Catalysis of the benzilic acidrearrangement by alkali amides

Item Type text; Thesis-Reproduction (electronic)

Authors Fenn, Clarence Junius, 1932-

Publisher The University of Arizona.

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Link to Item http://hdl.handle.net/10150/319330

CATALYSIS OF THE BENZILIC ACID REARRANGEMENT BY ALKALI AMIDES

t y

C larence J • Penn

A T h es is

su b m itted to the f a c u l t y o f the

Department o f Chem istry

in p a r t i a l f u l f i l l m e n t o f the req u irem en ts f o r the d egree of

MASTER OF SCIENCE

i n th e Graduate C o l l e g e , U n iv e r s i t y o f A rizona

1956

Approved:D ir e c t o r o f e s i s Date

, I IJ

This t h e s i s has been su bm itted i n p a r t i a l f u l f i l l m e n t of

req u irem en ts f o r an advanced d eg ree a t the U n iv e r s i t y of

A rizona and i s d e p o s i te d in the L ib rary to be made

a v a i la b l e to borrowers under r u l e s o f the L ib r a ry . B r ie f

q u o ta t io n s from t h i s t h e s i s are a l lo w a b le w ith o u t s p e c i a l

p e r m is s io n , p rov id ed th a t a ccu ra te acknowledgment of

sou rce i s made• R equests f o r p e r m is s io n fo r extended

q u o ta t io n from or r e p r o d u c t io n o f t h i s m anu scrip t in

whole or in p a r t may be g ra n ted by the head o f the major

departm ent or the dean of the Graduate C o lle g e when i n

t h e i r judgment the proposed u se o f the m a t e r ia l i s in the

i n t e r e s t s o f s c h o la r s h ip . In a l l o th er i n s t a n c e s , however,

p e r m is s io n must be o b ta in ed from the a u th o r .

SIGNED

• The a u th o r w ish e s to. e x p re s s h i s th an k a to D r « -

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OF OONm m s

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. ' Benzi 11 o acid , rea rran g em en t® 0 ® 00®»«o o»»*»0 0 0 0 0 o ® o. 11

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P r e p a r a t i o n o f ' s o d i u m ' - e t h o x l d e © © © ©' ©,© © © © © © © © © © ©'© © © 17

S o d i u m e t h o x l d e e a t a l y s - i s ® © © © © = © »> © © ® © © ©,©©'©.©'©© © ® * 17 .

' Summary:® © © ©>©©©© © © © © © © © © .© © ;© © © © © .© © ©, ©. © © .© © © ©. © © © © © © © © © © ©.®. 19

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INTRODUCTION

The mechanism fo r the b e n z i l i c a c id rearrangem ent as

proposed by Wheland i n d ic a t e s t h a t the hydroxide io n i s the

s p e c i f i c c a t a l y s t f o r the rearrangem ent ( ! ) • As a b a s i s

fo r h i s mechanism Wheland u se s the r e s u l t s o f k i n e t i c

s t u d i e s w hich have shown the r a te o f r e a c t io n to be

p r o p o r t io n a l to the c o n c e n tr a t io n o f hydroxide io n as

w e l l as b e n z i l , and the f a c t th a t the rearrangem ent i s

independent o f b a ses such as phenoxide io n and _o-ch loro-

phenoxide io n ( 2 ) ,

Using the hydroxide io n as the c a t a l y s t , the mechanism

a cco rd in g to Wheland (1 ) i s i l l u s t r a t e d as f o l lo w s ;

CO -O o -0 < rC^VV C - C - C ^ - 4 OW --------------- » C f c V ^ - C - C ^ v < ---------------- > C fcvX*-C -C -C -l„VW

bVX ov\

I '-o or

4 ^ C,- C* CkAs'* CVXt

From t h i s the f u n c t io n o f the hydroxide io n i s s e e n to be

the n e u t r a l i z a t i o n of the p o s i t i v e charge on one carbon in

order th a t the second carb on y l group may r e so n a te a f u l l

p o s i t i v e charge onto the carbon w ith o u t v i o l a t i n g the

a d ja c e n t charge r u l e . This would then produce the open

s e x t e t o f e l e c t r o n s th a t i s a n e c e s s a r y in te r m e d ia te in

% o*C -C -C A

" o C .V 4-

W hifepr© 2: s h i f t s 0 However5, o t h e r b a ses . , w h ic h do -no t

c a t a l y z e th e r e a r r a n g e m e n t # a u e h ap e th o x id © i o n and

p h e n o x id e i o n $, w ould be j h s t a s e f f e c t i v e i n t h i s r e s p e c t .

a s : th e h y d ro x id e i o n 0 i h i s mechanism^' t h e r e f o r e P does n o t

e x p l a i n f u l l y th e f u n c t i o n o f th e c a t a l y s t o

Prom s t u d i e s o f th e d i p o l e moment o f b e n z i l i n

d i f f e r e n t s o l v e n t s - (5 ) .and from ;X»ray s t u d i e s o f c r y s t a l ­

l i n e b e n z i l ( 4 } # th e m o le c u la r s t r u c t u r e h a s b e e n shown to

be one i n w h ic h th e p l a n e s o f th e two CgHg-CtsO g ro u p s a r e

a t a p p r ox im a te r i g h t a n g le s to e a c h o t h e r o T husfl th e

h y d ro x id e ion*, when i t add s to the- b e n z i l j , i s s e e n to be

v e r y c lo s e to th e a d j a c e n t oxygen® . H t i l l z l n g t h i s skewed

a r r a n g e m e n t of th e b e n z i l m o le c u l e * th e f u n c t i o n o f th e

h y d ro x id e i o n m ig h t a l s o be th e f o r m a t io n o f an i n t e r n a l

h y d ro g e n bond a s d e s c r i b e d by S p r o v l e r i ( 5)o I n f a c t P I n

th e s tu d y o f th e m ig r a to r y p r e f e r e n c e s o f d i f f e r e n t g ro u p s

i n s u b s t i t u t e d b e n z l l s by O t t and S m ith (6 ) s th e h y d ro x id e

io n is- p i c t u r e d as, f orm ihg a c y c l i c h y d ro g e n bonded com plex

a s an i n t e r m e d i a t e i n th e r e a r r a n g e m e n t | a l t h o u g h t h i s

p o i n t i s n o t b r o u g h t o u t i n t h e i r d i s c u s s i o n | and th e y

u t l l i k e - th b o r i g i n a l Yf he l a n d mechanism.o vi<' ;i'. ' ’

Once t h i s f u n c t i o n of th e h y d ro x id e i o n - — th e fo rm a­

t i o n o f a n i n t e r n a l . h y d r o g e n b o n d h = - ls a c c e p te d * i t i s

e a s i l y : s e e n t h a t the r e a r r a n g e m e n t Should be c a t a l y z e d by

any b a se w h ich i s c a p a b le o f fo rm in g an i n t e r n a l h y d ro g en

bondo The e a s e s o f th e phenoxid© i o n and o t h e r s i m i l a r

b a s e s s w h ic h !a3?e n o t C apable o f fo rm in g h y d ro g e n b o n d s a r e ^

i n p e r f e c t a g re e m e h t w i t h t h i s mechanism^ The s t r o n g

/ e v i d e n c e : f o r t h i s l d e a s h o w e v e rs i s o b t a in e d from th e ; ; >

r e p o r t s i n th e l i t e r a t u r e of th e . c a t a l y s i s o f th e - b e n z l l i c

a c i d r e a r r a n g e m e n t w i t h sodium amide by K asiw ag l (7 ) and

H a l l e r (8.) 1 The c r i t l e i a m of th e work by K a s iw a g l (7 ) w i th ;

s odium amide c a t a l y s i s h a s b e e n t h a t w a te r was, add ed

d i r e c t l y to th e s o l u t i o n i n o r d e r to i s o l a t e th e p ro d u o ts o -

I n t h i s s t e p th e , r e a c t i o n o f w a te r w i t h th e u n r e a c t e d amide

w ould p ro duce , h y d ro x id e io n s w h ic h c o u ld c a u se th e r e a r r a h ^ :

gem ent o f the- b en s 11 o- Howeverg t h i s same c r i t i c i s m c a n -b e

a p p l i e d to th e work done by S p r o v l e r i (5 ) i n h i s i n v e s t i ^

g a t i o n o f amide c a t a l y s i s o f b e n s 11 s i n c e he a l s o added

w a te r d i r e c t l y to th e r e a e t i o n m ix tu r e w h ic h c o n ta in e d an

e x c e s s of the. sodium amide 6 A lso p. s i n c e the. m echanism

p ro p o s e d f o r th e r e a c t i o n p r e d i c t s t h a t sodium amide

c a t a l y s i s s h o u ld g iv e b e n z i la m ld e . a s a p ro d u c t^ and s i n c e

no am ides were i s o l a t e d among th e p r o d u c t s by S p r o v l e r i o r

K asiw ag ip th e u se -'of w a te r i n d i r e c t c o n t a c t w i t h th e ■

r e a c t i o n m ix tu r e i s q u e s t io n a b le © .

, The p u rp o se o f t h i s r e s e a r c h was to i n v e s t i g a t e -

f u r t h e r th e p o s t u l a t e d m eehanism “ “ - ° th a t any s t r o n g l y .

b a s i c e a t a l y s t c a p a b le o f fo rm in g an I n t e r n a l h y d ro g en ‘

bond s h o u ld cau se , th e b e n z i l to r e a r r a n g e ^ '—w i t h o u t

a l lo w in g w a te r to c o n t a c t t h e s o l u t i o n o f b e n z l l and

u n r e a e t e d sodium amidep sodium a n l l i d e y o r sodium .

. H-me t h y l a n l l i d e © . - ' . ■ : - - ' . ' - -

4

; Thus b e n z l i .w a s t r e a t e d w i t h t h e s e b a s i c c a t a l y s t s and

th e p r o d u c t s ' lO T e s t i g a t e d f o r t h e am ides of b e n z i l i c acid®

&GCording .to th e , p p s t u l a t e d m echanism f o r t h i s r e a c t i o n , .

sodlum amide and sodium a n i l i d e , ■ sh o u ld c a u s e th e r e a r : r a n g e .

m en t to g i v e b e n z i la m ld e and b e n z i l a n l i i d e j w h i le sodium

N - m e th y la n i l id e s h o u ld n o t .cause any rea r ran g e m en t®

: . . / D i s c i m i o E . ■

I n th e p r e v io u s w/b3?k on th e sodlum amide c a t a l y s t s by .

K as lw ag l (7 ) and. S p r o v i e r i ( 5 ) 5 w a te r was in t ro d u c e d ,

d l r e e t l y I n t o th e r e a c t i o n i n th e s e p a r a t i o n o f tlie

r e a r r a n g e d p r o d u c t s from th e u n r e a c t e d b en z tl® T h is

p ro c e d u r e i s h i g h l y q u e s t i o n a b l e s i n c e th e e x c e s s sodium

amide c a t a l y s t h y d r o ly z e s v e r y r e a d i l y i n w a t e r » Ih e

h y d r o x i d e : Iona th u s p ro d u c e d c o u ld c au se c o n s i d e r a b l e

r e a r r a n g e m e n t of th e u n r e a c t e d b e n z i lo T h e re fo re a

p r o c e d u r e w h ldh w ould e l i m i n a t e t h i s p r o b a b le s o u rc e o f

e r r o r was i n v e s t i g a t e d ® I t was fo u n d t h a t by a d d in g an

' a c i d i c s u b s t a n c e s u c h as t r im s thylammonium c h l o r i d e th e

.b e n z l l= b a s e com plex c o u ld be decom posed and th e e x c e s s

b a s e n e u t r a l i z e d ^ Then by e x t r a c t i n g th e b e n z l l i e a c i d ;

o u t o f th e s o l u t i o n w i t h fo rm am id e s th e b e n z l l i e a c i d c o u ld

be s e p a r a t e d from u n r e a c t e d 'benz l 1®. The b e n z i l i c a c i d

c o u ld be p r e c i p i t a t e d from th e form am ide upon a d d i t i o n o f

w a te r and d i l u t e s u l f u r i c acid® Hpon a p p l i c a t i o n o f t h i s

p r o c e d u r e to a sodium h y d ro x id e c a t a l y z e d r e a c t i o n ^ an

89^ y i e l d of b e n z i l i c a c i d w i t h a m e l t in g p o i n t o f 149=

150 d e g re e s was o b t a i n e d = T h is h i g h y i e l d i n d i c a t e d the

p r o c e d u r e was v a l i d and u s a b l e f o r s e p a r a t i o n a n d i s o l a t i o n

o f b e n z i l i c acid®

- A c c o rd in g to th e f o l l o w i n g p ro p b se d m echanism f o r th e •

6

rearran gem ent, sodium amide c a t a l y s i s sh ou ld produce

h en z ila m id e as a p r o d u c t .

B efore the above procedure cou ld be used on a sodium

amide c a t a l y s i s o f b e n z i l , i t was n e c e s s a r y to prepare a

known sample o f b en z ila m id e to check i t s p r o p e r t i e s •

S e v e r a l methods o f p rep ar in g b en z ila m id e were t r i e d

numerous tim es w ith o u t s u c c e s s ( 9 ) , ( 1 0 ) , (1 1 )# A method

t h a t f i n a l l y met w ith s u c c e s s was one which f i r s t r e s u l t e d

in the p r e p a r a t io n o f the < x -c h lo r o a c id c h lo r id e o f b e n z i l l c

a c i d , then the o c -o h lo r o b e n z i la m id e , and f i n a l l y , by hydro­

ly z in g the o c -c h lo r o group , the amide of b e n z i l l c a c id ( 1 2 ) .

Using the procedure d e s c r ib e d above f o r sodium hydrox­

i d e , a fo u r and o n e -h a l f hour r e a c t i o n of sodium amide on

b e n z i l was c a r r ie d o u t . The product i s o l a t e d from the

formamlde f a i l e d to g iv e an e le m e n ta l t e s t f o r n i t r o g e n ,

but i t gave the in t e n s e red c o lo r i n c o n c e n tr a te d s u l f u r i c

a c id , w hich i s c h a r a c t e r i s t i c o f b e n z i l l c ac id# On r e c r y ­

s t a l l i z a t i o n from w ater a 34$ y i e l d of b e n z i l l c a c id

m e lt in g a t 149 d e g r e e s was o b ta in e d . Because the y i e l d of

b e n z i l l c a c id was low , the benzene s o l u t i o n was i n v e s t i g a t e d

f os : u n r e a e te d , b e n z i lo No. b e n z i l was found, i n th e s t i c k y

brown r e s i d u e r e s u l t i n g from th e e v a p o r a t i o n o f th e .

benaen© soX utiono S in c e 3. 50% e x c e s s of th e sod ium amide

© a t a l y s t was us© dP i t was p o s s i b l e t h a t fixe e x c e s s amid©

m ig h t ha 'fe deoom posed p a r t o f th e b a n z i l i A n o th e r r e a c t ! on

was t h e n r u n u s i n g o n ly e q u i v a l e n t am ounts of so d ium amide

and b e r i z i l w i t h a f o u r h o u r r e a c t i o n time® The p r o d u c t

t h u s o b ta in e d c o n ta in e d no n i t r o g e n and am ounted o n ly to

a 2 1 09% y i e l d o f b e n z i l i e a c id o -Her® a g a in ^ a f t e r th e

b en zen e s o l u t i o n was e v a p o r a t e d , o n ly a s t i c k y brown

r e s i d u e r e m a in e d , from, w h ic h no .b e n z i l c o u ld be i s o l a t e d o

T h e .p ro p o s e d m echanism f o r th e amide i o n c a t a l y s i s

p r e d i c t s t h a t b e n z i la m id e should., be the r e a r r a n g e d p r o d u c t !

h o w e v e r , .no n i t r o g e n c o n t a i n i n g p r o d u c t was i s o la t e d ® -

S in c e no .•w ater Was ad d ed to tb© r e a c t i o n m i x t u r e , i t i s

n o t l l l c e l y ’ t h a t b e n z i la m id e h y d r o ly z e d to th e acid©

P e rh a p s th e f o r m a t io n and s u b s e q u e n t d e c o m p o s i t io n o f an

u n s t a b l e i n t e r m e d i a t e m ig h t e x p l a i n th e low y i e l d o f

b e n z l l i e a c i d i n s t e a d o f b e n z i 1a m id e c : .•

A d i f f e r e n t p ro c e d u r e was t h e n t r i e d f o r decom posing

th e compiex and c a t a l y s t w i t h a b s o l u t e e t h a n o l » A r e a c t i o n

u s i n g e q u i v a l e n t am ounts o f sodium am ide and b e n z l l was ru n

f o r f o u r h o u ra and th e n 25 -ml» o f e t h a n o l was added to

decompose th e b e n z i1 - b a s e com plex and th e u n r e a c t e d sodium,

amide c a t a l y s t * A f t e r f i l t e r i n g , th e b en zen e so .iu .f ion was :

e v a p o r a t e d to d r y n e s s i n s t e a d o f e x t r a c t i n g w i t h fo rm am ld e e

The s t i c k y bs?own f e s 1 d u e ? w h ich s m e l le d s t r o n g l y o f benzw

a ld e h y d e p gave a s t r o n g e l e m e n t a l t e s t f o r n i t r ogeri) b u t no

b e n z i la m id e was r e c o v e re d ^ Only a 16% y i e l d o f b e n z l l i e

a c i d r e s u l t e d from th e f e a c t i o n and s t i l l no b e n s 11 was-

r e c o v e re d * S in c e no b e n s 11 was r e c o v e r e d a n d : s in c e the \

y i e l d o f b e n s l l i c a o id was low>: e x t e n s i v e d e c o m p o s i t io n

mus t have t a k e n p l a c e o

, The same r e a c t i o n was r u n a g a i n e x c e p t th e r e a c t i o n

t im e was ch ang ed from f o u r h o u r s t o t h i r t y m in u te s * T his

t im e th e r e s i d u e s. w h ic h a g a i n s m e l le d s t r o n g l y o f bensal™

, dehydep f a i l e d to g iv e a p o s i t i v e n i t r o g e n - t e s t * On

w o rk in g up th e r e s i d u e a s b e f o r e s an 18^ y i e l d of. b e n z i l l e

a c i d r e s u l t e d p b u t no b e n z i l was recovered® T h is i n d i c a ^

t e d th e s h o r t e r r e a c t i o n tim e was' j u s t a s e f f e c t i v e a s . the-

l o n g e r one a s f a r a s y i e l d o f b e n z i l l e a c i d was co n ce rn ed *

S in c e e v en th e t h i r t y m in u te r e a c t i o n tim e i n d i c a t e d

e x t e n s i v e decom pos1 t l o n s a r eac t i on was r u n f o r o n ly f i f t e e n

m lnutes® I n s t e a d of a d d in g e t h a n o l o r trim ethylam m onlum -

c h l o r i d e . to decompose th e com p lex9 th e s a l t o f any r e a r r “ .

anged p r o d u c t and u n r eac t e d c a t a l y s t w ere f i l t e r e d , out® The

b enzen e s o l u t i o n c o n ta in i n g t h e deep b lo o d r e d b e n z l l= b a s e

- c omplex and u n r e a c t e d b e n z l 1 was ad ded dropW ise to a d i l u t e

s o l u t i o n o f s u l f u r i c acidp. The r e s u l t i n g y e l lo w - o r a n g e

b en zen e s o l u t i o n on e v a p o r a t i o n g a v e an o ra n g e —brown

r e s i d u e from w h ic h 5*8 gram s ( §0%) o f p u re b e n z i l was

r e c o v e re d * A lso lo 4 gram s o f an o ran g e m a t e r i a l p w h ic h

p fo b a t ) ly Gomtalngd some; 'b e n s i l^ was r e c o v e re d ^ From th e

o r i g i n a l p r e e i p i t a t e f i l t e r e d from the r e a c t i o n m i x t u r e , .

a. 5 o7^ y i e l d o f h e n z i l i e a c i d was o b ta in e d ^ U s in g th e ;

same p ro e © d u re > a r e a o t i bn w i t h e q u i v a l e n t am qunts o f ’ .

r e a c t a n t s was r u n f o r one and. o n e ^ h a l f h o u r s » From t h i s

was o b t a i n e d a 1 7 c5% y i e l d o f b e n z i l i e a e i d and 2 06 gram s .

(2 5 ^ y i e l d ) o f f a i r l y p u re b e n z i l a lo n g w i t h lo 3 gram s of

a h ; o ran g e c o l o r e d m a t e r i a l w h i c h ;a g a i n p r o b a b ly c o n ta in e d

c o n s i d e r a b i e b e n z l l o On ru n n in g a n o th e r r e a c t i o n f o r two

and one - h a l f h o u r s ; a 2:0 @8% y i e l d o f b e n s i l i e a c i d waa ’ : -

o b t a i n e d , b u t no u n r e a c t e d b e n z i l c o u ld be r e c o v e r e d

Only a s t i c k y h r own m a t e r i a l : was d e f t© - : ::

I n o r d e r to compare th e s e , r e s u l t s u s i n g e q u i v a l e n t

am ounts of sodium amide c a t a l y s t and b e n z i l w i t h the

r e a c t i o n c a t a l y z e d by .h y d ro x id e i o n , a r e a c t i o n w i t h o

e q u i v a l e n t am ounts o f h y d r o x id e ’arid b e n z i l was r u n f o r

one and b n e - h a l f h o u r s 0 I n t h i s c a s e o n ly a 5 1 ^ .y i e l d of

b e n z i l i e a c i d was o b t a in e d wi t h 2 »1 gram s (2 0 ^ ) o f b e n z i l

b e in g reco v ered ® . T h is d e c r e a s e d y i e l d of. b e n z i l i e a c i d

i n d i c a t e s t h a t p e rh a p s the: u se o f o n ly e q u i v a l e n t am ou n ts

o f amide i o n r e s u l t s i n low y i e l d o f r e a r r a n g e d .p ro d u c ts

A l th o u g h f a i l u r e to i s o l a t e a n y b e n z i la m id e i n th e

amide I o n c a t a l y s 1 s h a s thrOwn some d q u b t on th e v a l i d i t y

o f :-the>vbrop0sed'.;'re a r ra n g e m e n t , m echanism , th e f a c t t h a t a n y

r e a r r a n g e m e n t o c c u r s i s s t i l l s i g n i f i c a n t ® .S u b s e q u e n t ly , ,

r e a c t i o n s w ere r u n i n v o l v i n g c a t a l y s i s ’ by th e a n l l i d e i o n

and th e H»m© th y l a n l l i d e Io n a Ac c o rd in g -to th e p ro p o s e d

i ;v : f ... : ■ llniv, .of' AnzonaUbraif i : : V. : :

me©b.anlsmy ttie a n i l i d e i o n P s in c e i t i s c a p a b le o f I n t e r n a l

h y d ro g e n bond ingp s h o u ld cause- th e : r e a r r a n g e m e n t # the same

d a s th e amide i o n j w h i le w i t h th e H=»me t h y l a n i l l d e s th e

. b e n s i l s h o u ld ' no t;; r e a r r a n g e » The " r e s u l t s of th e r e d o t i o n sp

!b o t h ru n f o r one and b n e ^ h a l f h o u r s P; . s t r o n g l y s u p p o r t t h i s

1 d e a • ^ h o a n 1 l i d d ‘ 1 on p ro d u c e d an IBfo y i e l d o f b e h z i l l c

a e i d p w h i le t h e E H n e th y la n l l id e g a v e o n ly a 4o9% y i e l d o f

th e acid® I n n e i t h e r e a s e was any b e n g i l reco v ered ® . The

4®9^ y i e l d wi t h M ^ m e th y la n l l id e c o u ld have, a r i s e n from ,

in c o m p le te d r y in g Of the r e a g e n t s o r f r o m a b s o r p t i o n o f

w a te r from th e a tm o sp h e re d u r in g p r e p a r a t i o n o f th e

; a n i l i d e io n s s i n c e i t to o k a p p ro x im a te ly n i n e t e e n h o u rs

o f r e f l u x l n g o - . . ■ - .

I n o r d e r to t e s t f u r t h e r th e b e l i e f t h a t a b a se " m u s t

be c a p a b le o f i n t e r n a l - p r o t o n b o n d in g b e f o r e i f w i l l

c a t a l y z e th e r e a r r a n g e m e n t^ a r e a c t i o n o f e th o x i d e i o n

on b e n z i l was r u n f o r one and o n e - h a l f h o u r s ® H ere no

m e a s u ra b le amount o f benz1 11c a c i d w a s . i s o l a t e d « T h i s $

t h e r e f o r e f i s i n p e r f e c t a g re e m e n t w i t h th e b e l i e f

e x p r e s s e d above@ ..v" : /' %d .

EXPERIMS'M TAIi;

M a t e r i a l s 0 B e n z i l was: r e e f y s t a l l i z e d from o a r bon t e t r a » ;

c b lo r I d a u n t i l ' i t was: fou nd to m e l t s h a r p l y a t ; 9.40 5 s-

A nhydrbua b en zen e was p r e p a r e d by f i r s t d i s t i l l i n g o u t; ’ ;

l0^g r e f l u x l n g th e r e s i d u e w i t h f r e s h l y c u t Sodium f o r two

h o u rsg th e n d i s t i l l i n g o u t 80^ o f . ; th e : r e s i d u e i n th e f l a s k Q

T h is d l s t i l i e d b en zene was th e n u s e d i n th e r e a c t i o n s e The

so d iu m ;a m id e s w h ich h ad b e en p r e v l o u s l y opened^ was manu*=» ;■

f a c t u r e d by [ F a r chan R e s e a r c h 1 L a b o r a t o r i e s ^ .- 'T heran l l i n e s •

#=me t h y l a n i l i n e g Which w ere d i s t i l l e d • ' im m e d ia te ly -b e fo re

u s i n g ; and th e fo rm am lde were E as tm an 'K o dak m a t e r i a l s *

The tr lm ethy lanm ionlum C h lo r id e Was p r e p a r e d by t r e a t l h g .

t r im e th y lam in a 3. a l s o ah; E as tm an Kodak p ro d u e t p i n anhydr ou s; •

. e t h e r w i t h h y d ro g e n c h l o r i d e g a s a t 0 ® :: : ■

Apparatuso» ; A l l . r e a c t i o n s , were; c a r r i e d o u t i n a 50Q. ml*

ro u n d -’bottom ^ t h r e e r h e c k ; f l a s k w i t h g round , g l a s s j o i n t s s to

W hich was a t t a c h e d a F r i e d r i c h e o n d e h s e r w i t h a c a lc iu m

c h l o r i d e d r y in g id be * A G l a s c o l h e a t l n g m a n t le was - u s a d »

A l l d i s t l l l a t i o h s i n v o lv i n g p r e p a r a t i o n o f m a t e r i a l s were

c a r r i e d o u t W ith e q u ip m e n t f i t t e d w i t h g ro u n d g l a s s

' ConneGtidha^/" : ; '' / ,/ ; ■

B e n z i l i c # c l d . r e a r r a n g e m e n t The e f f e c t i v e n e s s o f a b a se

i n c a t a l y z i n g th e b e n z i l i c . a c i d r e a r r a n g e m e n t was t e s t e d i n

b e n z e n e ; ; ln . : .a l l 'bases.«-' ,• S e v e r a l . t r i a l s / w e r e r u n wl t h sodium :V’;

: - ' : : ' . ' ■ v ; - 12

h y d ro x id e a s t h e . c a t a l y s t and u s in g d i f f e r e n t e x t r a c t i o n '

p r o e e d d r e s * The p r o c e d u re w h ic h gav e th e b e s t r e s u l t s i s

d e sc .r lb e d a ■ :

Sodium h y d ro x id e e a f a l y s l s s A 4 gram p o r t i o n ( 0 o10 m o le }

o f .sodium h y d ro x id e p e l l e t s was p u l v e r i s e d i n a m o r ta r

u n d e r 75 ml* o f d r i e d b e n z e n e » The r e s u l t i n g s l u r r y was

t r a n s f e r r e d to a 500 m lc ro u n d ^ b o tto m f l a s k w i t h 200 ml® o f

- / 'henasne*- '; ' From t h i s m i x t u r e , 1 5 0 ml* o f b en zen e was d l s t i l t , : ,

l e d to remove any w a t e r t h a t th e sodium h y d ro x id e m ig h t

have absorbed® S u f f i c i e n t b e n ze n e was ad d ed to . ' t h e m ix tu re

u n t i l 200 ml# was p r e s e n t i ' Then 10«5 gram s ( O® 05 m o le ) o f

b e n z l l w ere added ' and th e .m ix tu re w a s ; r e f luX ed a n d s t i r r e d

f o r f o u r hours® : ■ :

Oh e o o l in g to room t e m p e r a t u r e P some o f t h e l i g h t

brown m a t e r i a l su s p e n d e d i n t h e s o l u t i o n s e t t l e d o u t* To

t h i s m ix tu r e :w a s added 9®96 gram s {0®10 m ole) o f t r i m e t h y l s

ammonium c h lo r i d e ' i n ra s i n g l e p o r t i o n ^ and th e m ix tu r e was

s t i r r e d fo r . t e n m inutes® A f t e r th e s o l u t i o n was s t i r r e d

f o r s e v e r a l m in u te s s m ost o f th e s o l i d m a t e r i a l d i s s o lv e d , ,

and th e s o l u t i o n tu r n e d c l e a r y e llo w # The r e m a in in g s o l i d . "

m a t e r i a l was f i I t e r e d . a ,and th e f i T f r a t e was e x t r a c t e d

tw ice w i t h a 25 ml® p o r t i o n o f form am ideo M ost o f the

y e l lo w c o lo r was e x t r a c t e d I n t o t h e formamide® On a c i d i c

. . . f l o a t ion . w i t h 30 ml® o f 12 N s u l f u r i c a c ld > a f l o ecu l e n t 1

.w h i t e . p r e c i p i t a t e r e s u i t e d ^ • l e a v i n g a c l e a r so l u t l oh® •Hiis

. was.' f i l t e r e d b y s u c t i o n and w ashed wi t h c o ld w a t e r B The ,

s t i l i d m a t e r i a l from th e r e a c t i o n m i x t u r e 9 when d i s s o l v e d :

i n 50 ml o' o f wa tes? and e a i ’e f u l l y a c i d i f i e d w i t h 6 N : -

s u l f u f i e a o id g gave a •white p r e e l p i t a t e ' l A f t e r d r y in g . i n ■:

••.the oven to c o n s t a n t w e ig h t a t 100 ? a c ru d e y i e l d o f

h e n z i l i c a c id p 10••94 gram s o r 96%s m e l t in g p o i n t 142 9 was/

o h ta ln e d o On r e c r y s t a l l i z a t i o n from 5 0 0 .m l0 o f h o t w a t e r » ;

9: o 74 gram s (09%) o f benz 1 l i e a c i d * m e l t in g ; p o i n t 149 @5% . r

• was- ob ta ined® ' • : . v : ■ ; : " : ' :

P r e p a r a t i o n o f b e n z i l a m i d e » I n 100 t n le ro u n d -b o t to m ■

f l a s k 1*7 g ram s (0*005 m o le ) o f b e n z l l i e a c i d was m ixed

w i t h 10*6 gram s (0*11 m ole) o f p h o sp h o ru s p e n ta e h lo r id e ®

The. f l a s k was ' f i t t e d w i th r e f lu x c o n d e n se r and w a s h e a t e d

’ to 120S"150® wi t h a h e a t i n g m a n t le f o r 45 minu tes® Then /

15 ml® o f b en zene was a d d e d P and t h e s o l u t i o n was r e f lu x ed

f o r 20 m in u te s ® The p h o sp h o ru s o X y o h lo f ld e and th e b e n zen e

were d i s t i l l e d out@ The l i q u i d rem a in in g , i n th e f l a s k

s o l i d i f i e d .upon' b e in g p o u re d i n t o Cold .w a te r o;: The - s o l i d ■ ' '

ee^chloroaoid- c h l o r i d e of b e n z i l i e a c i d was f i l t e r e d and

w ashed w i t h c o ld w a t e r » The p r o d u c t was d r i e d o v e r n i g h t

i n a vacuum d e s i c c a t o r w i t h c a lc iu m c h l o r i d e e On r e c r y «

s t a l l i z i n g f ro m p e t ro le u m e t h e r p th e y i e l d o f «5C-chloro=-

d e i d c h l o r i d e was 5<0 -gram s (4 4 ^ ) 5 .m»p0 48^*49® » T h is was

- d i s s o l v e d i n 100 ml® o f a n h y d r o u s ’e t h e r - a t 0 ° an d t r e a t e d

w i t h a n h y d ro u s ammonia f o r one h o u r «, d u r in g w h i c h t im e

c o n s i d e r a b l e p r e c i p i t a t e form ed^ To t h e e t h e r s o l u t i o n

75 ml® o f .W ate r was added: and t h e m ix tu r e .was warmed on

a iio't p l a t e to s v a p o r at© th e e t h e r = T h e n t b e a q u eo u s .

' s p lu t i o n was b o l i e d f o r :5 0 m ln u te s s co o led ^ and f l i t e r e d ® :

The p r e e i p i t a t e was o rea m ^o o lo red e On r e o r y s t a l l i z a t i o n

from ch le ro fo rm i) 1^07 grama (19/6) o f snow w h i te b e n z l l # .

amide^ m®p, 154 ® a was o b t a i n e d e . .

Sodium amide o a t a l y a l s o r A® D e c o m p o s i t io n w i t h t r l m e f h y l «

ammonium c h lo r id e ® fd & ;500 mla ro u n d ^ b o tto m f l a s k f i t t e d

w i t h :a s t i r r e r and r e f l u x c o n d e n se r was ad d ed 200 ml*, o f

d r i e d b en zene p 10»51 gram s (0*05 m o le ) of- b e n z i l 5 and 1*95

g ram s (0®05 m ole) -of sodium amide® The m ix tu r e was

r e f l u x e d w i t h s t i r r i n g f o r f o u r h o u r s / d u r in g w h ich tim e

c o n s i d e r a b l e b lo o d r e d p r e c i p i t a t e fo rm e d e The m ix tu r e

was c o o le d to room te m p e r a tu r e a f t e r w h ich 4®78 gram s of

tr im ethylam m onium c h l o r i d e was added,, and th e m ix tu r e was

. s t i r r e d f o r 10 m i n u t e a / S h o r t l y a f t e r a d d in g th e t r i «

me thylammohium c h lo r i d e ^ th e re d s o lu t i o n changed t o ' ,

yellow® The p r o d u c t was th e n w.orked up e x a c t l y a s i n the

h y d ro x id e c a t a l y z e d r e a c t i o n * The y i e l d was 2 / 5 gram s

, ( 21»g%); -of b e n z i l i e - a e l d s. m0p® MB'®® A. t e s t f o r n i t r o g e h

:Wids;hegatiV©'.® ;:‘ . /■' i / / . / ' . : ' ( \ ' ' h- '

B® D e c o m p o s i t io n w i t h a b s o l u t e e thano l® ' To a s o l u t i o n o f

10®51 g ram s (0*05 m ole ) of b e n z i l i n 200 ml® o f d r i e d

b enzen e was .added 1® 95 gram s (0 0 05 m o le ) of s odium amide®

The m ix tu r e was r e f l u x e d / w i t h s t i r r i n g s f o r 4 hours® To •

th e h o t s o lu t i o n 25 ml* o f a b s b lu te ©th an o i- was added ’ /

r a p i d l y w i t h d ro p p in g fun'nel® The s o lu M o n chang ed f ro m

de©ga W d to d e e p v i o l e t o r pur-ple ® T h e s o l u t i o n wa-s

r© f lu x e d f o r 10 i n i n u t e s , c o o led ^ and f i l t e r e d » The f i I fc ra te

was e v a p o r a t e d to d r y n e s s o v e rn ig h t^ l e a v in g a d a r k brown

- . s t l e k y r e s i d u e « I h i s ^was d i s s o l v e d i n 35 ml® o f h o t

e ' t J ^ h o X ti tW a te r :wa's ;adddd d ro p w ise .to th e h o t e t h a n o l and

m o st of: th e h r own m a t e r i a l s e p a ra te d ® On a d d ! t l on o f 11 ml®

o f d i l u t e s u l f u r i c a e i d s a l a r g e am ount o f l i g h t o ran g e

p r e o l p l t a t e : formed® A f t e r th e p r e c i p i t a t e was f i l t e r e d ou 1;.

o u t j th e wa t e r « e t h a n o l s o l u t i o n was e v a p o r a te d to one “ h a l f .

: voltimdj,' h u t no f u r t h e r p r e e i p i t a t e . fo rm ed o^ On re e ry s t3 .1 1 i .«

z a t l o n from h o t w a t e r s l e82 gram s (16%) o f b e n z l l i e a e i d s

mop® 1 4 8 o5®g was reco v ered ® •' ' • ' '■ '•il' ' -

Cm D e o o m p o s i t io n w i t h s u I f u r 1 c a o l d ® To 200 ml* o f d r i e d

"benzene i n a 500 ml® found^bottom j, th r e e ^ n e e k f l a s k were

a d d e d . ,10® 5 gram s (0 ®05) mol.e) o f b e n z l 1 and 1*95 gram s o f

sodium amide® The m ix tu r e was r e f l u x e d and s t i r r e d f o r

1®'5 h o u r So Then i t was c o o le d to room t e m p e r a t u r e » and

th e r e d p f e c i p i t a t © ;was f i l t e r e d ou t® The r e d f i l t r a t e , i ' '

up o n a d d i t i o n dropW ise to 120 ml* o f 6 s u l f u r i c a c i d s

tu r n e d y e l l o w « Thi s y e l lo w b e n ze n e a o lu t i on upon evap** ' =

o r a t i o n l e f t a : y e l lo w - o ra n g e r e s i d u e w h ich y i e l d e d 2®6 ;

gram s o f b e n z l 1® The r e d p r e c i p i t a t e was d i s s o l v e d i n .

150 ml® o f w a t e r s t o u g i v B l a r e d d s p lu t lo n ® Upon a o i d l f i d ­

e a t i o n w i t h 5 ml® o f d i l u t e s u l f u r i c •a e i d s - a l i g h t o ran g e

p r e c i p i t a t e formed® T h is was s e p a r a t e d and r e e r y s t a l l l z e d

fro m h o t -watero The y i e l d of b e n z i l i c a c i d was 210 gram s

: ■ .-'v ;:v; _ ■ . .v":.-v' : ; .. Y ■ ; ' Y : y , < ' YlB. ■

9 ' : ; Y: ; Y- Y • '

P r e p a r a t i o n of. sodium an5„lld.ee To 10 mlo ( 0 o l2 m ole) o f

f r e s h l y i d i s t i l l e d . ■anilineY w ere added 1*20 gram s ( 0 „055

m ole) o f f r e s h l y on t sodium and #12 gram s o f pow dered '

oopper® The m ix tu r e was h e a t e d to 100® and s t i r r e d f o r one

h o u r « The sodium r e a e t e d v i g o r o u s l y o . Then 10 ml® o f d r i e d

b en zen e Were added and t h e m ix tu r e h e a t e d 30 m in u te s more®

The s o l u t i o n was v e ry d a rk brown®

C a t a l y s i s by sodium a n l l i d e » A s o l u t i o n o f 10»5 grams

( 0 o050 m o le ) o f b e n z l l i n 190 ml© of d r i e d b en ze n e was

added to th e 500 ml® ro u n d -b o t to m f l a s k c o n t a i n i n g th e

;s Odium a n i l ld e ® The m ix tu r e was r e f l u x e d f o r one and one®

h a l f h o u r s ^ % s o l u t i o n was v e r y d a rk brown or b la c k o I t

was f i l t e r e d and t h e f i l t r a t e ad d ed d ro p w ise to 120 ml® o f

6 N s u l f u r l . c a c id o The benzene , s o l u t i o n was e v a p o r a t e d to

d r y n e s s s l e a v i n g a d a rk brown r e s id u e o 'A f t e r d i s s o l v i n g

th e brown ^ p r e c i p i t a t e from th e r e a c t i o n m ix tu r e I n 100 ml®

o f w a te r a n d a c i d i f y i n g s a l i g h t brown p r e c i p i t a t e was

o b ta in e d ^ The y i e l d o f b e n z i l i e a e l d s a f t e r r e c r y s t a l l i - .

z a t i o n from h o t w a t e r s was 2 ®OT gram s ( p m®po 148® 5®e -

P r e p a r a t i o n o f sodium l - m e t h y la n i T i d e o I n a 500 ml® round®

b o tto m f l a s k 1®20 gram s (0®055 m o le ) o f f r e s h l y c u t sodium

and o l gram o f co p p e r powder were added to 11 ml® (0®11

m ole) o f .S - m e t h y l a h i l l n e <, The f l a s k was h e a t e d to 1 9 0@

and a b i r r e d f o r , 6 h o u rs a f t e r w h ich t im e t h e r e '-was eons id®

e r a b l e sodium s t i l l un re& ctedo A 100 ml® p o r t i o n o f

■benzene was a d d e d s and the, s o l u t i o n was r e f l u x e d f o r 9 more

h o u r s u n t i l a l l . th e sodium had r e a c t e d * The r e s u l t i n g .

■ S o l u t i o n ■■was'''.qhii^! browhivn. ' ' ' :';‘:' / \ ' ' ’':-''V' i ' - ■

Sodium i r - m e th y l a n i l l d e .o a t a l y s i s » A s o lu t i o n o f 1Q=6 gram s

(0*05 m o le ) o f b e n z i l i n 100 mlo o f d r i e d b e n ze n e was added

to th e sodium H^me t h y l a n i l i d e «, The s o l u t i o n was r e f l u x e d

f o r lc.5 ho u r So ' The s o lu t i on was v e r y d a rk b lu e •"•to lack®

A f t e r , GOolingp th e s o l u t i o n was f i l t e r e d and w orked up

e x a c t l y a s i n t h e ' a n i l i d e c a t a l y s i s o A. y i e l d of =>48; gram s

:,;(S»1$D o f b e n z l l i c a c id y mo^p. 1 4 9 a nd no b e n z i l r e s u l te d ®

P r e p a f a t i on. o f sod lum e t h o x i d e ® S odium e th o x id e was p r e - : :....

p a r e d by th e d i r e c t a c t i o n o f 1®2 g r a m s .(0 * 0 5 5 m o le ) o f

sodium on 25 mlo o f a b s o l u t e e thanol® ' M ost o f th e e x c e s s

e th a n o l f w a s •removed b y ad d in g 100 ml® o f d r i e d b e n ze n e and

d i s t i l l i n g ou t 80 mlo The f i n a l s o lu t i on was d a rk b r own9

and i t s o l i d i f i e d oh c o o l in g t o room tem p era tu re®

Sodium e th o x id e c a t a l y s i s ® To th e sodium e th o x id e i n Ar-" wi IT—msafuaiw TUjmm c y -rnmm '■■■mssbr .i1.— r.' yr-y ,r.'l i,:m 1 =-""T '

500 ml® ro u h d ^ b o tto m f l a s k was ad d ed 80 ml® o f d r i e d

benzenep and th e m ix tu r e was h e a t e d to r e f l u x t e m p e r a tu r e s

A. s o lu t i on o f 10® 51 gram s (0*05 m o le ) of b e n z i l i n 100 ml®

of b en zen e was a d d e d " d ro p w ise to th e sod ium e th o x id e o v e r

a 30 m in u te ' p e riod® - Theni a f t e r one and o n e « h a l f h o u rs o f

r e f l u x l n g j , th e r e s u l t i n g d a rk b lu e o r b l a c k s o l u t i o n was

e o o le d to room te m p e ra fu re and f i l t e r e d ® A v e r y s m a l l

amount o f s o l i d m a t e r i a l .w a s se p a ra te d ® On w o rk in g u p th e

18

s o l u t i o n and the p r e c i p i t a t e e x a c t ly as in the a n i l i d e

r e a c t i o n s , no h e n z i l i c a c id was ob ta in ed nor was any

b e n z i l r ec o v er ed from the benzene s o lu t io n *

TABLE I

SUMMARY OF THE ACTION OF VARIOUS BASES WITH BENZIL

0 .0 5 mole o f b e n z i l In 200 ml* of benzene used i n each r e a c t i o n

Moles o f c a t a l y s t

R e a c t io n time

in hours

Complex decomposed w ith

Y ie ld b e n z i1 1 c

a c id

M elt in g i p o in t of i

p r o d u c t:

0 .1 0HW 4 .0 0 .1 0 mole (CH3 ) 3 NHC1 89% 149* I

0 .0 7 5 NHg- 4 .5 0 .0 7 5 mole (CH^NHCl 54% 148° j

0 .0 5 NBg- 4 .0 *0.05 mole (CH3 )3NHC1 21.9% 148° :

0 .0 5 NHg" 4 .0 25 m l. e th a n o l 16% 1 4 8 .5 ° •

0 .0 5 NHg" .5 10 m l. e th a n o l 18% 149* :

0 .0 5 NHg" .25 120 m l. 6 N KgS04 5.7% 147.5* :

0 .0 5 NH2 W 1 .5 120 m l. 6 N HgS04 17.5% 148* s

0 .0 5 NHg" 2 .5 120 m l. 6 N H_SO„ — 2 4 20.8% 149* :

0 .0 5 OH" 1 .5 120 m l. 6 N HgS04 51% 148.5®:

0 .0 5 5NHG6H5~ ; 1 .5 120 m l. 6 N H_SO„ — 2 4

18% 1 4 8 .5 ° :

0 .0 5 5 ]V e V 1 .5 120 m l. 6 N HgS04 4.9% 148* :

0 .0 5 5

0C2 H5" 1 .5 120 m l. 6 N H_SO„ — 2 40%

SIBfflARY

A meohaniain M s b e e n p o s t u l a t e d f o r th e b e n z i l i e a c i d

r e a r r a n g e m e n t w h ic h s e e k s to e x p l a i n more f u l l y th e r o l e o f

th e b a se i n b r i n g i n g abou t th e r e a c t i o n » An e s s e n t i a l : ;

f e a t u r e of t h e f u n e t l o n o f t h e b a s e i s th e f o r m a t i o n ' o f an

. i n t e r n a l h y d ro g e n bond w i t h th e a d j a c e n t c a r b o n y l g roup ? :.

P r e l i m i n a r y work i n d i c a t e s ' t h a t the. m echanism i s

p a r t i a l l y c o r r e c t ih - t h a t th o s e b a s e s ' w h ic h a r e ' c a p a b le o f '

h y d ro g e n b o n d in g c au se th e r e a r r a n g e m e n t w h i le t h e e th o x id e

io n and t b e ! l^me t h y l a n i l i d e i o h do n o t Q From t h i s me c h a n -

ism i t can be p r e d i c t e d t h a t any s t r o n g b a se of the type

slB«H w i l l c a t a l y z e th e f o r m a t io n o f b e n z i l l c a c i d from •

b e n z i l i i f t h e atom; B ' i s - . su c h a s . to a l lo w th e h y d ro g e n to ;

e n t e r i n t o a h y d ro g e n bond f o r m a t i oh© I t . i s p o s s i b l e t h a t

a b a se o f th e t y p e ; ' such a s sodium NpH8^ d ip h e n y l^

h y d ra z id e p w i l l , a l s o c a t a l y z e th e b e n z i l l c a c i d r e a r r a n g e ­

m ent s i n c e th e h y d ro g en b o n d e d i n te rm e d ! a t e w ould c o n t a i n -

a f i v e » s l d e d r i n g r a t h e r t h a n t h e more s t r a i n e d f o u r ^ s id e d -

h y d ro g en bonded r i n g fo rm ed vf.l t h th e amide ion*

; ' BXBIZOGRAEHY: ; - ■ - ; ■ ' : ’

lo • G» WheXands ^Advanced O rg a n ic O h e m is try * s 2rid e d » Joh n W iley and Sons^ New Torkg 1949g pp* 4 8 3 s 493=40

2 o / F® Ho l e s t h e i m e r P JovAm® Ohem® S o c o s 58 , 2209 (1936)

: 3® ■; 0® Ge C a ld w e l l and R *, J 0 .R eFevre , N a tu re . , 143^ 803 ": R \ / X ; : 1 9 3 0 ) 4 / : - V ™

4 o E.o Knaggs and K® ■ L o n sd a le ', N a tu re , 1 43 , 1023 (.1939.)

5o S a lv a to r e - Spr o v l e r i S® The s i s . U n i v e r s i t y ofA r iz o n a , ' pp® 3 , 5 , 13=14 (1954) ® - ■

■6o D® G® O t t and G® G0 S m ith , Jo AtHo Chem» Soo'o, U1? ,: r S S ^ ; ^ 9 6 B ' ) / :; :: ; o : v ; . . V U v r : ■■ -

7 V o l o E a s iw a g i , B u l lo Ghem® Soo=. J a p a n , % 66 (192.6) ^C* 8 ,- ;2 4 9 : 'C l9 2 6 )@ v; -'.HvA ' ''.V ..

8® Ao H a l l e r , Bull® soc & ohim®, 3 1 , 1141 ( 1 9 2 2 ) 0 .

9©. B rd c ® -In d ia n Acado o f S o l s 12A, 266=9 (1940) jG® A® , 3 5 , ,1598 (1941) ©' ?;■.;( >v-=h'" \ • ■

: 10#' Ma E a o ,, JA . Ghem® Soc®, 1931 , 443®

11® H® B u r to n , J® Ghemo S o c », 1950, . 2400® • ■ ' .

12.® ' Ber ® , 22 , ,1538=9 i (1 8 8 9 ) ® : . ( : ■