The Preparation of Some Derivatives of 2,4,6-Trinitrotoluene

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P U R D U E U N IV ER SITY

THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION

R. D. Lowrey

BY

ENTITLED

THE PREPARATION OF SOME DERIVATIVES OF

2,4>6"TRINITR0T0LUENE

COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES

AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS

FOR THE DEGREE OF

M a ste r o f S c ie n c e

P r o f e s s o r in C h a r g e o f T h e s is

H ea r o f S chool, o r D epa r tm en t

F e b ru a ry ,

19

49

TO THE LIBRARIAN;-

M THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL.

PROFESSOR t t r OBARGR

BRGI6TRAS FORM 10—7 .4 7 — IM

THE HÎEPAEÎATION OF SOME DERIVATIVES OF 2 , 4 ,6-TRINITROTODDEm A T h e s is S u b m itte d t o t h e F a c u l t y of P u rd u e U n i v e r s i t y by R . D» L ow rey In P a r t i a l F u lf illm e n t o f th e R equi re m e n ts f o r t h e D e g re e of M a s te r o f S c ie n c e F e b r u a r y , 1949

ProQuest Number: 27708644

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

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ACKNOlïIEDGa/ESITT

!Ehe a u th o r w is h e s t o e x p r e s s h i s s i n c e r e a p p r e c i a t i o n t o P r o f e s s o r H. B* H a ss f o r h i s v a lu a b l e s u g g e s tio n s a n d e n co u ra g e m e n t t h r o u ^ o u t t h e w ork* The a u t h o r a l s o w is h e s t o th a n k M r, E l i L i l l y a n d t h e P u rd u e R e s e a r c h F o u n d a tio n vho s p o n s o re d t h i s work*

TABLE OF CONTEOTS P ag e

ABSTRACT................................................. INTRODUCTION EXPERnŒNTAL

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

i *.................................................

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

2

P re p a ra tio n o f jj^ ,4 ,6 - tr in itr o p h e n y le tlia n o l P r e p a ra tio n o

1

* .» .* .*

2

4 ,6 -trin itro p h e n y le th y l a c e ta te • • • • « • .* • •

2

#.*.#,*.*#*#***

2

P r e p a ra tio n o f e s t e r s in benzene

R e a c tio n o f ^ 2 ,4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e w i t h so d iu m c a r b o n a te .,* * * .# * # # # # .* # # .* * * .* * * # .* # * # # # # * * # * * # * * » » *

3

R e a c tio n o f ^ - 2 ,4 ,6 - t r i n i t r o p h e n y i e t h a n o l w ith i s o v a le r y l c h lo rid e

3 5

DISCUSSION..................................................... s u m m R Y .................... BIBLIOaRAIHY

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

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

6 7

THE HïEPARATION OF SOIÆE DERIVATIVES OF 2 , 4 , 6-TRINITROTOLUENE By H. B . H a ss an d R , D . Low rey ( C o n t r i b u t i o n fro m D e p a rtm e n t o f C h e m is try and P u rd u e R e s e a r c h F o u n d a tio n , P u rd u e U n i v e r s i t y , L a f a y e t t e , I n d ia n a ) AN ABSTRACT V ender (1) p r e p a r e d 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h a n o l b y r e a c t i n g

(1)

V e n d e r, Gazz ohim* i t a l , , 4 5 , I I , 97

'-5'}

2 , 4 , 6 - t r i n i t r o t o l u e n e w ith fo rm a ld e h y d e i n t h e p r e s e n c e o f a l k a l i . V e n d e r m e n tio n e d i n h i s p a p e r t h e f o r m a tio n o f a c r y s t a l l i n e a c e t a t e e s t e r o f t h i s a lc o h o l a n d t h i s s u g g e s te d t h a t t h e e s t e r s o f ^ 2 , 4 , 6 t r i n i t r o p h e n y l e t h a n o l m ig h t s e r v e a s s o l i d d e r i v a t i v e s o f o r g a n i c a c i ds. 3 - 2 , 4 , 6 - T r i n i t r o p h e n y l e t h a n o l was p r e p a r e d a t f i r s t b y V e n d e r’ s p r o c e s s and th e n b y an im p ro v ed m ethod w h ic h was d e v e lo p e d in th i s la b o ra to ry .

T h is im provem ent c o n s i s t e d o f u s i n g a s o l v e n t

su c h a s e th a n o l f o r t h e r e a c t i o n a n d a llo w in g t h e m ix tu r e t o r e f l u x f o r a s h o r t tim e on a s te a m b a t h .

The a c e t a t e e s t e r o f t h e a l c o h o l

was p r e p a r e d by h e a t i n g g l a c i a l a c e t i c a c i d w i t h th e a l c o h o l a n d t h e n d i s t i l l i n g t h e e x c e s s a c id fro m t h e m i x t u r e .

T%en t h i s m eth o d w as

u s e d w i t h p r o p i o n i c a c i d a c r y s t a l l i n e p r o d u c t w as o b t a i n e d w h ic h m e lte d a t 121®C. a f t e r r e c r y s t a l l i z a t i o n . gave a d a rk c o lo r e d o i l *

B u t y r i c a c i d , h o w e v e r,

11

T i n d a l l (2) p r e p a r e d some e s t e r s o f n i t r o a l c o h o l s b y re a c t*

(2 )

T i n d a l l , I n d . E n g . C hem .,

65 (1941)

in g t h e a l c o h o l a n d a c i d i n a b e n ze n e s o l u t i o n .

The b e n z e n e rem oved

t h e w a t e r fo rm ed i n t h e r e a c t i o n i n t h e fo rm o f t h e b e n z e n e - w a te r a z e o tr o p e a n d t h e b e n z e n e was th e n r e t u r n e d t o t h e r e a c t i o n a f t e r c o n d e n s a tio n an d s e p a r a t i o n fro m t h e w a t e r .

T h is m ethod w a s a tte m p te d

u s i n g 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e th a n o l a n d n - b u t y r l c a c i d b u t th e p r o d u c t a g a in w as a n o i l . The n e x t a tte m p t t o e s t e r i f y t h e a l c o h o l was c a r r i e d o u t w ith an a c i d c h l o r i d e . a v a ila b ility .

I s o v a l e r y l c h l o r i d e w as u s e d b e c a u s e o f i t s

The am ount o f h y d ro g e n c h l o r i d e e v o lv e d w as m e a s u re d

and a f t e r t h e r e a c t i o n w as c o m p le te d th e u n r e a c t e d a c i d c h l o r i d e w as d i s t i l l e d from t h e r e a c t i o n v e s s e l an d t h e r e s i d u e w as a n a ly z e d f o r n itro g e n .

The n i t r o g e n a n a l y s i s show ed: C a lc , f o r CisHisNgOg N

1 2 .3

Found 1 2 .2

The e s t e r s o f n i t r o a l c o h o l s c a n b e u s e d to p r e p a r e n i t r o o l e f i n s i n a l i p h a t i c c h e m is tr y (3 ) an d s i n c e 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l (3 )

N ig h tin g a le a n d J a n e s , J . Am, Chem, S o c . , 6 6 , 352 ( 1 9 4 4 ) .

e t h a n o l was p r e p a r e d by a r e a c t i o n s i m i l a r t o t h a t o f a n i t r o p a r a f ­ f i n w ith fo rm a ld e h y d e , i t seem ed r e a s o n a b l e t o e x p e c t 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e to fo rm 2 , 4 , 6 - t r i n i t r o s t y r e n e i f s u b j e c t e d t o th e p r o p e r c o n d i t i o n s .

The p r o d u c t o f t h e r e a c t i o n was a brow n

iii

pow der W iich d i d n o t m e lt w hen i t w as h e a te d up t o 3 5 0 ®C.

T h is p o w d er

was i n s o l u b l e i n w a t e r , e t h a n o l , a n d e t h e r , b u t w a s s o l u b l e i n a c e to n e . The pow der was p r o b a b ly a low m o le c u la r w e ig h t p o ly m e r o f 2 , 4 , 6 - t r i ­ n i t r o s t y r en e .

I t b u rn e d w i t h a s o o ty f la m e .

iv

EXPERIMENTAL A t y p i c a l e x p e r im e n t f o r t h e p r e p a r a t i o n o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y le th a n o l w as c a r r i e d o u t i n t h e f o ll o w i n g m anner* A 10*0 g* sam ple o f 2 , 4 , 6 - t r i n i t r o t o lu e n e was d i s s o l v e d i n 100 m l. o f 95% e t h a n o l a n d 7*0 g . o f f o r m a l i n w as a d d e d w i t h 0 . 1 g . o f sodium c a r b o n a t e .

The s o l u t i o n tu r n e d r e d and dyed a n y c l o t h o r

h a i r w i t h w h ich i t came i n c o n t a c t .

The m ix tu r e w as r e f l u x e d 3 h o u r s

on a s te a m b a th and t h e n p o u re d i n t o c o ld w a t e r (1 6 ®C.)* w as a llo w e d t o

The m ix tu r e

s ta n d o v e m i ^ t a n d t h e c r y s t a l s o f 3 - 2 , 4 , 6 - t r i n i t r o -

p h e n y le th a n o l s e p a r a t e d fro m t h e s o l u t i o n .

T hese c r y s t a l s w e re

f i l t e r e d fro m t h e s o l u t i o n a n d p u r i f i e d by s o l u t i o n i n e t h a n o l , t r e a t m e n t w i t h a c t i v a t e d c a r b o n , an d t h e n r e c r y s t a l l i z a t i o n .

The

p u r i f i e d p r o d u c t w e ig h ed 8 .0 g . , r e p r e s e n t i n g a 71% y i e l d , b a s e d on 2 ,4 ,6 - tr in itro to lu e n e • P r e p a r a t i o n o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e w as c a r r ie d o u t i n th e fo llo w in g w ay.

A 1 0 .0 g . sam ple o f 3 - 2 , 4 , 6 - t r i ­

n i t r o p h e n y le th a n o l was p l a c e d i n a 100 m l. ro u n d b o tto m f l a s k f i t t e d w ith a r e f l u x c o n d e n s e r.

F o r t y m l. o f g l a c i a l a c e t i c a c i d w a s a d d e d

a n d t h e s o l u t i o n was r e f l u x e d one h o u r .

The a c e t i c a c i d w as th e n

d i s t i l l e d from t h e f l a s k , l e a v i n g a r e s i d u e o f y e llo w c r y s t a l s .

T h e se

c i y s t a l s w e re d i s s o l v e d i n a b s o l u t e e t h a n o l a n d r e c r y s t a l l i z e d t o p a l e y e llo w p l a t e l e t s w h ic h m e lte d a t 97®C. T i n d a l l ’ s m ethod o f p r e p a r i n g e s t e r s o f n i t r o a l c o h o l s w as c a r r i e d o u t b y t h e f o ll o w i n g p r o c e d u r e .

A 20 g . sam p le o f 3 - 2 , 4 , 6 -

t r i n i t r o p h e n y l e t h a n o l w as d i s s o l v e d i n 100 m l. o f b e n z e n e and 0 .5 m l. o f c o n c e n t r a t e d s u l f u r i c a c i d w as a d d e d .

E i ^ t gram s o f b u t y r i c a c i d

vjas t h e n a d d e d , a n d t h e s o l u t i o n w as r e f l u x e d f o r 8 h o u r s .

The

b e n z e n e - w a te r a z e o tr o p e d i s t i l l e d fro m t h e r e a c t o r , w as c o n d e n s e d , and th e n s e p a r a t e d i n t o b e n z e n e an d w a t e r l a y e r s . th e n re tu r n e d to th e r e a c tio n v e s s e l .

The b e n z e n e was

A f te r th e r e a c t i o n had

p ro c e e d e d 8 h o u r s , t h e b e n z e n e w as d i s t i l l e d fro m t h e r e a c t i o n v e s s e l , le a v in g a r e s id u e o f a d a rk c o lo re d o i l .

The o i l was p u r i ­

f i e d b y t r e a t m e n t o f th e b e n z e n e s o l u t i o n o f t h e o i l w ith a c t i v a t e d c a r b o n , b u t i t r e t a i n e d i t s d a r k c o l o r w hen i t w as r e c o v e r e d . The r e a c t i o n o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e w i t h sod iu m c a r b o n a te w as c a r r i e d o u t i n a t t e m p t i n g to p r e p a r e 2 , 4 , 6 trin itro s ty re n e .

A 20 g . s a rg jle o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e iScP

jS 'O

t a t e was a d d e d t o a m ix tu r e o f SOÔ- m l. o f m e th a n o l a n d xOO- m l. o f 0 .5 N sodium c a r b o n a te s o l u t i o n .

The s o l u t i o n t u r n e d r e d a t r e f l u x

te m p e r a t u r e s a n d a brow n pow der s e p a r a t e d i n a s h o r t t i m e .

The

m ix tu r e was r e f lu x e d f o r 8 h o u r s an d t h e n t h e brown pow der was s e p a r a t e d fro m t h e s o l u t i o n b y f i l t r a t i o n .

T h is po w d er d i d n o t

m e lt M ien h e a te d t o 3 5 0 ®C*, w as s o l u b l e i n a c e t o n e , b u t i n s o l u b l e in w a te r , a lc o h o l, and e t h e r .

THE REPARATION OF SOI# DERIVATIVES OF 2 , 4 , 6-TRINITROTOLUENE INTRCDUCTION The p u rp o s e o f t h i s r e s e a r c h w as t o a t t e m p t t o f i n d a u s e f o r t h e 2 , 4 , 6 - t r i n i t r o t o l u e n e w h ic h w as a v a i l a b l e i n l a r g e q u a n t i t i e s f o llo w in g W o rld War I I . A s e a r c h o f th e l i t e r a t u r e

d i s c l o s e d t h a t V e n d e r (5) h a d

p re p a re d 3 - 2 ,4 ,6 - tr in itr o p h e n y le th a n o l by r e a c tin g 2 ,4 ,6 - t r i n i t r o ­ t o l u e n e w ith fo rm a ld e h y d e i n t h e p r e s e n c e o f a l k a l i .

He a l s o p r e ­

p a r e d 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e an d 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l­ e th y l n i t r a t e .

He d i d n o t m e n tio n a n y o t h e r e s t e r s o f t h i s a l c o h o l

o r any a tte m p ts to p re p a re o th e r e s t e r s . B ecau se o f t h e s i m i l a r i t y o f t h e r e a c t i o n o f 2 , 4 , 6 - t r i n i t r o to lu e n e an d f o i n a l d e h y de t o fo rm a n i t r o a l c o h o l t o t h e r e a c t i o n o f a n i t r o p a r a f f i n w ith fo rm a ld e h y d e t o f o m a s i m i l a r p r o d u c t , i t seem ed l o g i c a l t o s e e i f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y le th a n o l r e a c t e d l i k e an a l i ­ p h a tic n itr o a lc o h o l.

T i n d a l l (4) e s t e r i f i e d a l i p h a t i c n i t r o

a lc o h o ls

b y t r e a t i n g them w ith a c i d i n a b e n z e n e s o l u t i o n , re m o v in g t h e w a te r fo rm ed i n t h e r e a c t i o n b y b o i l i n g t h e b e n z e n e - w a te r a z e o tr o p e fro m t h e re a c tio n .

S e v e r a l w o rk e rs ( 1 , 2 , 2 ) have p r e p a r e d n i t r o

n itro e s te r s .

o l e f i n s fro m

T hese two r e a c t i o n s w e re a tte m p te d u s i n g 3 - 2 , 4 , 6 - t r i -

n i t r o p h e n y le th a n o l a n d i t s a c e t a t e e s t e r .

EXRHIMENTAL P r e p a r a t i o n o f 3 - 2 ,4 » 6 - t r i n i t r o p h e n y l e t h a n o l A 10 g . sam ple o f 2 , 4 , 6 - t r i n i t r o t o l u e n e w a s d i s s o l v e d i n 100 m l, o f 95% e t h a n o l a n d 7 g . o f f o r m a l i n w ith 0 . 1 g . o f so d iu m c a r b o n a te was added t o t h e s o l u t i o n .

The m ix tu r e w as r e f l u x e d on

a ste a m b a t h f o r 3 h o u rs an d t h e n p o u re d i n t o c o ld w a t e r .

The m ix­

t u r e was a llo w e d to s t a n d o v e r n i g h t w h ile c r y s t a l s o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h a n o l fo rm e d .

The c r y s t a l s w ere f i l t e r e d fro m t h e

l i q u i d and p u r i f i e d b y d i s s o l v i n g i n e t h a n o l , d e c o l o r i z i n g w i t h a c tiv a te d c arb o n , and th e n r e c r y s t a l l i z i n g .

The p u r i f i e d c r y s t a l s

m e lte d a t 1 1 2 ®C. a n d w e ig h e d 8 g . , a 71% y i e l d b a s e d on 2 , 4 , 6 - t r i n i t ro t o l u e n e . P r e p a ra tio n o f 3 - 2 ,4 ,6 - tr in itr o p h e n y le th y l a c e ta te A 40 m l. sam ple o f g l a c i a l a c e t i c a c i d w as p la c e d i n a 100 m l. ro u n d b o tto m f l a s k f i t t e d w i t h a r e f l u x c o n d e n s e r .

A 10 g*

sam ple o f 3 - 2 , 4 , 6 - t r i n i t i D p h e n y l e t h a n o l was a d d e d t o t h e f l a s k an d t h e f l a s k w as t h e n h e a t e d one h o u r a t t h e r e f l u x te m p e r a tu r e o f t h e a c e tic a c id .

The e x c e s s a c e t i c a c i d w a s t h e n d i s t i l l e d fro m t h e

f l a s k , le a v i n g a r e s i d u e o f a y e llo w c r y s t a l l i n e

s o l i d w h ic h w as

p u r i f i e d b y t r e a t i n g an e t h a n o l s o l u t i o n o f t h e e s t e r w i t h a c t i v a t e d c arb o n .

The p u r i f i e d c r y s t a l s m e lte d a t 9 7 ° 0 .

P r e p a r a tio n o f e s t e r s i n benzene A 20 g . sam ple o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h a n o l w as d i s ­ s o lv e d i n 100 m l. o f b e n z e n e a n d 0 . 5 m l. o f c o n c e n t r a te d s u l f u r i c

a c i d was a d d ed w ith 8 .0 g . o f b u t y r i c a c i d .

The s o l u t i o n w as h e a t e d

an d t h e b e n z e n e - w a te r a z e o tr o p e was d i s t i l l e d fro m t h e m i x t u r e , an d c o n d en se d i n a s p e c i a l p i e c e o f a p p a r a t u s w h ic h r e t u r n e d t h e b e n z e n e t o t h e r e a c t i o n m ix tu r e w h ile t h e w a te r w as d i s c a r d e d .

A fte r 8 h o u rs ,

th e b e n z e n e was d i s t i l l e d fro m t h e r e a c t i o n , l e a v i n g a d a r k o i l a s a re s id u e .

The r e s i d u e w as d i s s o l v e d i n b e n z e n e a n d t r e a t e d w i t h

a c t i v a t e d c a r b o n , b u t o n l y th e d a r k o i l c o u ld b e r e c o v e r e d fro m t h e benzene. R e a c tio n o f P - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e w i t h so d iu m c a r b o n a te A 20 g . sam ple o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e w as ad d ed t o a m ix tu r e o f 150 m l. o f m e th a n o l and 150 m l. o f 0 . 5 N sodium c a rb o n a te .

The m ix tu r e tu r n e d r e d a t r e f l u x te m p e r a t u r e an d a brow n

pow der s e p a r a t e d .

m ix tu r e w as r e f lu x e d 8 h o u rs an d t h e n t h i s

pow der w as f i l t e r e d fro m t h e r e a c t i o n m i x t u r e .

The m e l t i n g p o i n t o f

t h e pow der w as o v e r 4 0 0 ®C. an d i t was i n s o l u b l e i n w a t e r , a l c o h o l , and e t h e r b u t w a s s o lu b le i n a c e t o n e . A n a ly s is C a lc , f o r 2 , 4 , 6 - t r i n i t ro s ty r e n e %N

1 7 .5

Found 1 7 .1

R e a c tio n o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y le th a n o l w i t h i s o v a l e r y l c h l o r i d e A 10 g . sam ple o f 3 - 2 , 4 , 6 - t r i n i t r o p h e n y le th a n o l was p l a c e d i n a 50 m l, 3 -n e c k f l a s k .

The f 3 a s k w as f i t t e d w i t h a c o n n e c t i o n to

a s o u r c e o f d ry n i t r o g e n w h ich c o n s i s t e d o f a t r a i n w h ic h d r i e d n i t r o g e n fro m a c o m m e rc ia l c y l i n d e r .

The o t h e r tvro c o n n e c tio n s t o

t h e f l a s k w ere f i t t e d w itii a d ro p p in g f u n n e l a n d a r e f l u x c o n d e n s e r#

The to p o f t h e r e f l u x c o n d e n s e r w as c o n n e c te d t o two so d iu m h y d ro x id e t r a p s i n s e r i e s su c h t h a t a n y g a s p a s s i n g th ro u g h t h e c o n d e n s e r b u b b le d th ro u g h t h e s e tw o s o l u t i o n s o f so d iu m h y d r o x id e .

The f l a s k

was sw e p t o u t w i t h n i t r o g e n an d t h e n 1 5 .0 g* o f i s o v a l e l y l c h l o r i d e was a d d ed t h r o u ^ t h e d ro p p in g f u n n e l*

The f l a s k w as h e a te d o n a n

o i l b a th f o r 4 h o u r s a t 5 0 ®C* a n d th e n t h e f l a s k w as f l u s h e d a g a i n w ith n i t r o g e n .

The s t a n d a r d s o l u t i o n o f so d iu m h y d ro x id e w as t h e n

b a c k t i t r a t e d w i t h s t a n d a r d s u l f u r i c a c id * The am ount o f b a s e n e u t r a l i z e d b y h y d ro g e n c h l o r i d e e v o lv e d i n t h e r e a c t i o n w as 4 .1 2 m l. o f .C ^982 N sodium h y d r o x id e .

The am ount

o f h y d ro g e n c h l o r i d e was 1 .4 5 g . w h ile t h e t h e o r e t i c a l v a lu e w as 1 .4 7 g .

T h is r e p r e s e n t s a 99% y i e l d o f h y d ro g e n c h l o r i d e . The r e s i d u e i n th e f l a s k w as h e a te d t o 1 2 5 ®C. t o rem ove t h e

e x c e s s i s o v a l e r y l c h l o r i d e a n d th e o i l r e m a in in g b e h in d w a s d r i e d i n a vacuum d e s i c c a t o r .

A 0 .2 g . sam ple o f t h i s o i l w as t h e n a n a ly z e d

f o r n i t r o g e n a n d t h e f o ll o w i n g r e s u l t s w e re o b t a i n e d . C a l c , f o r th e e s t e r %N

1 2 .3

Found 1 2 .1

DISCIBSLOH When a c i d s o f g r e a t e r m o le c u la r w e ig h t th a n p r o p i o n i c a r e r e a c t e d w i t h g - 2 , 4 , 6 - t r i n i t r o p h e n y le th a n o l ^ t h e p r o d u c t i s a n o i l . T h ese o i l s h ave a n i t r o g e n c o n te n t c o r r e p o n d i n g t o t h a t o f t h e e s t e r b u t a l l a t t e m p t s to c r y s t a l l i z e th e m f a i l e d .

The e a s e w i t h

w h ich 2 , 4 , 6 - t r i n i t ro s ty r e n e fo rm s may b e due t o t h e i n c r e a s e d p o s s i b i l i t i e s f o r re s o n a n c e i n 2 , 4 , 6 - t r i n i t r o s t y r e n e •

Two fo rm s

are : HC=CH2 OoN

OoN

NOa

NO;

The p o s i t i v e c h a rg e o n t h e end c a r b o n may a i d c o n s i d e r a b l y in i t s p o ly m e riz a tio n .

SÜHMAHY 0 - 2 , 4 , 6 - T r i n i t r o p h e n y l e th a n o l w as p r e p a r e d u s i n g V e n d e r’ s m ethod* p re p a re d *

A n e w e s t e r , 0 - 2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l p r o p i o n a t e , w as P o ly m e riz e d 2 , 4 , 6 - t r i n i t r o s t y r e n e w as p r e p a r e d fro m 0 -

2 , 4 , 6 - t r i n i t r o p h e n y l e t h y l a c e t a t e a n d so d iu m c a r b o n a t e .

BIBLIOCmiHY 1.

N ig h tin g a le and J a n e s , J* Am* Chem, S o c * , 6 6 , S52 (1944)

2*

S c h m id t, R u tz , a n d T r e n e l , B e r . ,

3*

S u s i e , Ph.D * T h e s is , P u rd u e U n i v e r s i t y , 1939

4,

T i n d a l l , I n d . E n g . C hem .,

5.

V e n d e r, G azz. ch im . i t a l . , 45 I I , 97^^‘T‘O

472 (1928)

65 (1941)