ace ta l m et with no

m ore su c ce ss than did those with th io aery lam id e . In a ll c a se s , t a r s ,

rec o v ere d s ta r tin g m a te r ia l, o r frac tio n s too sm all to pu rify w ere the

re s u lt (see experim en ta l).

To de te rm ine the na tu re of a poss ib le com petitive reac tio n ,

th iom ethacry lam ide was re fluxed .in ethanol with a t r a c e of hydroch lo ric

14

acid in the absence of ch lo ro ace ta l. R em oval of the so lvent y ielded a

fo rm , carbon te tra c h lo rid e , acetone, and dioxane, but soluble in w ater,

m ethanol, ethanol, and d im ethyIsulfoxide. This m a te r ia l had an

inheren t v isco s ity of 0 .117 in d im ethylsulfoxide. If th is reac tio n takes

place rap id ly enough under the reac tio n conditions, it would explain the

fa ilu re to obtain the d e s ired th iazo les , since the th ioam ide is thus

e ssen tia lly rem oved from the reac tio n m ix tu re . Its so lub ility in w a ter

would cause it to be lo s t in the reac tio n workup, explaining the reco v ery

of only ch lo ro ace ta l.

Since it now appeared unfeasib le to u se these th ioam ides in the

sy n thesis of vinyl th iazo les , a tten tion was tu rned to the possib ility of

po lym erizing a, /3 -u n sa tu ra ted th ioam ides.

F re e rad ic a l po lym eriza tion would not be expected to yield high

m o lecu la r weight p o ly m ers, since the -SH group would ac t as a chain

t r a n s fe r agent.

Studying the b a se -ca ta ly zed po lym eriza tion of acry lam id e ,

28B reslow found that he obtained, not the expected sim ple vinyl po lm er,

but one which a ro se from a proton tr a n s fe r m echanism :

po lym eric white solid , m .p . > 250°, which was inso lub le in ch lo ro -

OCH 3

CH2 = CH -C-N H -CH 2 -CH -C-N H > CH2 = CH -C-N H -CH 2 -CH -C-N H

15

M arvel and Yoda obtained s im ila r re s u lts with jD -styrenesulfona-

29m ide. The polym er re su ltin g from the b a se -in itia te d po lym eriza tion

of th is m onom er proved to be one with m ixed re c u rr in g un its , som e

a ris in g from sim ple vinyl po lym eriza tion and o th ers fro m the proton

tr a n s fe r reac tio n , which would y ield a s tru c tu re (XIV). They assum ed

tha t the

SO N H—

XIV

p ro to n - tra n s fe r reac tio n was o ccu rrin g because of the d e c re a se in the

-NH- s tre tc h in g band at 3310 and 1615 cm *.

T h ioacry lam ide and th iom ethacry lam ide w ere po lym erized with

po tassium t-bu tox ide accord ing to M arv e l's p ro ced u re . They both

yielded white, powdery so lid s , m elting above 275°. The po lym er

obtained from th ioacry lam ide had an in heren t v isco sity of 0. 055, while

that of the th iom ethacry lam ide po lym er w as som ew hat h igher, 0 .171 .

The -NH- s tre tc h in the in fra re d sp ec tru m of po ly th ioacry lam ide

appears at the sam e w avelength as it does in the m onom er, 3325 and -1

3175 cm , while the po lym er obtained from th iom ethacry lam ide shows

the -NH- s tre tc h at som ew hat h igher w avelengths than does the m onom er,

-1 -1 3430 and 3180 cm as opposed to 3380 and 3175 cm

16

Two obvious s tru c tu re s a re possib le fo r the po lym er

n

SH

A B

B ecause of the deshielding effect of —C— and —NH— the pro tons bound to

carbon in s tru c tu re B would be expected to appear at considerab ly low er

fie lds than carbon bound protons in A.

The n. m . r . sp ec tru m of the th iom ethacry lam ide po lym er, while

poorly reso lv ed , shows no abso rp tion at low er fields which would in d i­

cate pro ton t r a n s fe r . Two broad peaks, at 8. 75'X and 8. OSTf, having

re la tiv e peak a re a s of 3:2, seem to ind ica te that po lym eriza tion in th is

case o ccu rs p r im a rily , if not exclusively , through a sim ple vinyl

m echan ism , and that the po lym er has s tru c tu re A(R=CH^).

The n. m . r . sp ec tru m of the th ioacry lam ide po lym er, p resen ts

a m ore com plex p ic tu re . The absence of peaks in the reg ion lO'X to

8. 5 would seem to ind ica te that, in th is c ase , no sign ifican t amount

of vinyl po lym er is fo rm ed . The sp ec tru m shows peaks at 7. O S 't,

7. 21+t , 6. 9 0 f , and 6. 75 . It is possib le tha t the po lym er contains

se v e ra l types of re c u rr in g u n its . T hese can be postu lated read ily from

the m echan istic view, but a re difficult to a ss ig n to the sp ec tru m without

b road g en era liza tio n s .

17

One of these un its , of co u rse , is the one a ris in g from proton

t ra n s fe r , which would y ield a polym er of s tru c tu re (XV).

4-C H g -C H g -N H -f

(XV)

The prob lem with assign ing th is s tru c tu re is that the m ethylene

signals would be expected to appear as m u ltip le ts , w hereas the observed

signa ls a re apparen tly s in g le ts . Although the evidence is fa r from

32exhaustive, th e re is a p o ss ib ility that p ro tons a to C=S and £ to —NH—

fa ll in roughly the sam e a re a of the sp ec tru m as those in the re v e rse

c ase . The p robab ility of the two se ts of p ro tons having the sam e

chem ical sh ift, and appearing as a s ing le t is too unlikely to consider

se rio u s ly a t th is tim e .-1

The fact that the po lym er shows im ine abso rp tion at 1650 cm

in the in fra re d , which cannot be assigned to —C=NH as it could w ereSH

vinyl po lym er p re se n t, m akes possib le ano ther postu la tion concerning

the s tru c tu re of the po lym er, nam ely

-K:h2̂ h24 -̂6-^c

This s tru c tu re could a lso a r is e by the p ro ton tr a n s fe r m echanism ,

but involves a d ifferen t attack ing sp ec ie s than that req u ire d fo r B.

A ssum ing —SH to be the m ost acid ic sp e c ie s in the m onom er, th is

m echanism could be as follow s:

CH =6-C = N H

t-BuO

H-> c h = 6- c = n h

* &

NH NH

c n f h

=NH___

NH

18

CH

A -C -S -C H --C H -C^Cx sh_ H

EXPERIM ENTAL

M elting points a re unconnected. In fra re d sp e c tra w ere

de te rm ined on a P e rk in -E lm e r In fraco rd , c a lib ra ted against

po lysty rene; n. m . r . sp e c tra w ere de te rm ined on a V arian Model

A -60 (60 Me. )sp e c tro m e te r using te tram e th y ls ilan e as in te rn a l o r

ex te rn a l s tandard , M icroana ly ses w ere p e rfo rm ed by tbe M icro -

Tech L ab o ra to rie s , Skokie, Illino is. Solvents u sed w ere a ll reagen t

g rade and not red is tille d , w ith the exception of benzenp, which was

d ried over calcium ch lo ride and d is tilled , and d im ethy lfo rm am ide,

which w as d ried and d is tilled over calcium hydride. L iquid reag en ts

w ere d is tilled and so lid reag en ts re c ry s ta lliz e d p r io r to use w h erev e r

p o ss ib le . A nhydrous oxalic acid w as obtained by sub lim ation from

the d ihydrate . Hydroquinone w as added to a ll rea c tio n s in which

po ten tia lly po lym erizab le compounds w ere used ,

A. F r ie d e l-C ra f ts R eaction of C hloroaoety l C hloride and

16Ethylene

C hloroacety l ch lo ride w as p re p a re d from ch lo ro ace tic acid and

30thionyl ch loride by the m ethod of M cM aster and Ahwann. ' This

compound, boiling at 96-98°, showed carbonyl abso rp tion at 1790_ 1 ^

cm in the in fra red , ind icative of an acid ch lp ride .

19

C hloroacety l ch loride (4Qd g„ , 3. 54 m ole) was added slow ly to

a s t i r r e d m ix tu re of 2000 m l. of carbon disdlfide and 575 g. (4„ 3 m ole)

of anhydrous alum inum ch lo ride . The m ix tu re w as cooled to 0° w ith

s t i r r in g and d ry ethylene p assed into it fo r 7 hours, The m ix tu re

was heated on a s team bath at 40-45° un til b r isk evolution of HCl

dim inished and w as then allowed to stand at room te m p e ra tu re

overnight. The re s id u e w as poured onto ice to decom pose the

alum inum ch lo ride com plex, resu ltin g in a two phase sy stem . The

o rgan ic la y e r w as w ashed with dilute hyd roch lo ric acid, w a ter, and

dilute sodium bfcarbpnate un til an alkaline reac tio n w as obtained. .

The re su ltin g s ligh tly t a r r y solution w as d is tilled at a tm ospheric

p re s s u re to rem ove the so lvent. The re s id u e in the d is tillin g flask

was a black, infusib le , inso luble solid , w hich was not identified.

B. M ethyl Vinyl Ketone and T hioacetam ide w ith Sulfuryl

19C hloride

T hioacetam ide (36 g . , 0. 48 m ole) w as d isso lved in 14 g. (0 .2

m ole) of m ethyl vinyl ketone and the m ix tu re cooled in an ic e -s a lt

bath. Sulfuryl ch loride (27 g . , 0. 2 m ole) was added slow ly enough

to keep the exo therm ic rea c tio n to a m inim um . When addition was

com plete, the t a r r y m ix tu re was heated on a steam bath fo r 15

m inu tes. The re su lta n t ta r w as e x trac ted w ith e th e r, but e v ap o ra ­

tion of the e th e r y ielded only a: film on the inside of the flask .

21

C, M ethyl Vinyl Ketone and T hioacetam ide w ith Iodine '*'̂

T hioacetam ide (30 g„, 0„ 4 m ole) was d isso lved in 14 g„ (0. 2 m ole) of

m ethyl v inyl ketone and 50. 8 g. (0. 2 m ole) of iodine added portionw ise

th rough a re flux condenser. The rea c tio n w as highly exo therm ic , and

gave off dense white fum es. When addition w as com plete and the r e ­

action subsided , the m ix tu re w as refluxed gently fo r 2 hours. The

resu ltin g b lack ta r was diluted, w ith w ater and heated un til m axim um

solution o c cu rred . The aqueous solution w as m ade b asic w ith con­

cen tra ted am m onium hydroxide and e x trac ted w ith anhydrous e ther.

The com bined e th e rea l e x tra c ts w ere d ried oversigh t over solid

sodium hydroxide, and the e th e r rem oved under vacuum . A ttem pts

to d is till the re s id u a l o il re su lte d in the fo rm ation of a b lack so lid in

the d istilling flask .

D. M ethyl Vinyl Ketone and T hioacetam ide w ith Thionyl

C h lo rid e '*' ̂

T hioacetam ide (3 0 g ., 0. 4 m ole) and 14 g. (0. 2 m ole) of m ethyl

vinyl ketone in a D ry Ice - acetone bath w ere tre a te d 11.9 g. (0.1

m ole) of thionyl ch lo ride . The resu ltin g b lack ta r w as w orked up

in the m anner d esc rib ed above (see C) w ith the sam e re s u lt.

20E. A cry lp n itrile and Hydrogen Sulfide

A cry lo n itrile (222 g. , 4. 2 m ole) w as d isso lved in 232 m l. of

pyrid ine and 101 g. (1. 0 m ole) of tr ie th y lam in e w as added. Hydrogen

22

sulfide was bubbled through the m ix tu re in a steady s tre a m for 3. 5

hours. The m ix tu re w as poured into d is tilled w a te r and the organic

la y e r rem oved. The aqueous la y e r w as ex trac ted w ith e th e r. The

com bined organic frac tio n s w ere d is tilled to rem ove so lven ts, and

the re s id u a l v ile -sm e llin g red oil cooled in a D ry Ice -acetone bath

in an e ffo rt to p rec ip ita te the suspended c ry s ta ls . F iltra tio n and

re c ry s ta ll iz a tio n from ethyl ace ta te y ielded 4. 0 g. of a pale yellow

solid, m . p. 35-36°. The in fra re d sp ec tru m of th is so lid showed-1

strong n itr ile absorp tion at 2250 cm and peaks in the reg ion 730 -

-1 21 780 cm , strong ly suggestive of the -C H ^-S-C H g- linkage.

F u rth e rm o re , the n. m . r . sp ec tru m showed no vinyl p ro tons, a com ­

plex m ultip le! at 7. 1 T , and s ing le ts at 8. 0 and 9. 55MT , both of

which a re p robably caused by im p u ritie s . This compound was

assum ed to be NCCH^CH^SCH^CH^CN, a ris in g from the cyanoethy-

la tion of hydrogen sulfide.

15F. A crylam ide and P hosphorus P en tasu lfide in Xylene

To 71 g. (1 m ole) of acry lam ide suspended in xylene in an ice -

sa lt bath w as added 35 g. (0. 16 m ole) of phosphorus pen tasulfide

w ith v igorous s t i r r in g over a period of two hours. The m ix tu re was

then left overnight w ith s t ir r in g . The xylene was se p a ra te d from the

re s id u a l solid and the so lid ex trac ted w ith e ther. C oncentration of

the com bined organ ic la y e rs and the addition of pe tro leum e th e r

23

(30-60°) re su lte d in the p rec ip ita tio n of a white solid , which, a fte r

re c ry s ta lliz a tio n from ethyl ace ta te , was shown to be u n reac ted

s ta r tin g m a te r ia l on the b a s is of in fra re d spectrum and m ixed

m elting point. T otal y ield of u n reac ted s ta r tin g m a te r ia l - 65 g.

(93%).

G. A crylam ide and Phosphorus P en tasu lfide in C hloroform

A cry lam ide (200 g. , 2. 82 m ole) w as d isso lved in 400 m l. of

ch lo ro fo rm and 100 g. (0. 45 m ole) of phosphorus pen tasu lfide added

w ith s t ir r in g at 50-60° over a pe riod of 2 hours. The m ix tu re was

s t i r r e d w ithout heating overn ight and then allowed to stand without

s t i r r in g fo r 48 hours. The re su ltin g tw o -lay e r sy s tem was ex trac ted

with anhydrous e th e r and the e th e r concen tra ted on a s team bath

under a sp ira to r vacuum . On the addition of pe tro leum e th e r (30-60°)

a white so lid p rec ip ita ted . Two re c ry s ta ll iz a tio n s from ethyl ace ta te

yielded 6 g. (15.3%), m. p. 67-68°. (R epetition of the p rocedu re

eventually in c re a sed the yield to 18 g. (45. 9%) ). The n. m . r . sp e c ­

tru m showed vinyl absorp tion at 4. 25 ~C and 3. 75‘C and a sharp

sing let at 7. 84 ■T which w as assigned to -SH on the b a s is of com ­

p a riso n w ith the sp ec tru m of th ioace tam ide . The in fra re d spectrum

showed the d isappearance of the carbonyl band.

Anal. C alcd. fo r C^H^NS: C, 41. 34; H, 5. 78; N, 16.07.

Found: C, 41. 38; H 5. 97: N, 15. 95

24

EL M ethacry lam ide and P hosphorus P en tasu lfide in C hloroform

M ethacrylam ide (200 g„ , 2. 38 m ole) w as d isso lved in 400 m l. of

ch lo ro fo rm (gentle heating) and w as 'tre a te d with 100 g. (.0. 45 mole)

of phosphorus pen tasu lfide in the m anner d escrib ed in (G r). Workup

w as the sa tne except that the reac tio n m ix tu re did not stand, fo r 48

hours a fte r overnight s t ir r in g . The y ield of w hite, pow dery solid , m. p.

101-102° a fte r re c ry s ta ll iz a tio n from ethyl ace ta te w as 20 g. (44%).

A nal: C alcd. fo r C ^ N S : C, 4-7. 50; H, 6. 83; N, 13.85.

Found: C, 48.01; H, 7. 15 ;N , 13. 73.

22I. T h ioacry lam ide and C hloroacetaldehyde

T hioacry lam ide (5 g . , ,0. 057 m ole) w as d isso lved in 75 m l. 95%

ethanol and 4. 5 g. (0. 057 m ole) ch loroacetaldehyde added. The m ix tu re

w as then refluxed fo r 8. 5 hours, a fte r which it w as poured into w ater,

m ade b asic w ith sodium hydroxide, and ex trac ted w ith anhydrous e th e r.

The e th e r e x tra c ts w ere d ried , and the e th e r rem oved under vacuum .

D istilla tion of the re s id u a l red d ish brow n oil yielded 2 m l, of a c le a r,

c o lo rle ss liquid, b. p. 25° (0. 5m m .). The n. m . r . sp ec tru m showed

no vinyl p ro tons, and the in fra re d sp ec tru m showed a s tro n g carbonyl -1

band at 1750 cm . The product contained no su lfu r o r n itrogen , but

did contain ch lo rine . This product w as not fu rth e r identified .

25

J , T hioacry lam ide and C M oroacetal in E thanol

T h ioacry lam ide (34. 8 g. t 0. 4 m ole) and 61. 04 g. (0. 4 m ole) of

ch lo ro ace ta l w ere heated on a steam bath in 175 m l. 95% ethanol

until the ethanol evaporated . The re s id u e w as w orked up in the u sua l

m anner (see I..). D istilla tion of the re s id u a l liquid y ielded 50 g. of

a c le a r , c o lo rle ss liquid, b. p. 44-47° ( 5. 5mm) which contained no

su lfu r o r n itrogen , but did contain ch lorine; The in fra re d sp ec tru m

of th is m a te r ia l w as superim posab le on tha t of ch lo roace ta l.

27K. A cry lam ide, Phosphorus P en tasu lfid e , and C hloroacetone

A m ix tu re of 150 g. (2. 11 m ole) and 100 g. (0. 45 m ole) of phor-

phorus pentasu lfide w as added to 100 m l. of dry benzene. To th is

w as added 20 m l. of a m ix tu re of 200 m l. of ch loroacetone in 75 m l,

of d ry benzene. The flask w as heated on a w a te r bath to in itia te the

reac tion , a fte r which the bath w as rem oved and the re m a in d e r of the

ch lo roacetone-benzene added portionw ise through a re flu x condenser.

A fter about o n e -th ird of the m ix tu re had been added, a so lid form ed

in the flask , m aking s t i r r in g im possib le and n ece ss ita tin g shaking

the flask a fte r each addition in o rd e r to obtain at le a s t p a r tia l m ixing.

When all of the ch lo roacetone-benzene m ix tu re had been added, the

flask, was heated on a steam bath fo r 1 /2 hour and .375 m l. of w ater

was added. The rea c tio n m ix tu re w as then allowed to stand at room

tem p e ra tu re fo r 2 hours. A fter th is tim e, the tw o-phase sy stem was

26

sep a ra ted . The low er la y e r , a deep re d oil, w as m ade.basic-w ith

po tassium hydroxide and ex trac ted w ith e th e r. The e th e r e x tra c ts

w ere d ried , f ilte re d , and the e th e r rem oved. D istilla tio n yielded

5 g. of a s ligh tly v iscous orange liquid, b„ p. 76-83° (2-2 . 5mm), th e .

in fra re d sp ec tru m of which showed strong carbonyl absorp tion at -1

1720 cm and whose n. m . r . sp ec tru m indicated the absence of

a rom atic p ro tons.

2 5L. T hioacry lam ide and C h lo roaceta l in H ydrochloric Acid

T hioacry lam ide (17. 8 g . , 0. 204 m ole) and 30. 8 g. (0. 204 mole)

of ch lo ro ace ta l w ere refluxed Under n itrogen in 100 m l, 6N hydro -

ch lo ric acid for 1 hour. The dark, v iscous m ix tu re w as w orked up

in the u su a l m anner (see I . ), and, a f te r evaporation of the e ther,

th e re rem ained on ly a.few drops Of a brow n oil - not enough to d is till.

23M. T hioacry lam ide and C h lo roaceta l w ith Anhydrous O xalic Acid

A m ix tu re of 19. 4 g. (0. 127 m ole) of ch lo ro ace ta l and 11.4 g.

(0.127 m ole) of anhydrous oxalic acid w as heated under a reflux

ocondenser in an oil ba th at 140 un til gas evolution ceased . To the

solution w as then added 11.0 g; (0. 127 m ole) of th io acry lam id e .

Gentle heating in itia ted a b r is k reac tio n , w hereupon heat w as rem oved

and the reac tio n allowed to p roceed un til it subsided (about 1/2 hour),

oThe d ark m ix tu re w as then heated fo r an additional hour at 100 ,

allowed to cool, and diluted w ith 100 m l. of dilute hydroch lo ric acid

27

and 100 m l. of w a te r. F iltra tio n rem oved the p rec ip ita ted so lid s,

and the c le a r , d a rk f i ltra te w as m ade b asic w ith 5N po tassium

hydroxide and ex trac ted w ith e th e r. An attem pt to d is till the r e s i ­

dual d a rk oil under vacuum a fte r rem ova l of the e th e r re su lte d in

the fo rm ation pf a so lid in the d is tilla tio n flask (bath tem p era tu re

< 100°). T his solid , d ifficu lty soluble in m ost o rgan ic so lven ts,

could not be re c ry s ta ll iz e d , rem ain ing a brow n sludge a fte r all

a ttem pts.

N. T h ioacry lam ide and C h lo roaceta l in Ethanol (Acid Catalyzed)

A m ix tu re of 8. 7 g. (0. 1 m ole) of th ioacry lam ide , 15. 3 g. (0, 1

m ole) of ch lo roace ta l, and 3 ml. of concen tra ted hydroch lo ric acid

was refluxed in .95% ethanol fp r 12 h ou rs. The dark m ix tu re was

allowed to cool and w orked up in the u su a l m anner (see I , ). D is til­

lation of the re s id u a l d a rk liquid under a sp ira to r vacuum yielded

3. 5 g. of ch loroacetaldehyde and 11. 5 g. of ch lo ro ace ta l (identified

by its in fra re d spectrum ),

O. . T h iom ethacry lam ide and C h lo roaceta l w ith A nhydrous

Oxalic Acid

The p rocedu re d esc rib ed in (M .) w as followed, using 10,1 g,

(0.1 m ole) of th iom ethacry lam ide , 15. 3 g. (.0.1 m ole) of ch lo roace ta l,

and 9. 0 g. (0. 1 m ole) of anhydrous oxalic acid. The re s id u e re m a in ­

ing a fte r rem oval of the e th e r w as not enough to d is till, .even" in

m ic ro -a p p a ra tu s .

28

P. Thiom ethacryXam ide and C h lo race ta l in D im ethylform am ide

T hiom ethacry lam ide (10. 1 g . , 0. 1 m ole) and 15. 3 g„ (0. 1 mole)

of ch lo roace ta l in 50 m l. of d im ethylform am ide w ere heated with

os t ir r in g in a w a ter ba th at 95 fo r 4 h ou rs. When the heating was

com pleted, the dark brow n m ix tu re w as w orked up as d esc rib ed

above (see I. ), A ttem pt to d is till the re s id u a l oil re su lte d in the

fo rm ation Of an und istillab le t a r in the d is tilla tio n flask .

Q. T hioacry lam ide and Cyclopentadiene

A m ix tu re of 8. 7 g. (.0. 1 m ole) of th ioacry lam ide and 6. 6 g.

(0. 1 m ole) of cyclopentadiene (d is tilled im m ed ia te ly befo re use

through a 12-inch colum n packed w ith g la ss he lices and caught in a

D ry Ice-coo led receiving, flask) w as refluxed in 100% ethanol fo r 6

hours. Rem oval of the so lvent yielded 7. 4 g. of a white solid , m, p.

198-199°. Its low so lub ility in m ost o rgan ic so lven ts m ade c h a ra c ­

te r iz a tio n difficult, but the n. m . r . sp ec tru m showed the d isappearance

of the vinyl p ro tons of th ioacry lam ide , and the appearance of h igher

33field peaks c h a ra c te r is t ic of the bicycloheptene sy stem , although

the low field peaks appear to be absent.

R. T hiom ethacry lam ide and Cyclopentadiene

M ixtures of 12, 1 g. (0. 12 m ole) of th iom ethacry lam ide and 7. 92 g.

(0, 12 m ole) of f re sh ly d is tilled cyclopentadiene w ere tre a te d as follow s:

1, In anhydrous e th e r at room te m p e ra tu re fo r 12 hou rs.

29

2. In refluxing ch lo ro fo rm fo r 8 hours.

3. In refluxing absolute ethanol fo r 18 hours.

All reac tio n s re su lte d in an e sse n tia lly quantitative re c o v e ry of

s ta r tin g m a te ria l, as de te rm ined by sp e c tra and m ixed m elting point.

S. T h iom ethacry lam ide w ith H ydrochloric Acid in Ethanol

A m ix tu re of 5 .0 g. (0 .05 m ole) of th iom ethacry lam ide , 2 m l. of

concen tra ted hydroch lo ric acid, and 50 m l. of 95% ethanol was r e -

fluxed fo r 6 hours. Rem oval of the g re a te r p a rt of the solvent on a

ro ta ry ev ap o ra to r y ielded 3. 8 g. of a white solid . The crude

m a te r ia l, m . p. > 250°, was insoluble in ch loroform , carbon t e t r a ­

ch loride, acetone, and dioxane, and soluble in w ater, m ethanol,

ethanol, and dim ethylsulfoxide. The so lid was d isso lved in d im ethy l-

sulfoxide and poured into ch lo ro fo rm , resu ltin g in the p rec ip ita tion

of a fine, white pow der, w hich was f ilte re d and d ried in vacuo at 70°

fo r 12 hours. rCj (0. 5% in DMSO) 1. 06; ^ 0. 117.

29T. B ase-C ata lyzed P o ly m eriza tio n of T hioacry lam ide

P o ta ss iu m t-bu tox ide w as p rep a red by adding 39 g. of fre sh ly

cut po tassium to 74. 1 g. of d ry t-b u ty l alcohol (d ried and d is tilled

over sodium ) and refluxing the m ix tu re fo r 15 hours. The excess

t-b u ty l alcohol w as d is tilled under reduced p re s su re , and the product

was obtained as a white pow der free from the alcohol.

30

A solution of 3. 87 g. of th ioacry lam ide in 20 m l. of d ry d im ethy l-

fo rm am ide in a 100-m l 3-necked flask equipped with a m agnetic s t i r r e r

and reflux condenser w as heated w ith 0. 00 54 g. of phenyl- (3 -naphthala-

quickly added 0.0598 g. of po tassium t-bu tox ide, and the m ix ture

s t i r r e d at the sam e te m p e ra tu re fo r 30 hours. Solid m a te r ia l was

noted in the flask a fte r about 10 hours.

The reac tio n was quenched by pouring into w a ter containing 10%

ethanol and a tra c e of hydroch lo ric acid. Much of the solid m a te ria l

d isso lved , so the aqueous m ix tu re w as poured into m ethanol, r e s u l t ­

ing in a m ore copious p rec ip ita te . The so lid was f ilte re d and dried

in vacuo at 70° fo r 12 hours, yielding 2. 5 g. of a white powder, m. p.

U. B ase-C ata lyzed P o ly m eriza tio n of T h iom ethacry lam ide

The sam e m ethod d esc rib ed above, using 4. 38 g. of th io m e th acry ­

lam ide, 0 .0027 g. of phenyl-j3 -naphthalam ine, and 0.0293 g. of

po tassium t-bu tox ide. The reac tio n m ix tu re was heated under helium

for 36 hours, so lid being noted a fte r about 8 hours.

E x trac tion of the f iltra te w ith e th e r and evaporation yielded 0. 8 g.

of u n reac ted th iom ethacry lam ide . T otal y ield of po lym er a fte r drying:

3. 0 g. of white pow der, m . p. > 275°. rn r e ̂ (0. 0 5% in DMSO) 1. 009;

m ine at 135° under n itrogen fo r 1 hour. To th is m ix tu re w as then

> 275 o (0. 05% in DMSO)re l

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31

32

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