US4233242_1980_KETAZINE PRODUCTION.pdf

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United S t a t e s Patent [ 1 9 1 [ 1 1 1 4 , 2 3 3 , 2 4 2

[ 4 5 ] N o v . 1 1 , 1 9 8 0a g a t o - ‘ l e t a l .

[ 5 4 ] PROCESS FO R PRODUCING KETAZINE BY,REACI‘ING A KETONE WITH AMMONIA‘AND A PEROXIDE

[ 7 5 ] I n v e n t o r s : N o b u y u k i N a g a t o , W a k o ; Y u i c h iS u g i y a m a , T o k y o , b o t h o f J a p a n

[ 7 3 ] " 1 A s s i g n e e : S h o w n D e n k o K a b u s h i k i K a i s h a ,

T o k y o , J a p a n

[ 2 1 ] A p p l . N o . : 2 7 , 8 9 5

[ 2 2 ] F i l e d : A p r . 6 , 1 9 7 9

[ 3 0 ] F o r e i g n A p p l i c a t i o n P r i o r i t y D a t a

Apr. 1 3 , 1 9 7 8 [ J P ] Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53-42647

Apr. 1 3 , 1 9 7 8 [ J P ] Ja pa n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53-42648

[ 5 1 ] I n t . Ch ‘ . . . . . . . . . . . . . . . . . . C07C 1 0 9 / 1 2 ; C07C 1 0 9 / 1 4 ;

C07C 1 0 9 / 1 6 ; C07C 1 1 9 / 0 0

[ 5 2 ] US. l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564/249; 252/449;

2 5 2 / 4 6 0

[ 5 8 ] Field of Search . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 6 0 / 5 6 6 B

[ 5 6 ] R e f e r e n c e s C i t e d

U . S . PATENT DOCUMENTS

3, 892, 805 7 / 19 7 5 E ic henhofe r e t a l . . . . . . . . . . . . 2 6 0 / 5 6 6 B

3,972,876 8/l976 Schirmann et al . . . . . . . . . . . 260/566 B

3 , 9 7 2 , 8 7 8 8 / 1 9 7 6 Schirmann e t a l . 2 6 0 / 5 6 6 B

3 ,97 8,049 8 / 1 9 7 6 Sc h i r m a n n e l a l . . . . . . . . . . . . . . 2 6 0 / 5 6 6 B

P r i m a r y E x a m i n e r — F l o y d D . H i g e l

A t t o r n e y , A g e n t . o r F i r m - — A r m s t r o n g , N i k a i d o ,

M a r m e l s t e i n & Kubovcik

[ 5 7 ] ABSTRACT

K e t a z i n e s h a v i n g t h e g e n e r a l f o r m u l a ( I )

RI RI 7 ( I )

C=N-N=C

R 1 R 1

w h e r e i n R 1 r e p r e s e n t s a l k y l g r o u p h a v i n g 1 t o 4 c a r b o n

a t o m s a n d R2 r e p r e s e n t s ( i ) a n a l k y l g r o u p h a v i n g 1 t o 4

carbon atoms o r ( i i ) a p h e n y l group o p t i o n a l l y s u b

s t i t u t e d w i t h a n a l k y l group h a v i n g 1 t o 4 c a r b o n a t o m s ,

an alkoxy group having 1 t o 4 carbon a toms o r a h a l o ~

g e n g r o u p , a n d R 1 a n d R2 t o g e t h e r w i t h t h e c a r b o n

atom t o which t h e y a r e both bonded m a y form a r i n g ,

a r e a d v a n t a g e o u s l y m a n u f a c t u r e d by r e a c t i n g a n a l i

p h a t i c o r a r o m a t i c k e t o n e h a v i n g t h e f o r m u l a ( I I )

R 1 ( 1 1 )

C=O

R 2

wherein R 1 and R2 a r e a s de?ned a b o v e , w i t h a m m o n i a

and a p e r o x i d e co m p o un d o r compou nds i n t h e p r e s

ence of a m o r p h o u s s i l i c a o r palladium compounds, a s a

c a t a l y s t , a t a t e m p e r a t u r e of from 0 ° t o 1 2 0 ° C . , i n a

l i q u i d p h a s e .

1 0 C l a i m s , No D r a w i n g s



1

V PROCESS FOR PRODUCING KETAZINE BY

REACT NG A KETONE WITH AMMONIA AND A

PEROXIDE

Th e p r e s e n t i n v e n t i o n r e l a t e s t o a p r o c e s s f o r p r o d u c

i n g k e t a z i n e s . More s p e c i ? c a l l y , i t r e l a t e s t o a p r o c e s s ,f o r p r o d u c i n g k e t a z i n e s b y r e a c t i n g k e t o n e s w i t h a m

monia and a p e r o x i d e co m p o un d o r compou nds i n t h e

p r e s e n c e o f , a s a c a t a l y s t , s i l i c a o r p a l l a d i u m co m

pounds.

R e c e n t l y , s i n c e s y n t h e t i c p r o c e s s e s o f h y d r a z i n e v i a

k e t a z i n e s h a v e b e e n d e v e l o p e d , v a r i o u s p r o c e s s e s f o rp r o d u c i n g k e t a z i n e s h a v e b e e n p r o p o s e d . Among t h o s e

p r o c e s s e s , p r o c e s s e s u s i n g , a s s t a r t i n g m a t e r i a l s , k e

t o n e s , ammonia a n d h y d r o g e n p e r o x i d e a r e known i n

t h e a r t . F o r i n s t a n c e , U . S . P a t . N o s . 3 , 8 6 9 , 5 4 1 , 3 , 9 4 3 , 1 5 2

a n d 3 , 9 7 2 , 8 7 6 d i s c l o s e p r o c e s s e s i n w h i c h t h e s t a r t i n g

m a t e r i a l s a r e r e a c t e d w i t h e a c h o t h e r i n t h e p r e s e n c e o f

n i t r i l e s o r a m i d e s a c c o r d i n g t o t h e f o l l o w i n g r e a c t i o n

s e q u e n c e s .

However, t h e s e p r o c e s s e s p r e s e n t a s u b s t a n t i a l e c o

nomic d i s a d v a n t a g e s i n t h a t n i t r i l e s o r a m i d e s must b e

p r e s e n t i n t h e r e a c t i o n s y s t e m and t h e y a r e c o n v e r t e d t o

t h e a m i d e s o r t h e a m m o n i u m a l t s o f t h e c a r b o x y l i c a c i d

o f which s e p a r a t i o n , r e c o v e r y a n d p u r i ? c a t i o n s t e p s a r e

t r o u b l e s o m e a n d c o s t l y .

I n a d d i t i o n , B r i t i s h p a t e n t s p e c i ? c a t i o n N o . 1 , 4 4 6 , 2 7 9

d i s c l o s e s t h e u s e o f s e l e n i u m and/or t e l l u r i u m o r c o mpounds o f t h e s e e l e m e n t s a s a c a t a l y s t i n o r d e r t o p r e

vent t h e u s e of t h e above-mentioned n i t r i l e s o r a m i d e s .

However, s i n c e s e l e n i u m and t e l l u r i u m which a r e u s e d

a s a c a t a l y s t a r e t o x i c s u b s t a n c e s , t h e r e a r e s t i l l p r o b - .

l e m s , f r o m t h e i n d u s t r i a l p o i n t o f v i e w , t h a t t h e c a t a l y s t

must b e c a r e f u l l y h a n d l e d and t h e w a s t e w a t e r d e r i v e d

f r o m t h e p r o d u c t i o n s t e p m u s t b e p u r i ? e d .

A c c o r d i n g l y , a n o b j e c t o f t h e p r e s e n t i n v e n t i o n i s t o

o b v i a t e t h e a b o v e - m e n t i o n e d d i s a d v a n t a g e s o r p r o b

l e m s o f t h e p r i o r p r o c e s s e s a n d t o p r o v i d e a n i m p r o v e d

p r o c e s s f o r i n d u s t r i a l l y a d v a n t a g e o u s l y p r o d u c i n g a

k e t a z i n e f r o m k e t o n e , a mmonia a n d p e r o x i d e co m

pounds. ' '

I n a c c o r d a n c e w i t h t h e p r e s e n t i n v e n t i o n , t h e r e i s

p r o v i d e d a p r o c e s s f o r p r o d u c i n g a k e t a z i n e h a v i n g t h e

g e n e r a l f o r m u l a ( I )

4 , 2 3 3 , 2 4 2

R 1 R 1 ( 1 )

wherein R1 r e p r e s e n t s a l k y l group h a v i n g 1 t o 4 carbon

2 0

2 5

3 0

3 5

45

5 0

5 5

6 5

a t o m s a n d R2 e p r e s e n t s ( i ) a n a l k y l g r o u p h a v i n g 1 t o 4c a r b o n a t o m s o r ( i i ) a p h e n y l g r o u p o p t i o n a l l y s u b s t it u t e d w i t h a n a l k y l g r o u p h a v i n g 1 t o 4 c a r b o n a t o m s ,

a n a l k o x y group h a v i n g 1 t o 4 c a r b o n atoms o r a h a l o

g e n g r o u p , a n d R 1 a n d R2 t o g e t h e r w i t h t h e c a r b o n

atom t o which t h e y a r e b o t h bonded m a y form a r i n g ,w h i c h p r o c e s s c o m p r i s e s r e a c t i n g a n a l i p h a t i c o r a r o

m a t i c k e t o n e h a v i n g t h e f o r m u l a ( I I )

R 1 ( 1 1 )

w h e r e i n R1 and R2 a r e a s de?ned a b o v e , w i t h a mmoniaa n d a p e r o x i d e compou nd o r compounds i n t h e p r e s

ence of s i l i c a , a t l e a s t one p a l l a d i u m c o m p o u n d o r a

m i x t u r e t h e r e o f , a s a c a t a l y s t , a t a ‘ t e m p e r a t u r e o f from

0 ° t o 1 2 0 ° C . , i n a l i q u i d p h a s e . Th e k e t a z i n e ( I ) t h u s

p r o d u c e d , a f t e r s e p a r a t i o n , c a n b e r e a c t e d w i t h w a t e r

a n d / o r a n a q u e o u s s t r o n g a c i d t o f o r m h y d r a z i n e hy

d r a t e a n d / o r h y d r a z i n e s a l t a n d r e g e n e r a t e t h e s t a r t i n gk e t o n e ( I I ) a c c o r d i n g t o t h e f o l l o w i n g r e a c t i o n s e q u e n

ces. 4

T h u s , t h e r e g e n e r a t e d k e t o n e ( I I ) c a n b e u s e d a g a i n a s a

s t a r t i n g m a t e r i a l f o r t h e p r o d u c t i o n o f t h e a z i n e ( I ) .

T h e s e p r o d u c t i o n p r o c e d u r e s o f h y d r a z i n e f r o m a z i n e sa r e k n o w n and d e s c r i b e d i n , f o r e x a m p l e , U S. P a t . No.

3 , 8 6 9 , 5 4 1 J a p a n e s e P a t e n t P u b l i c a t i o n ‘ N o s .

4 4 - l 4 0 9 3 ( l 9 6 9 ) a n d 4 9 4 8 6 4 0 0 9 7 4 ) . P e r t i n e n t p o r t i o n so f t h e d e s c r i p t i o n s o f t h e s e r e f e r e n c e s a r e i n c o r p o r a t e d

i n t o t h e b o d y o f t h e . p r e s e n t s p e c i ? c a t i o n . The k e t a z i n e

i s a l s o s u i t a b l e f o r u s e i n t h e p r o d u c t i o n o f p h a r m a c e u t i

c a l p r e p a r a t i o n s , d y e s , p e s t i c i d e s a n d t h e l i k e .The s t a r t i n g k e t o n e s e m p l o y e d i n t h e p r e s e n t i n v e n

t i o n a r e r e p r e s e n t e d b y t h e a b o v e - g e n e r a l f o r m u l a ( I I ) .T y p i c a l e x a m p l e s o f s u c h k e t o n e s a r e a c e t o n e , m e t h y l

e t h y l k e t o n e , m e t h y l i s o b u t y l k e t o n e , c y c l o h e x a n o n e ,a c e t o p h e n o n e , m e t h y l 3 - m e t h y l p h e n y l k e t o n e , m e t h y l

4 - m e t h o x y p h e n y l k e t o n e a n d m e t h y l 3 - c h l o r o p h e n y lk e t o n e . I n t h e c a s e where t h e p r e s e n t k e t a z i n e produc

t i o n p r o c e s s i s c a r r i e d o u t a s one s t e p f o r t h e p r o d u c t i o n

o f h y d r a z i n e , k e t o n e s s u c h a s a c e t o n e , which a r e e a s i l y



4 , 2 3 3 , 2 4 23

h a n d l e d and r e a d i l y a v a i l a b l e a t l ow c o s t , c a n b e p r e f e r - ‘

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

e c o n o m i c a l p o i n t o f v i e w . T h i s i s b e c a u s e t h e p r o d u c e d

k e t a z i n e i s h y d r o l y z e d t o form h y d r a z i n e a n d , a s a by

p r o d u c t , t h e s t a r t i n g k e t o n e , a n d t h e k e t o n e i s r e c o ve r e d .

Th e t y p i c a l p e r o x i d e c o m p o u n d employed i n ‘ t h ep r e f e r a b l e embodiment o f t h e p r e s e n t i n v e n t i o n i s hy

d r o g e n p e r o x i d e . H o w e v e r , o t h e r p e r o x i d e c o m p o u n d sc a n a l s o b e u s e d a s a p e r o x i d e c o m p o u n d i n t h e p r e s e n t

i n v e n t i o n ; s u c h a s , f o r e x a m p l e , a l i q u i d p h a s e o x i d a t i o n

r e a c t i o n p r o d u c t o f s e c o n d a r y a l c o h o l ( e . g . i s o p r o p a

n o l , s e c . b u t a n o l , c y c l o h e x a n o l a n d l - p h e n y l e t h a n o l )

w i t h oxygen i n c l u d i n g an oxygen c o n t a i n i n g g a s s u c h a s

a i r ; a r e a c t i o n p r o d u c t o f t h e k e t o n e RlCORz a n d h y l .

drogen p e r o x i d e ; a r e a c t i o n p r o d u c t o f t h e k e t o n e

R1COR2, h y d r o g e n p e r o x i d e a n d a m m o n i a . The k e t o n e

u s e d i n t h e a b o v e two r e a c t i o n s f o r p r e p a r i n g p e r o x i d e

compou nds can be p r e f e r a b l y t h a t which i s u s e d a s a

s t a r t i n g m a t e r i a l f o r t h e k e t a z i n e p r o d u c t i o n . T y p i c a l

e x a m p l e s o f t h e a b o v e ~ m e n t i o n e d p e r o x i d e compounds

a r e h y d r o x y h y d r o p e r o x i d e s a n d a m i n o h y d r o p e r o x i d e sh a v i n g t h e f o l l o w i n g f o r m u l a ( I I I ) ,

OH ( I l l )

wherein Rlvand R2 a r e a s d e f i n e d above and Y e p r e

s e n t s OH r NHZ, a s w e l l a s any secondary r e a c t i o n

p r o d u c t s t h e r e of a n d h a v i n g , f o r e x a m p l e , t h e f o l l o w i n g

f o r m u l a e ( I V ) , ( V ) a n d ( V I ) .

( V )

2

( V I )

wherein R1 and R2 a r e a s d e f i n e d above.

T h e s e p e r o x i d e compounds a n d t h e r e a c t i o n mecha

nism t h e r e o f a r e w e l l k n o w n and a r e d e s c r i b e d i n , f o re x a m p l e , EUROPEAN CHEMICAL NEWS, p a g e 2 7

( J a n . 2 4 , 1 9 6 9 ) ; HYDROCARBON ROCESSING 4 ,N o . 7 , 1 1 6 ( 1 9 6 5 ) ; J . A . C . S . 7 7 1 7 5 6 ( 1 9 5 5 ) ; J . C . S .

1 1 8 0 ( 1 9 5 2 ) ; J . A . C . S . 6 1 , 2 4 3 0 ( 1 9 3 9 ) ; CHEMICAL AB

STRACT 1 , l 0 l 4 3 e ( l 9 6 9 ) ; a n d ; J . Chem. S o c . ( 0 )2 6 6 3 ( 1 9 6 9 ) . The p e r t i n e n t d e s c r i p t i o n s o f t h e s e r e f e re n c e s a r e i n c o r p o r a t e d i n t o t h e b od y o f t h e p r e s e n t

s p e c i ? c a t i o n . Other k n o wn s y n t h e s e s c a n b e a l s o u t i

l i z e d f o r t h e p r o d u c t i o n o f t h e p e r o x i d e c o m p o u n d s .

T h e s e p e r o x i d e c o m p o u n d s i n c l u d i n g h y d r o g e n p e r

o x i d e can be used a l o n e o r any mixture t h e r e o f . Th e

h y d r o g e n peroxide can be used i n an aqueous or no n

aqueous s o l u t i o n of a ny c o n c e n t r a t i o n . I n t h e c a s e

where a n a q u e o u s hydrogen p e r o x i d e s o l u t i o n i s u s e d ,

t h e p r e f e r a b l e c o n c e n t r a t i o n o f h y d r o g e n p e r o x i d e i nt h e s o l u t i o n i s w i t h i n t h e r a n g e o f from 1 0 t o 90% by

w e i g h t . I n t h e c a s e where t h e above-mentioned p e r o x

i d e compounds a r e u s e d , p r e f e r a b l e c o n c e n t r a t i o n o f t h e

1 0

2 5

30

3 5

45

5 5

6 0

6 5

4p e r o x i d e compounds i n t h e s o l u t i o n i s w i t h i n t h e r a n g e

o f f r o m 0 . 3 t o 4 0% by w e i g h t , i n t e r m s o f hydrogen

p e r o x i d e . T h e s e r e a c t i o n p r o d u c t s c a n b e u s e d d i r e c t l y

o r a f t e r d i l u t i o n o r c o n c e n t r a t i o n . Examples o f s u i t a b l e

n o n - a q u e o u s s o l v e n t s a r e a l c o h o l s , e s t e r s , e t h e r s , h y d r oc a r b o n s a n d h a l o g e n a t e d h y d r o c a r b o n s .

The ammonia e m p l o y e d i n the present invention ca nb e i n l i q u i d , gaseous or dissolved form. I n the case

where a n a q u e o u s am monia s o l u t i o n i s u s e d , t h e p r e f e r a

b l e c o n c e n t r a t i o n o f a mmonia i n t h e s o l u t i o n i s w i t h i n

t h e r a n g e o f f r o m 5 t o 2 8 % by w e i g h t .

The c a t a l y s t e m p l o y e d i n t h e p r e s e n t i n v e n t i o n i nc l u d e s s i l i c a , e s p e c i a l l y a m o r p h o u s s i l i c a a n d p a l l a d i u m

c o m p o u n d s , e s p e c i a l l y p a l l a d i u m ( I I ) c o m p o u n d s a n dany m i x t u r e thereof.

By t h e t e r m “amorphous i l i c a " u s e d i n t h i s s p e c i ? c a

t i o n i s m e a n t s u b s t a n t i a l l y d e h y d r a t e d , p o l y m e r i z e d

s i l i c a which m a y b e c o n s i d e r e d a s a c o n d e n s a t i o n p o l y

m e r o f s i l i c i c a c i d . T y p i c a l amorphous s i l i c a which c a n

be u s e d i n t h e p r e s e n t i n v e n t i o n i n c l u d e s s i l i c a g e l , p r e

c i p i t a t e d s i l i c a , fumed s i l i c a o r t h e l i k e . Amorphou ss i l i c a which i s c o n v e n t i o n a l l y u s e d a s a d e s i c c a n t , an

a d s o r b e n t , a c a t a l y s t , a c a t a l y s t c a r r i e r , a f i l l e r o r t h e ,

l i k e c a n b e u t i l i z e d w i t h o u t any s p e c i a l t r e a t m e n t i n t h e

r e a c t i o n a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n . Am o rp h o u s s i l i c a i n any f o r m s s u c h a s b e a d s , g r a n u l e s ,

c r u s h e d p a r t i c l e s , powders and t h e l i k e c a n b e u s e d i n

t h e p r e s e n t i n v e n t i o n .

I n t h e c a s e where amorphous s i l i c a i s u s e d a s t h e

c a t a l y s t , s i n c e b e t t e r r e s u l t s a r e o b t a i n e d wh e n t h e

a m o un t o f water p r e s e n t i n t h e r e a c t i o n m e d i u m i s

s m a l l , t h e i n v e n t o r s o f t h e p r e s e n t i n v e n t i o n p r e f e r t o

u s e n o n - a q u e o u s p e r o x i d e compounds. For t h i s r e a s o n ,

t h e d i r e c t u s e o f t h e l i q u i d - p h a s e o x i d a t i o n r e a c t i o n

m i x t u r e o f a secondary a l c o h o l a s t h e p e r o x i d e c o mp o u n d r e s u l t s i n t h e p r a c t i c a l a d v a n t a g e t h a t o n l y s l i g h ta m o u n t s of w a t e r , which a r e f o r m e d a s a by-product

d u r i n g t h e l i q u i d - p h a s e o x i d a t i o n o f t h e s e c o n d a r y a l c o

h o l , a r e i n c o r p o r a t e d i n t o t h e r e a c t i o n s y s t e m . E s p e

c i a l l y , when a s e c o n d a r y a l c o h o l c o r r e s p o n d i n g t o t h e

s t a r t i n g k e t o n e f o r t h e p r o d u c t i o n o f k e t a z i n e i s u s e d , a l l

c o m p o n e n t s c o n t a i n e d i n t h e l i q u i d - p h a s e o x i d a t i o n

r e a c t i o n m i x t u r e o f t h e s e c o n d a r y a l c o h o l a r e e f f e c

t i v el y u s e f u l f o r t h e p r o d u c t i o n o f t h e k e t a z i n e . For

i n s t a n c e , when a c e t o n e - a z i n e i s p r e p a r e d f r o m a c e t o n e ,

t h e o x i d a t i o n r e a c t i o n m i x t u r e o f i s o p r o p a n o l i s e f f e c

t i v e l y u s e d a s t h e p e r o x i d e compound. That s , t h e o x i

d a t i o n r e a c t i o n m i x t u r e o f i s o p r o p a n o l c o n t a i n s t h e

u n r e a c t e d i s o p r o p a n o l , t h e d e s i r e d p e r o x i d e s s u c h a sh y d r o g e n p e r o x i d e , Z - h y d r o x y i s o p r o p y l h y d r o p e r o xi d e , and t h e l i k e , a s w e l l a s a c e t o n e . S i n c e t h e s e c o m p o

n e n t s a r e t h e s o l v e n t and s t a r t i n g m a t e r i a l s o f t h e p r e s

e n t p r o c e s s , r e s p e c t i v e l y , and s i n c e t h e r e a c t i o n m i x t u r e

i s s u b s t a n t i a l l y n o n - a q u e o u s , t h e d e s i r e d r e a c t i o n e f f e c

t i v e l y p r o c e e d s b y t h e a d d i t i o n o f t h e c a t a l y s t , ammoniaa n d a d d i t i o n al a c e t o n e .

Although t h e amount o f t h e amorphous s i l i c a t o b e

used a s a c a t a l y s t i s n o t c r i t i c a l i n t h e p r o c e s s according

t o t h e p r e s e n t i n v e n t i o n , t h e p r e f e r a b l e a mou nt o f t h e

amorphous i l i c a i s g e n e r a l l y w i t h i n t h e r a n g e o f f r o m 2

t o 5 0% by w e i g h t , a n d m o r e p r e f e r a b l y w i t h i n t h e

r a n g e o f f r o m 5 t o 3 0% by w e i g h t , b a s e d upon t h e t o t a l

weight o f t h er e a c t i o n

m i x t u r e . When h e a mou nt o f t h eamorphous s i l i c a c a t a l y s t i s t o o s m a l l , t h e r e a c t i o n r a t ebecomes s o slow t h a t i t i s n o t p r a c t i c a l l y p r e f e r a b l e ,

a n d , a l s o , s i n c e t h e c a t a l y t i c a c t i v i t y o f t h e a m o r p h o u s

s i l i c a i s s omewha t a f f e c t e d by t h e p r e s e n c e o f water i n



4 , 2 3 3 , 2 4 25

t h e r e a c t i o n m i x t u r e , t h e r e a c t i o n r a t e i s l i a b l e t o f u r t h e r

u n p ' r ' e f e ‘ r a b l y d e c r e a s e w i t h t h e i n c r e a s e o f t h e amounto f w a t e r ' i n t h e r e a c t i o n m i x t u r e . C o n t r a r y t o t h i s , e v e n

i f t h e amount o f t h e amorphous s i l i c a i s t o o l a r g e , f u r

t h e r i n c r e a s e i n t h e r e a c t i o n r a t e ca n n o t b e e x p e c t e d

a n d , a l s o , t h e e c o n o m i c a l b u r d e n , i n c l u d i n g t h e c o s t s f o rs e p a r a t i n g a n d r e c o v e r i n g t h e a m o r p h o u s s i l i c a f r o m

t h e r e a c t i o n m i x t u r e , u n p r e f e r a b l y i n c r e a s e s .An y p a l l a d i u m ( l l ) c o m p o u n d s , s u c h a s t h o s e i n t h e

f o r m o f t h e i n o r g a n i c a c i d , o r g a n i c a c i d o r c o m p l e x s a l t ,ca n b e u s e d , a s a c a t a l y s t , i n t h e p r o c e s s a c c o r d i n g t o

t h e p r e s e n t i n v e n t i o n . E x a m p l e s o f s u c h p a l l a d i u m ( I I )c o m p o u n d s a r e p a l l a d i u m c h l o r i d e , p a l l a d i u m ? u o r i d e ,p a l l a d i u m b r o m i d e , p a l l a d i u m n i t r a t e , p a l l a d i u m s u l f a t e ,p a l l a d i u m c y a n i d e , p a l l a d i u m o x y c h l o r i d e , p a l l a d i u ma c e t a t e , p a l l a d i u m p r o p i o n a t e , p a l l a d i u m o x a l a t e , p a l l ad i u m d i p y r i d y l c h l o r i d e , p a l l a d i u m d i p y r i d y l n i t r a t e ,s o d i u m p a l l a d i u m c h l o r i d e , p o t as s i u m p a l l a d i u m c h l o

r i d e , p a l l a d i u m a c e t y l a c e t o n a t e a n d p a l l a d i u m ( I D - 1 . 4n a p h t h o q u i n o - S - o l e a t e .

A l t h o u g h t h e a m o u n t o f t h e p a l l a d i u m compound t o

be u s e d a s a c a t a l y s t i s n o t c r i t i c a l i n t h e p r o c e s s accordi n g t o t h e p r e s e n t i n v e n t i o n , t h e p r e f e r a b l e amount o f

t h e p a l l a d i u m c a t a l y s t i s g e n e r a l l y w i t h i n t h e r a n g e o f

from 0 . 0 0 1 t o 5 . 0 m o l , and m o r e p r e f e r a b l y w i t h i n t h e

r a n g e o f from 0 . 0 0 5 t o 0 . 5 m o l , b a s e d upon 1 g o f t h e

r e a c t i o n m i x t u r e . When t h e amount o f t h e p a l l a d i u m

c a t a l y s t i s t o o s m a l l , t h e r e a c t i o n r a t e t e n d s t o b ecome

s l o w a n d , t h e r e f o r e , i t i s n o t p r a c t i c a l l y p r e f e r a b l e . Ont h e o t h e r h a n d , when t h e amount o f t h e p a l l a d i u m c a t a

l y s t i s t o o l a r g e , t h e r e i s some d a n g e r t h a t t h e s t a r t i n g

p e r o x i d e c o m p o u n d may b e d e c o m p o s e d a n d , a l s o , t h e

e c o n o m i c a l b u r d e n u n p r e f e r a b l y i n c r e a s e s .The p a l l a d i u m ( I I ) c o m p o u n d s u s e d i n t h e p r e s e n t

i n v e n t i o n a r e n o t n e c e s s a r i l y t h o s e which a r e o f h i g h l y

p u r i t y , a n d p a l l a d i u m ( 1 1 ) c o m p o u n d s a v a i l a b l e f r o mt h e c o m m e r c i a l m a r k e t c a n b e u s e d w i t h o u t a n y p u r i ?

c a t i o n . O c c a s i o n a l l y , p a l l a d i u m c o m p o u n d s c o n t a i n i n gi m p u r i t i e s w h i c h d e c o m p o s e t h e p e r o x i d e c o m p o u n dd e c r e a s e t h e e x p e c t e d y i e l d o f t h e d e s i r e d k e t a z i n e .H o w e v e r , t h e i n v e n t o r s o f t h e p r e s e n t i n v e n t i o n h a v e

f o u n d t h a t , w h e n t h e p a l l a d i u m c o m p o u n d c o n t a i n i n gs u c h i m p u r i t i e s i s p r e v i o u s l y t r e a t e d w i t h s i l i c a g e l , ar e m a r k a b l y h i g h e r y i e l d o f t h e d e s i r e d k e t a z i n e c a n b e

o b t a i n e d i n c o m p a r i s o n w i t h t h e n o n - t r e a t e d p a l l a d i u m

c o m p o u n d . F o r e x a m p l e , t h e t r e a t m e n t o f p a l l a d i u m

compounds w i t h s i l i c a g e l c a n b e c a r r i e d o u t a s f o l l o w s .

Th e p a l l a d i u m compound o b e t r e a t e d i s ? r s t d i s s o l v e d

i n a s u i t a b l e s o l v e n t o r i n a p o r t i o n o f t h e s t a r t i n g r e a c

t a n t a n d s i l i c a g e l i s t h e n added i n t o t h e s o l u t i o n . Th e

m i x t u r e s o formed i s a g i t a t e d f o r a b o u t 3 0 m i n u t e s and

t h e n f i l t e r e d . Th e mother l i q u o r t h u s o b t a i n e d c a n b e

u s e d i n t h e p r o c e s s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n .

A l t e r n a t i v e l y , t h e s o l u t i o n c o n t a i n i n g t h e p a l l a d i u m

compou nd d i s s o l v e d t h e r e i n c a n b e t r e a t e d by p a s s i n g i t

t h r o u g h a c o l u m n p r o v i d e d w i t h s i l i c a g e l p a c k i n g

l a y e r .A l t h o u g h t h e r a t i o o f t h e k e t o n e , a mmonia a n d p e r

o x i d e compound s n o r m a l l y s t o i c h i o m e t r i c ( i . e . 2 : 2 : 1 i n

a mo] r a t i o ) i n t h e p r o c e s s a c c o r d i n g t o t h e p r e s e n t

i n v e n t i o n , one or t wo of t h e s e t h r e e r e a c t a n t s can be

u s e d i n a mounts i n e x c e s s of o r l e s s t h a n t h e s t o i c h i o

m e t r i c r a t i o . However, i n v i e w o f t h e k e t a z i n e y i e l d ,

a n d a l s o f r o m a n e c o n o m i c a l p o i n t o f v i e w , t h e i n v e n

t o r s o f t h e p r e s e n t i n v e n t i o n p r e f e r t o u s e 0 . 5 t h r o u g h 3 5

m o l , a n d more p r e f e r a b l y 1 . 4 t h r o u g h 1 0 m o l , o f t h e

k e t o n e and n o t l e s s t h a n 1 m o l , and m o r e p r e f e r a b l y 2

t h r o u g h 2 0 m o l , o f ammonia, b a s e d upon 1 mol o f t h e

O

5

2 0

2 5

4 5

60

6 5

6p e r o x i d e compound i n t h e p r o c e s s a c c o r d i n g t o t h e

p r e s e n t i n v e n t i o n . I n a d d i t i o n , t h e s e r e a c t a n t s can be

t o t a l l y mixed p r i o r t o t h e r e a c t i o n , o r any r e a c t a n t o r a

p o r t i o n t h e r e o f c a n b e a d d i t i o n a l l y c h a r g e d i n t o t h e

r e a c t i o n m i x t u r e a f t e r t h e r e a c t i o n s t a r t s u p .

I n a d d i t i o n t o t h e c a t a l y s t , s t a b i l i z e r s which ca n p r e

v e n t t h e p o s s i b l e d e c o m p o s i t i o n o f t h e p e r o x i d e com

p o u n d c a n b e e f f e c t i v e l y i n c o r p o r a t e d i n t o t h e r e a c t i o ns y s t e m , e s p e c i a l l y when t h e r e a c t i o n t e m p e r a t u r e i s t o o

h i g h o r t h e r e i s s ome danger t h a t t h e p e r o x i d e co m

pound i l l b e decomposed d u e t o t h e p r e s e n c e o f impu

r i t i e s c o n t a i n e d i n t h e s t a r t i n g m a t e r i a l s o r t h e c a t a l y s t .

Examples o f s u c h s t a b i l i z e r s a r e p o l y c a r b o x y d e r i v a —

t i v e s o f a m m o n i a o r a l k y l e n e p o l y a m i n e , s u c h a s , f o r

e x a m p l e , i m i n o d i a c e t i c a c i d , i m i n o d i p r o p i o n i c a c i d ,n i t r i l o t r i a c e t i c a c i d , e t h y l e n e d i a m i n e d i a c e t i c a c i d , e t h ~y l e n e d i a m i n e t e t r a a c e t i c a c i d , e t h y l e n e d i a m i n e d i p r o

p i o n i c a c i d , h y d r o x y e t h y l e n e d i a m i n e t r i a c e t i c a c i d ,d i e t h y l e n e t r i a m i n e t r i a c e t i c a c i d , d i e t h y l e n e t r i a m i n et e t r a a c e t i c a c i d , d i e t h y l e n e t r i a m i n e p e n t a a c e t i c a c i dand t h e a l k a l i m e t a l s a l t s t h e r e o f ; a s w e l l a s p h o s p h o r i c

a c i d , p y r o p h o s p h o r i c a c i d and t h e a l k a l i o r a m m o n i u ms a l t s t h e r e o f . Although t h e amount o f t h e s t a b i l i z e r , i f i t

i s u s e d i n t h e p r e s e n t i n v e n t i o n , m a y be v a r i e d over a

wide r a n g e , t h e s u i t a b l e a m o u n t of t h e s t a b i l i z e r t o be

u s e d i n t h e p r o c e s s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n i s

l e s s t h a n a b o u t 4% y w e i g h t o f t h e r e a c t i o n m i x t u r e .

T h i s i s b e c a u s e , i f an e x c e s s i v e amount of t h e s t a b i l i z e r

i s u s e d , t h e d e c o m p o s i t i o n o f t h e p e r o x i d e compoundw i l l be l i a b l e t o occur i n t h e c a s e of a n a qu eou s r e a c t i o n

medium, and a l s o , i n t h e c a s e o f n o n - e q u e o u s r e a c t i o n

m e d i u m t h e s t a b i l i z e r ca n n o t be d i s s o l v e d i n t h e r e a c

t i o n m i x t u r e i n v i e w o f i t s s o l u b i l i t y .

S i n c e t h e k e t o n e , ammonia a n d p r o x i d e compoundc a n b e r e a c t e d w i t h each o t h e r by t h e p r e s e n c e o f t h e

c a t a l y s t , t h e p r o c e s s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o nc a n b e c a r r i e d o u t i n t h e a b s e n c e o f s o l v e n t s . However,

i n o r d e r t o o b t a i n a d e s i r e d product i n a s a t i s f a c t o r y

y i e l d , f r o m a p r a c t i c a l p o i n t o f v i e w , t h e p r o c e s s a c

c o r d i n g t o t h e p r e s e n t i n v e n t i o n i s p r e f e r a b l y c a r r i e d

o u t i n t h e p r e s e n c e o f a n y s u i t a b l e s o l v e n t . An y s o l v e n t s

which a r e s t a b l e a n d do n o t decompose t h e s t a r t i n g

m a t e r i a l s a n d t h e r e a c t i on p r o d u c t s , u n d e r t h e r e a c t i o n

c o n d i t i o n s c a n b e u s e d i n t h e p r e s e n t p r o c e s s . Examples

o f s u c h s o l v e n t s a r e w a t e r , a l c o h o l s , e s t e r s , e t h e r s , hy

d r o c a r b o n s , h a l o g e n a t e d h y d r o c a r b o n s , s u l f o n e s a n d

t h e l i k e . Fo r a p r a c t i c a l u s e , p r e f e r a b l e s o l v e n t s a r e

t h o s e which can d i s s o l v e t h e s t a r t i n g m a t e r i a l s t o a

g r e a t e x t e n t a n d which c a n b e e a s i l y s e p a r a t e d f r o m t h e

r e a c t i o n m i x t u r e , a n d a l s o , which a r e r e a d i l y a v a i l a b l e

a t a low o s t .

Th e p r o c e s s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n i s

g e n e r a l l y c a r r i e d o u t a t a t e m p e r a t u r e o f from 0 ° t o 1 2 0 °

C . , and m o r e p r e f e r a b l y from a n ambient t e m p e r a t u r e t o

1 0 0 ° C . , a t atmospheric p r e s s u r e o r a n e l e v a t e d p r e s

s u r e.

Th e p r e s e n t i n v e n t i o n w i l l n o w be f u r t h e r i l l u s t r a t e d

b y , b u t i s by no means l i m i t e d t o , t h e f o l l o w i n g E x a m

p l e s , i n which t h e y i e l d s o f k e t a z i n e a r e c a l c u l a t e d by

mol %, i n t e r m s o f h y d r o g e n p e r o x i d e , b a s e d upon t h e

a m o u n t o f t h e c h a r g e d p e r o x i d e c o m p o u n d s .

EXAMPLE

I n t o a 3 0 0 ml ? a s k , 1 8 0 ml o f i s o p r o p a n o l , 40 g o f

powdered s i l i c a g e l f o r a d e s i c c a n t ( S i O Z c o n t e n t i n d r yb a s e : 99.7% by w e i g h t , s u r f a c e a r e a : 7 2 0 m z / g ) , 0 . 0 5 g

o f d i s o d i u m e t h y l e n e d i a m i n e t e t r a a c e t a t e ( i . e . EDTA

2 N a ) a n d 3 . 7 8 g ( 0 . 1 m o l ) o f 9 0% a q u e o u s h y d r o g e n



4 , 2 3 3 , 2 4 27

p e r o x i d e were a d d e d , and t h e n , g a s e o u s a m m o n i a wa s

introduced t o t h e s t i r r e d r e s u l t a n t mixture a t a r a t e of

750 ml/min, i n a b a t h , a t 6 0 ° C . , w h i l e 8 g o f a c e t o n e

was a d d e d j u s t a f t e r t h e b e g i n n i n g o f t h e i n t r o d u c t i o n o f

t h e a m m o n i a . F i v e m i n u t e s a f t e r t h e b e g i n n i n g o f t h e

i n t r o d u c t i o n o f t h e ammonia, t h e r a t e o f t h e a m m o n i a

i n t r o d u c t i o n wa s re d uce d t o 2 5 m l / i n an d t h e r e a c t i o nwa s continued f o r 8 h o u r s . During t h i s r e a c t i o n period

1 g e a c h o f a c e t o n e was a dditiona l l y added to the re ac

t i o n m i x t u r e a t 3 0 m i n u t e s , 1 h o u r , 2 h o u r s , 3 h o u r s , 4

h o u r s a n d 6 h o u r s a f t e r t h e b e g i n n i n g o f t h e r e a c t i o n .

A f t e r t h e c o m p l e t i o n o f t h e r e a c t i o n , 7 . 2 8 g o f a c e t o n e

a z i n e , which was d e t e r m i n e d by g a s c h r o m a t o g r a p h y ,

wa s f o r m e d . T h i s c o r r e s p o n d s t o a 65% y i e l d based

u p o n t h e c h a r g e d h y d r o g e n p e r o x i d e .Th e r e a c t i o n m i x t u r e wa s ? l t e r e d , to t h e r e b y r e m o ve

s i l i c a g e l , and t h e s o l v e n t a n d o t h e r s were d i s t i l l e d o f f

from t h e ? l t r a t e . A c e t o n e - a z i n e t h u s o b t a i n e d wa s s e p a

r a t e d , b y d i s t i l l a t i o n , f r o m t h e r e s u l t a n t l i q u i d .I n t o 1 0 g o f 3 5 % b y weight o f a n aqueous a c e t o n e

a z i n e s ol u t i o n which wa s prepared from t h e a c e t o n e

a z i n e o b t a i n e d a b o v e , 5 . 9 g 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

wa s dropwise added a t a temperature of 2 5 ° C . , t o

t h e r e b y f o r m t h e p r e c i p i t a t i o n o f m o n o h y d r a z i n e s u lf a t e . Th e p r e c i p i t a t i o n wa s ? l t e r e d , washed with a s m a l l

amount o f c o l d w a t e r and d r i e d . T h u s , 4 . 0 g o f m o n o h y

d r a z i n e s u l f a t e wa s o b t a i n e d .

EXAMPLE

I n t o a 2 5 m l ? a s k , 2 g o f h i g h p u r i t y s i l i c a g e l f o r

t h i n - l a y e r c h r o m a t o g r a p h y ( F e c o n t e n t 0 . 0 0 2 % , Cuc o n t e n t 0.0005%, P b c o n t e n t 0 . 0 0 0 5 % ) , and 0 . 0 2 g o f

EDTA Na were c h a r g e d , and t h e n , 1 2 ml o f methanol

a n d 0 . 7 5 g ( 2 0 . 3 m o l ) o f a b o u t 9 0% a q u e o u s hydrogen

p e r o x i d e were a d d e d , a n d f u r t h e r , 1 ml o f a 1 / 1 ( v o l /

v o l ) o f methanol/acetone m i x t u r e s a t u r a t e d w i t h am

m o n i a t h e r e i n wa s added. G a s e o u s a m m o n i a wa s i n t r o

duced i n a s m a l l stream i n t o t h e s t i r r e d r e s u l t a n t mixture

i n an i l b a t h , a t a temperature o f 6 0 ° C . 1 ml each o f t h e

above-mentioned methanol/acetone mixture wa s addi

t i o n a l l y charged t o t h e r e a c t i o n m i x t u r e a t 3 0 m i n u t e s , 1

h o u r , 2 h o u r s , 4 h o u r s and 6 h o u r s a f t e r t h e b e g i n n i n g o f

t h e r e a c t i o n . E i g h t h o u r s a f t e r t h e b e g i n n i n g o f t h e

r e a c t i o n , a c e t o n e - a z i n e , which was d e t e r m i n e d b y g a s

chromatography, wa s o b t a i n e d with a y i e l d o f 4 6 . 6 %

( w h i c h c o r r e s p o n d s t o 70.7% b a s e d upon t h e r e a c t e d

h y d r o g e n p e r o x i d e ) .

EXAMPLE

2 g o f s i l i c a g e l f o r column c h r o m a t o g r a p h y , whichwere p a s s e d through a s i e v e having a s i z e o f 3 2 5 mesh,

a nd 0 . 0 2 g o f EDTA Na were charged i n t o a ? a s k , a nd

t h e n , 1 2 m l o f m e t h a n o l , 0 . 7 5 g ( 2 0 . 3 m o l ) o f a b o u t

9 0% a q u e o u s hydrogen p e r x i d e and 3 ml o f a c e t o n e

w e r e added. After gaseou s a m m o n i a wa s b u b b l ed i n t o

t h e m i x t u r e c o n t a i n e d i n t h e ? a s k , t o t h e r e b y s a t u r a t e

t h e m i x t u r e with ammonia, a m m o n i a g a s wa s i n t r o

duced i n a s m a l l s t r e a m i n t o t h e v i g o r o u s l y s t i r r e d r e s u l

t a n t m i x t u r e , i n a b a t h , a t a temperature of 6 0 ° C . Th e

r e a c t i o n wa s c o n t i n u e d f o r 8 h o u r s . A c e t o n e - a z i n e ,

which was determined by g a s chromatography, wa s

o b t a i n e d w i t h a y i e l d o f 48.9%.

EXAMPLE

The reaction w a s carried o u t i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Example , e x c e p t t h a t 5 g o f t h e s i l i c a

g e l u s e d i n Example 3 wa s u s e d . A f t e r 8 h o u r s r e a c t i o n ,

a c e t o n e - a z i n e , which was determined b y g a s chroma

1 5

2 0

2 5

4 0

4 5

5 5

6 0

8t o g r a p h y , wa s o b t a i n e d w i t h a y i e l d o f 6 2 . 6% (which

c o r r e s p o n d s t o 7 0 . 5 % , ‘ b a s e d upon t h e r e a c t e d hydro

g e n p e r o x i d e ) .

EXAMPLE

The reaction w a s carried out i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Exa mpl e , e x c e p t t h a t 2 g o f i l i c a g e lf o r c o l u m n c h r o m a t o g r a p h y , ha v ing a s i z e of 100

through 200 m e s h (manufactured b y WAKO PURE

CHEMICAL IND., LTD.), and 0 . 2 g o f EDTA 2 Na

were u s e d . A f t e r t h e c o m p l e t i o n of t h e r e a c t i o n , a c e

t o n e - a z i n e was formed w i t h a y i e l d o f 3 2 . 3 % .

EXAMPLE

2 g o f s i l i c a a e r o g e l ( m a n u f a c t u r e d b y NIPPONAEROSIL O . , L T D . ) , 0 . 4 g o f EDTA Na a n d 3 3 ml

o f methanol were charged i n t o a ? a s k . I n t o t h e m i x t u r e ,

0 . 7 5 g ( 2 0 . 3 m o l ) o f a b o u t 9 0% a q u e o u s hydrogen

p e r o x i d e a n d 2 ml o f t h e mixed s o l u t i o n o f m e t h a n o l ,

a c e t o n e and a m m o n i a u s e d i n Ex a m p l e 2 w e re a d d e d .

Th e r e a c t i o n wa s c a r r i e d out f o r 6 hours a t a temperat u r e o f 6 0 ° C . , w h i l e 2 m l each o f t h e mixed s o l u t i o n o f

m e t h a n o l , a c e t o n e and a m m o n i a were a d d i t i o n a l l y

charged f o u r t i m e s . Acetone-azine wa s o b t a i n e d with a

y i e l d o f 1 5 . 3 % .

EXAMPLE

The reaction w a s carried out i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Example 2 f o r 6 h o u r s , e x c e p t t h a t 2 g

o f s i l i c a g e l p o w d e r , w h i c h was p r e p a r e d b y g r i n d i n g

s i l i c a g e l f o r a d e s i c c a n t i n g r a n u l a r form i n a m o r t a r ,

w e re u s e d . Th e y i e l d o f t h e a c e t o n e - a z i n e wa s 4 4 . 5%

( w h i c h c o r r e s p o n d s t o 7 2 . 1 % , b a s e d upon t h e r e a c t e d

h y d r o g e n p e r o x i d e ) .

EXAMPLE

The reaction wa s carried out i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Example , e x c e p t t h a t 2 g o f s i l i c a g e l

u s e d i n Example 5 a n d , i n s t e a d o f a b o u t 90% aqueous

hydrogen p e r o x i d e , 2 m l ( 2 0 . 2 m o l ) o f a b o u t 3 0%aqueous hydrogen p e r o x i d e were u s e d . A f t e r t h e c o m

p l e t i o n o f 8 h o u r s r e a c t i o n , a c e t o n e - a z i n e wa s o b t a i n e d

with a y i e l d o f 20.7%.

EXAMPLE

The reaction was carried ou t i n a manner s i l i m a r to

t h a t d e s c r i b e d i n Example 8 , e x c e p t t h a t 2 g o f t h e s i l i c a

g e l u s e d i n Ex a m p l e 3 wa s u s e d . At 6 h o u r s a f t e r t h e

b e g i n n i n g o f t h e r e a c t i o n , a c e t o n e - a z i n ewa s

o b t a i n e d


EXAMPLE 0

The reaction w a s carried o u t , i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Example 3 , by u s i n g 2 g o f t h e s i l i c a

g e l u s e d i n Example 5 , 0 . 2 g o f d i s o d i u m p h o s p h a t e , 1 0

m l o f m e t h a n o l , 5 m l o f a c e t o n e and 2 m l ( 2 0 . 2 m o l )

o f a b o u t 3 0% a q u e o u s h y d r o g e n p e r o x i d e . E i g h t h o u r s

a f t e r t h e b e g i n n i n g o f t h e r e a c t i o n , a c e t o n e - a z i n e wa s

o b t a i n e d with a y i e l d o f 1 8 . 8 % .

EXAMPLES 1 1 TO 1 5

Th e f o l l o w i n g E x a m p l e s were c a r r i e d o u t by u s i n g

v a r i o u s s o l v e n t s . I n Examples 1 1 , 1 2 and 1 3 , t h e r e a c

t i o n s were c a r r i e d o u t u s i n g a r e a c t i o n procedure and

c o n d i t i o n s s i m i l a r t o t h o s e d e s c r i b e d i n Exa mpl e 2 . I n

Examples 1 4 and 1 5 , t h e r e a c t i o n s we r e c a r r i e d out i n a

ma nner s i m i l a r t o t h a t d e s c r i b e d i n Exa mpl e 3 , e x c e p t



4 , 2 3 3 , 2 4 2

t h a t t h e s i l i c a g e l u s e d i n Example 2 wa s u s e d . Th e

r e s u l t s a r e s h o w n i n Table 1 .

TABLE

R e a c t i o n K e t a z i n e

E x . N o . S o l v e n t T i m e ( h r ) Y i e l d ( % )

1 l l s o p r o p a n o l 8 4 5 . 1

1 2 l - P h e n y l E t h a n o l 8 3 8 . 9

1 3 2 , 4 - D i m e t h y l S u l f o l a n e 6 3 4 . ]

1 4 Benzene 6 2 8 . 3

l 5 E t h y l A c e t a t e 8 6 5 . 3

EXAMPLE 6

Th e r e a c t i o n was c a r r i e d o u t w i t h v i g o r o u s s t i r r i n g ,

i n a b a t h , a t a t e m p e r a t u r e o f 6 0 ° C . , w h i l e i n t o a mix

t u r e o f 2 g o f t h e s i l i c a g e l u s e d i n Example , 0 . 0 2 g o f

EDTA.2Na, 1 5 ml o f a c e t o n e and 2 0 . 3 m ol o f a b o u t

9 0% a q u e o u s h y d r o g e n p e r o x i d e , g a s e o u s ammonia was

i n t r o d u c e d . At 6 h o u r s a f t e r t h e b e g i n n i n g o f t h e r e a c

t i o n , a c e t o n e - a z i n e wa s o b t a i n e d w i t h a y i e l d o f 7.2%.

EXAMPLE 7

Th e r e a c t i o n wa s c a r r i e d out i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Example , e x c e p t t h a t 2 g o f t h e s i l i c a

g e l u s e d i n Example 5 wa s u s e d and t h e r e a c t i o n tem

p e r a t u r e was 4 0 ° C . At 6 h o u r s a f t e r t h e b e g i n n i n g o f

t h e r e a c t i o n , a c e t o n e - a z i n e wa s o b t a i n e d w i t h a y i e l d o f

7 . 2 % .

EXAMPLE 8

Th e r e a c t i o n wa s c a r r i e d out i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Example , e x c e p t t h a t 2 g o f t h e s i l i c ag e l u s e d i n Example 2 wa s u s e d a n d t h e r e a c t i o n tem

p e r a t u r e wa s r o o m t e m p e r a t u r e . E i g h t h o u r s a f t e r t h e

b e g i n n i n g o f t h e r e a c t i o n , a c e t o n e - a z i n e wa s o b t a i n e d

w i t h a y i e l d o f 2 . 2 % .

EXAMPLE 9

Th e r e a c t i o n was c a r r i e d o u t w i t h v i g o r o u s s t i r r i n g ,

i n a b a t h , a t a t e m p e r a t u r e of 6 0 ° C . , w h i l e g a s e o u s

a m m o n i a wa s introduced i n a very s m a l l stream i n t o a

m i x t u r e o f 2 g o f t h e s i l i c a g e l u s e d i n Example 5 , 1 5 m l

o f methanol and 8 m mol o f l , l ' - p e r o x y - d i i s o p r o p y l

a m i n e ( w h i c h was p r e p a r e d f r o m a c e t o n e , a mmonia a n d

h y d r o g e n p e r o x i d e a n d i s o l a t e d f r o m t h e r e a c t i o n m i x

t u r e b y d i s t i l l a t i o n ) . S i x h o u r s a f t e r t h e b e g i n n i n g o f t h e

r e a c t i o n , a c e t o n e - a z i n e was o b t a i n e d w i t h a y i e l d o f

4 2 . 0 % .

EXAMPLE 0To t h e s i l i c a g e l u s e d i n Example 5 , 1 2 ml o f metha

n o l , 5 ml o f a c e t o n e and 2 0 . 3 m ol o f a b o u t 9 0% aque

o u s hydrogen p e r o x i d e wa s a d d e d , a n d t h e n , t h e r e s u l

t a n t m i x t u r e wa s s a t u r a t e d with gaseous ammonia. Th e

r e a c t i o n wa s c a r r i e d o u t with s t i r r i n g a t a t e m p e r a t u r e

o f 6 0 ° C . , w h i l e g a s e o u s a m m o n i a wa s i n t r o d u c e d , i n a

v e r y s m a l l s t r e a m , i n t o t h e m i x t u r e . S i x h o u r s a f t e r t h e

b e g i n n i n g o f t h e r e a c t i o n , a c e t o n e - a z i n e was o b t a i n e d

w i t h a y i e l d o f 2 1 . 2 % .

EXAMPLE 1

The e a c t i o n wa s c a r r i e d out i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n ‘ E x a m p l e 2 0 , e x c e p t t h a t a b o u t 3 0%

a q u e o u s hydrogen p e r o x i d e was u s e d . a n d t h a t 8 ml o fa c e t o n e and 1 0 ml o f methanol were u s e d . E i g h t h o u r s

a f t e r t h e b e g i n n i n g o f t h e r e a c t i o n , a c e t o n e - a z i n e was

o b t a i n e d w i t h a y i e l d o f 1 5 . 6 % .

1 5

20

2 5

3 0

4 5

5 0

5 5

6 0

6 5

1 0

EXAMPLE 2

‘The reaction was carried ou t i n a manner similar to

t h a t d e s c r i b e d i n Example , e x c e p t t h a t 2 g o f i l i c a g e l

( w h i c h w a s p r e p a r e d b y c a l c i n i n g t h e s i l i c a g e l u s e d i n

Example 5 f o r 2 h o u r s , a t a te m p e r a t u r e o f 6 0 0 ° C . ) wa s

u s e d , a n d , a l s o , t h a t EDTA Na wa s o m i t t e d . Th e r e a c

t i o n wa s c a r r i e d o u t f o r 8 h o u r s . Th e y i e l d o f t h e a c e

t o n e - az i n e t h u s o b t a i n e d wa s 34.5%.

EXAMPLE 3

A f t e r t h e r e a c t i o n m i x t u r e o f Example 2 2 wa s a l

lowed t o s t a n d f o r one n i g h t , t h e s i l i c a g e l wa s recov

e r e d by ? l t r a t i o n and washed w i t h m e t h a n o l o n e . By

u s i n g t h e s i l i c a g e l t h u s r e c o v e r e d , t h e r e a c t i o n was

c a r r i e d our i n a m a n n e r s i m i l a r t o t h a t described i n

Example 2 . Th e r e a c t i o n wa s c a r r i e d o u t f o r 8 h o u r s .

Th e y i e l d o f t h e a z i n e t h u s p r o d u c e d was 2 1 . 6 % . Al

t h o u g h s i m i l a r o p e r a t i o n s were r e p e a t e d a f u r t h e r 9

t i m e s , s u b s t a n t i a l l y e q u a l y i e l d s w e r e o b t a i n e d .

EXAMPLES 4 TO 7

B y u s i n g v a r i o u s k e t o n e s , t h e f o l l o w i n g E x a m p l e s

were c a r r i e d o u t . The amounts of methanol ( s o l v e n t ) ,

hydrogen p e r o x i d e and EDTA Na u s e d were t h e same

a s i n Example 3 . The r e s u l t s a r e s hown i n Table 2 .

TABLE

Ex . Reaction Reaction Ketazine

N o . K e t o n e T e m p .( ° C . ) T i m e( h r ) Y i e l d ( % )

2 4 M e t h y l E t h y l K e t o n e 6 0 8 4 7 . 5

2 5 M e t h y l I s o b u t y l Ketone 6 5 1 2 3 3 . 0

2 6 C y c l o h e x a n o n e 6 5 1 2 2 4 . 4

2 7 Acetophenone 6 5 1 2 8 . 6

EXAMPLE 8

Th e e a c t i o n was c a r r i e d o u t by m o d e r a t e l y i n t r o d u c

i n g g a s e o u s ammonia, w i t h s t i r r i n g , i n t o a m i x t u r e o f 4

g o f t h e s i l i c a g e l u s e d i n Example , 2 0 g o f c y c l o h e x a

n o l , 8 . 8 g o f c y c l o h e x a n o n e , 3 . 0 g o f a b o u t 3 0% a q u e o u s

hydrogen p e r o x i d e a n d 0 . 0 4 g o f EDTA.2Na, a t a tem

p e r a t u r e o f 6 0 ° C . , f o r 6 h o u r s . C y c l o h e x a n o n e - a z i n e ,

which was d e t e r m i n e d by g a s c h r o m a t o g r a p h y , waso b t a i n e d w i t h a y i e l d o f 1 6 . 6 % .

EXAMPLE 9

Th e r e a c t i o n was c a r r i e d o u t by m o d e r a t e l y i n t r o d u c

i n g g a s e o u s a m m o n i a , w i t h s t i r r i n g , i n t o a m i x t u r e o f 3 0

g o f t h e r e a c t i o n m i x t u r e ( w h i c h was p r e p a r e d by o x id i z i n g c y c l o h e x a n o l w i t h o x y g e n a n d which c o n t a i n e d

0 . 9 9 5 m ol/g o f p e r o x i d e c o m p o u n d s ) , 8 . 8 g o f c y c l o

h e x a n o n e , 0 . 0 4 g o f EDTA Na and 4 g o f t h e s i l i c a g e l

u s e d i n Example 2 , f o r 6 h o u r s , a t a t e m p e r a t u r e o f 6 0 °

C . The i e l d o f t h e c y c l o h e x a n o n e - a z i n e t h u s p r o d u c e d

wa s 27. 7% .

EXAMPLE 0

Th e r e a c t i o n was c a r r i e d o u t b y . m o d e r a t e l y i n t r o d u c

i n g g a s e o u s a m m o n i a , w i t h s t i r r i n g , i n t o a m i x t u r e o f

1 7 . 0 g o f t h e r e a c t i o n m i x t u r e ( w h i c h was p r e p a r e d by

o x i d i z i n g l - p h e n y l e t h a n o l w i t h o x y g e n a n d which

c o n t a i n e d 1 . 2 6 3 m mol/g o f p e r o x i d e c o m p o u n d s ) , 2 g

o f a c e t o p h e n o n e , 0 . 0 2 g o f EDTA.2Na and 2 g o f t h es i l i c a g e l u s e d i n Example 2 , f o r 6 h o u r s , a t a t e m p e r a

t u r e o f 1 2 0 ° C . Th e y i e l d o f t h e a c e t o p h e n o n e - a z i n e t h u s

produced wa s 3 . 9 % .



1 1

EXAMPLE 1

I s o p r o p y l a l c o h o l was o x i d i z e d w i t h oxygen a n d . t h e

r e s u l t a n t r e a c t i o n mixture wa s c o n c e n t r a t e d under r e

duced p r e s s u r e . 2 . 3 4 g o f t h i s c o n c e n t r a t e d l i q u i d co n

t a i n i n g t h e p e r o x i d e s ( t h e c o n c e n t r a t i o n o f t h e p e r o x

i d e s were 4 . 1 1 m ol / ) wa s d i s s o l v e d i n 1 0 m l o f meth

a n o l , a n d f u r t h e r , 2 g o f t h e s i l i c a g e l u s e d i n Example 3

a nd 0 . 0 2 g of EDTA.2Na w e re added t h e r e t o . After 1

m l o f t h e m i x t u r e o f m e t h a n o l , a c e t o n e and ammonia,

obtained i n a m a n n e r s i m i l a r t o t h a t described i n Exam

p l e 2 , was added t o t h e r e s u l t a n t m i x t u r e , t h e r e a c t i o n

was c a r r i e d o u t b y i n t r o d u c i n g , w i t h s t i r r i n g , g a s e o u s

a m m o n i a i n t o t h e r e a c t i o n m i x t u r e , a t a t e m p e r a t u r e o f

6 0 ° C . 1 ml each o f t h e above-mentioned m i x t u r e o f

m e t h a n o l , a c e t o n e and a m m o n i a wa s a d d i t i o n a l l y

c h a r g e d a t 3 0 m i n u t e s , 1 h o u r , 2 h o u r s and 4 h o u r s a f t e r

t h e b e g i n n i n g o f t h e r e a c t i o n . Th e r e a c t i o n was c a r r i e d

out f o r a f u r t h e r 4 hours a nd wa s stopped a t 8 h o u r s , i n

t o t a l , a f t e r t h e b e g i n n i n g o f t h e r e a c t i o n . A c e t o n e - a z i n e ,

which was d e t e r m i n e d by a n a l y s i s , was t h u s o b t a i n e d

w i t h a y i e l d o f 6 2 . 6 % . T h i s y i e l d c o r r e s p o n d s t o 6 9 . 4 % ,

b a s e d upon t h e consumed p e r o x i d e .

EXAMPLE 2

I n t o 1 2 . 4 g o f t h e r e a c t i o n m i x t u r e c o n t a i n i n g p e r o x

i d e s which was o b t a i n e d by o x y d i z i n g i s o p r o p y l a l c o h o l

w i t h oxygen ( t h e c o n c e n t r a t i o n o f t h e p e r o x i d e s wa s

1 , 5 3 3 m o l / g ) , 0 . 0 2 g o f EDTA N a , 2 g o f t h e s i l i c a

g e l u s e d i n Example 1 and 0 . 5 m l o f a c e t o n e were

a d d e d . Th e r e a c t i o n wa s c a r r i e d o u t by m o d e r a t e l y

i n t r o d u c i n g g a s e o u s a m m o n i a , w i t h s t i r r i n g , i n t o t h e

r e a c t i o n m i x t u r e , a t a t e m p e r a t u r e o f 6 0 ° C . At 3 0 m in

u t e s , 1 h o u r , 2 h o u r s , 4 h o u r s a n d 6 h o u r s a f t e r t h e

b e g i n n i n g o f t h e r e a c t i o n , 0 . 5 ml e a c h o f a c e t o n e was

a d d i t i o n a l l y c h a r g e d . At 8 h o u r s a f t e r t h e b e g i n n i n g o f

t h e r e a c t i o n , t h e a c e t o n e - a z i n e , which was d e t e r m i n e d

by a n a l y s i s , was o b t a i n e d w i t h a y i e l d o f 5 5 . 4 % , which

c o r r e s p o n d s t o 6 9 . 0 % , b a s e d upon t h e consumed p e r o x

i d e .

EXAMPLE 3

2 . 2 4 g o f p a l l a d i u m a c e t a t e and 0 . 5 2 0 g o f EDTA.4Na

were d i s s o l v e d i n 3 6 g of 25% aqueous a m m o n i a a n d ,

t h e n , 1 5 . 8 g of acetone wa s a dded t h e r e t o . 5 . 5 4 g of

3 0 . 5 % a q u e o u s h y d r o g e n p e r o x i d e w a s v e r y s l o w l y

i n t r o d u c e d i n t o t h i s s o l u t i o n , over 7 . 5 h o u r s , a t a t em

p e r a t u r e o f 3 3 ° C . A f t e r 2 6 h o u r s , a c e t o n e - a z i n e , whichwa s d e t e r m i n e d b y g a s chromatography, was formed


EXAMPLES 34 TO 7

2 . 2 4 g o f p a l l a d i u m a c e t a t e a nd 0 . 5 2 0 g EDTA.4Na

were d i s s o l v e d i n 3 6 g of 25% aqueous ammonia, and

t h e n , t h e k e t o n e and t h e methanol l i s t e d i n T a b l e 3

b e l o w w e r e added. The ixture wa s heated t o a t e m p e r

a t u r e o f 5 0 ° C . , w i t h s t i r r i n g . 5 . 5 4 g o f 30.5% a q u e o u s

hydrogen p e r o x i d e were s l o w l y i n t r o d u c e d i n t o t h i ss o l u t i o n over 3 h o u r s , a n d t h e r e a c t i o n wa s c a r r i e d out

f o r a f u r t h e r 1 5 h o u r s . Th e corresponding k e t a z i n e wa s

obtained a s a s h o w n i n Table 3 .

TABLE

K e t a z i n e

E x . No. Ketone Methanol Y i e l d (%)

3 4 M e t h y l E t h y l K e t o n e ( 2 0 m l ) 1 0 m l 4 0 . 3

3 5 M e t h y l l s o b u t y l K e t o n e ( 2 0 m l ) 4 0 m l 8 . 23 6 C y c l o h e x a n o n e ( 2 0 m l ) 2 0 m l 2 3 . 1

4 , 2 3 3 , 2 4 2

1 5

2 5

40

1 2

TABLE - c o n t i n u e d

K e t a z i n e

E x . N o . K e t o n e M e t h a n o l Y i e l d (%)

3 7 A c e t o p h e n o n e ( 2 0 m l ) 6 0 m l 3 . 7

EXAMPLE 8

A c e t o n e - a z i n e was p r e p a r e d by u s i n g a p e r o x i d e

s o l u t i o n which was o b t a i n e d b y o x y d i z i n g i s op r o p a n o l

w i t h a i r . 4 . 7 6 g o f t h e p e r o x i d e s o l u t i o n ( c o n t a i n i n g 8 . 0 9

m ol o f p e r o x i d e s i n t e r m s o f hydrogen p e r o x i d e ) was

added t o a s o l u t i o n o f 2 . 2 4 g o f p a l l a d i u m a c e t a t e , 0 . 5 2 0

g of EDTA.4Na nd 7 . 9 0 g o f a c e t o n e d i s s o l v e d i n 1 8 g

o f 25% aqueous ammonia, and r e a c t e d f o r 4 h o u r s , a t a

t e m p e r a t u r e of 4 4 ° C . Acetone-azine wa s o b t a i n e d with

a y i e l d o f 8 0 . 6 % .

EXAMPLE 9

1 . 3 1 g o f 3 , 3 , 5 , 5 - t e t r a m e t h y 1 d i o x a z o l a n e ( 7 8 . 3 % b y

weight of a c e t o n e s o l u t i o n ) wa s added t o a s o l u t i o n of

0 . 5 6 g o f p a l l a d i u m a c e t a t e , 0 . 1 3 0 g o f EDTA.4Na and

3 . 9 5 g o f acetone d i s s o l v e d i n 5 g of 25% aqueous am

monia. The e s u l t a n t mixture wa s a l l ow ed t o r e a c t a t a

t e m p e r a t u r e o f 3 9 ° C . , f o r 2 d a y s . A c e t o n e - a z i n e was

o b t a i n e d w i t h a y i e l d o f 3 6 . 3 % .

EXAMPLES 0 TO 3

Th e p a l l a d i u m s a l t l i s t e d i n T a b l e 4 below was added

t o 4 . 0 5 g o f 2 5 % aqueous a m m o n i a a n d , t h e r e i n t o , 1 5 . 8

g of acetone a nd 0 . 5 2 g of EDTA.4Na were d i s s o l v e d .

Gaseous a m m o n i a wa s s l o w l y i n t r o d u c e d i n t o t h e r e a c

t i o n m i x t u r e , w i t h s t i r r i n g , a t a t e m p e r a t u r e o f 5 0 ° C .

Th e r e a c t i o n was c a r r i e d o u t by d r o p w i s e a d d i n g 5 . 5 4 go f 30.5% a q u e o u s hydrogen p e r o x i d e o v e r 3 h o u r s a n d

wa s continued f o r a f u r t h e r 2 1 h o u r s . Thus, acetone

a z i n e wa s produced. Th e r e s u l t s a r e s h o w n i n Table 4 .

TABLE

E x . No. P a l l a d i u m S a l t A c e t o n e - A l i n e Y i e l d (%)

4 0 P a l l a d i u m C h l o r i d e ( 1 . 7 7 g ) 1 2 . 0

4 1 P a l l a d i u m N i t r a t e ( 1 . 0 g ) 2 1 . 3

4 2 P a l l a d i u m S u l f a t e ( 1 . 0 g ) 1 5 . 0

4 3 P a l l a d i u m C y a n i d e ( 2 . 0 g ) 8 . 6

EXAMPLES 44 TO 46

Palladium a c e t a t e an d EDTA.4Na we r e d i s s o l v e d i n

36 g of 25% aqueous a m m o n i a i n amounts s h o w n i n

Table 5 b e l ow a n d , t h e n , 1 5 . 8 g of acetone wa s a d d e d .

The mi x t u re w a s warmed o n a n o i l bath a n d the reac

t i o n wa s c a r r i e d o u t by adding 5 . 5 4 g o f 30. 5% aqueous

hydrogen p e r o x i d e . T h u s , a c e t o n e - a z i n e was o b t a i n e d .

Th e r e s u l t s a r e s h o w n i n Table 5 .

TABLE

Exam p le No . 4 4 4 5 46

Palladium Acetate 7 0 mg 4 . 4 8 g 6 . 7 2 g

EDTA 4Na 1 6 . 3 mg 1 . 0 4 g 1 . 0 4 g

R e a c t i o n T e m p e r a t u r e ( ° C . ) 4 4 3 3 3 7

D r o p w i s e A d d i t i o n Time ( h r ) o f

Aqueous Hydrogen Pe r o x i d e 3 7 . 5 —

R e a c t i o n Time ( h r ) 9 1 1 . 5 7

Acetone~Azine Y i e l d (%) 4 . 2 4 5 7 . 2 6 6 . 6



4 , 2 3 3 , 2 4 21 3

EXAMPLES 7 TO 0

112 of p a l l a d i u m a c e t a t e was d i s s o l v e d i n 3 6 g o f

2 5 % a q u e o u s a m m o n i a . I n Example 4 7 a n d 4 8 , i n t o t h e

s o l u t i o n t h u s o b t a i n e d , 1 5 . 8 g o f a c e t o n e and 5 . 5 4 g o f

3 0 . 5 % a q u e o u s h y d r o g e n p e r o x i d e ( a n d 5 m mol o f

EDTA.4Na o n l y i n Example 4 8 ) w e r e a d d e d , a n d t h e

r e a c t i o n wa s c a r r i e d o u t f o r 1 0 h o u r s , a t a t e m p e r a t u r eo f 5 0 ° C . I n Example 4 9 a n d 5 0 , t h e a b o v e - m e n t i o n e d

r e a c t i o n wa s e p e a t e d , e x c e p t t h a t t h e p a l l a d i u m a c e t a t e

s o l u t i o n w a s t r e a t e d b y s i l i c a g e l b e f o r e t h e b e g i n n i n g o f

t h e r e a c t i o n . Th e t r e a t m e n t wa s c a r r i e d o u t i n such a

m a n n e r t h a t t h e s i l i c a g e l wa s added t o t h e s o l u t i o n and

t h e m i x t u r e was a g i t a t e d f o r 3 0 m i n u t e s , f o l l o w e d by

? l t e r i n g o f f t h e s i l i c a g e l . I n Example 5 0 , 5 m mol o f

EDTA.4Na wa s a l s o a dded t o t h e r e a c t a n t m i x t u r e .

The r e s u l t s a r e s hown i n Table 6 .

TABLE

A m o u n t o f

A m o u n t of EDTA 4Na S i l i c a G e l Acetone-Azine

E x . N o . u s e d u s e d Y i e l d (%)

47 —— — 10.0

4 8 5 m ol — 4 2 . 0

4 9 _ 0. 4 g 49.6

5 0 5 m m ol 0 . 1 g 5 7 . l

EXAMPLES 1 TO 5

P a l l a d i u m a c e t a t e , i n a n a m o u n t l i s t e d i n Table 7

b e l o w , was d i s s o l v e d i n 3 6 g o f 2 5 % a q u e o u s a m m o n i a

a n d t h e n , t h e p o l y c a r b o x y d e r i v a t i v e o f a mmonia o r

20

2 5

3 0

a l k y l e n e polyamine a s l i s t e d i n Table 7 wa s a d d e d . Th e

r e a c t i o n was c a r r i e d o u t , by a d d i n g 1 5 . 8 g o f a c e t o n e

a n d 5 . 5 4 g o f 3 0 . 5 % a q u e o u s h y d r o g e n p e r o x i d e , u n d e r

t h e r e a c t i o n c o n d i t i o n s shown i n T a b l e 7 . Th e y i e l d s o f

t h e a c e t o n e - a z i n e t h u s o b t a i n e d a r e a l s oshown n

T a b l e

7 .

l 4t o n e wa s u s e d , and a l s o , t h e r e a c t i o n p e r i o d wa s 7 2

h o u r s . Th e y i e l d o f t h e a c e t o n e - a z i n e t h u s o b t a i n e d wa s

3 3 . 1 % .

EXAMPLE 8

T h i s Example d e m o n s t r a t e s t h e f a c t t h a t a s i m i l a r

y i e l d o f a c e t o n e - a z i n e c a n b e o b t a i n e d b y a g a i n u s i n g

t h e r e c o v e r e d a q u e o u s p a l l a d i u m a c e t a t e s o l u t i o n from

t h e r e a c t i o n mixture a f t e r t h e a c e t o n e - a z i n e wa s ex

t r a c t e d w i t h o r g a n i c s o l v e n t .

PREPARATION OFAQUEOUS PALLADIUM

ACETATE

4 . 4 8 g o f p a l l a d i u m a c e t a t e and 1 . 0 4 g o f EDTA.4Na

were d i s s o l v e d i n 3 6 g o f 25% aqueous ammonia. T h i s

s o l u t i o n wa s u s e d f o r t h e ? r s t r u n a n d , t h e r e a f t e r , t h e

r e c o v e r e d p a l l a d i u m a c e t a t e s o l u t i o n s f r o m t h e r e a c t i o n

mixture w e r e used i n f u r t h e r r u n s .

SYNTHESIS OF ACETONE~AZINE

I n t o t h e a b o v e - m e n t i o n e d a q u e o u s p a l l a d i u m a c e t a t e

s o l u t i o n , 1 5 . 8 g o f a c e t o n e and 40 m l o f benzene were

a d d e d , and t h e m i x t u r e wa s h e a t e d t o a t e m p e r a t u r e o f

4 5 ° C . Gaseous a m m o n i a was m o d e r a t e l y i n t r o d u c e d

i n t o t h e m i x t u r e w i t h s t i r r i n g . 5 . 5 4 g o f 30.5% a q u e o u s

hydrogen p e r o x i d e was d r o p w i s e added o v e r 3 h o u r s

and t h e r e a c t i o n wa s f u r t h e r c o n t i n u e d . A f t e r 8 h o u r s ,

t h e b e n z e n e l a y e r was s e p a r a t e d a n d t h e a q u e o u s l a y e r

wa s e x t r a c t e d t w i c e w i t h 40 m l each o f b e n z e n e . Th e

r e s u l t a n t a q u e o u s l a y e r was u s e d a g a i n i n t h e s u b s e q u e n t

r u n ' a s a n a q u e o u s p a l l a d i u m a c e t a t e s o l u t i o n . Th e y i e l d s

o f t h e a c e t o n e - a z i n e t h u s o b t a i n e d a r e s hown b e l o w .

Ru n N o . Y i e l d o f A c e t o n e - A z i n e (%)

TABLE 1 6 0 . 5

P o l y c a r b o x y Amoun t o f R e a c - R e a c - 2 6 4 ~ 0

D e r i v a t i v e o f P a l l a d i u m t i o n t i o n A z i n e 4O 3 6 0 - 4

E x . A m m o n i a o r A c e t a t e Time Temp. Y i e l d 4 6 7 . 3

N o . A l k y l e n e P o l y a m i n e u s e d ( g ) ( h r ) ( ° C . ) ( % ) 5 6 6 . 5

5 1 - 6.72 7 . 5 3 7 21.8

52 EDTA 4Na 2 . 2 4 1 0 50 5 9 . 1

( 1 - 0 4 g )5 3 N i t m o m a c e d c 4 5 PREPARATION OF HYDRAZINE

A c ‘ d ( 0 1 . 3 9 5 ) 2 ' 2 4 8 4 6 4 0 - 2 The a c e t o n e - a z i n e o b t a i n e d wa s s e p a r a t e d from t h e54 Ethylenedramme . . . .

D i p m p i o n i c A c i d 2 2 4 8 4 6 3 7 , ; combined benzene l a y e r s by d i s t i l l a t i o n and 35% by

( l l - 3 4 6 s ) w e i g h t o f t h e a q u e o u s a c e t o n e - a z i n e s o l u t i o n was p r e

5 5 ? x g i i ' e ‘ i ' i ' l ‘ y b 5 0 p a r e d . 1 4 . 8 g 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 a s g r a d u

e t h y l e n e d i a m i n e a l l y added t o 2 5 g o f t h e a q u e o u s a c e t o n e - a z i n e s o l u t i o n ,

T r i a c e l a l e ( 0 - 3 4 g g ) 2 1 4 3 4 6 5 1 - 3 t o thereby form p r e c i p i t a t e s . These p r e c i p i t a t e s were

? l t e r e d , washed with a s m a l l a m o u n t o f c o l d water and

d r i e d . Thus 1 0 o f m o n o h d r a z i n e s u l f a t e was obEXAMPLE 6 5 5 m i n e d ’ g y

2 . 2 4 g o f p a l l a d i u m a c e t a t e and 0 . 5 2 g o f EDTA.4Nawere d i s s o l v e d i n 3 6 g o f 2 5 % by w e i g h t o f a q u e o u s

a m m o n i a a n d , t h e n , 4 g o f a c e t o n e wa s a d d e d . Th e

r e a c t a n t m i x t u r e wa s h e a t e d t o 5 0 ° C . a n d , t h e n , 5 . 5 4 g

o f 3 0 . 5 % a q u e o u s h y d r o g e n p e r o x i d e wa s d r o p w i s e

a dded over 3 h o u r s , while gaseous a m m o n i a wa s i n t r o

duced t o t h e m i x t u r e . The r e a c t i o n wa s continued f o r a

f u r t h e r 6 h o u r s . Th e y i e l d o f t h e a c e t o n e - a z i n e t h u s

obtained wa s 10.0%.

EXAMPLE 7

The reaction w a s carried ou t i n a m a n n e r s i m i l a r t o

t h a t d e s c r i b e d i n Example 4 9 , e x c e p t t h a t 1 0 0 g o f a c e

6 0

6 5

EXAMPLE 9

0 . 5 6 g o f p a l l a d i u m a c e t a t e and 0 . 5 2 g o f EDTA.4Na

wa s d i s s o l v e d i n 3 6 g o f 25% aqueous ammonia, and

t h e n , 1 5 . 8 g o f a c e t o n e and 5 . 5 4 g o f 3 0 . 5% aqueous

h y d r o g e n p e r o x i d e were a d d e d . T h e r e a f t e r , t h e m i x t u r e

wa s heated t o a temperature of 7 0 ° C . and allowed t o

r e a c t f o r 1 0 h o u r s . Th e y i e l d o f t h e a c e t o n e - a z i n e t h u s

obtained wa s 24.9%.What we claim i s :

1 . I n a p r o c e s s f o r producing a k e t a z i n e having t h e

f o r m u l a



4 , 2 3 3 , 2 4 21 5

R 2 R 2

w h e r e i n R 1 r e p r e s e n t s a l k y l g r o u p h a v i n g 1 t o 4 c a r b o natoms and R2 r e p r e s e n t s ( i ) a n a l k y l group h a v i n g 1 t o 4

c a r b o n a t o m s o r ( i i ) p h e n y l o r p h e n y l s u b s t i t u t e d by

a l k y l h a v i n g 1 t o 4 c a r b o n a t o m s , a l k o x y h a v i n g 1 t o 4

c a r b o n atoms o r h a l o g e n , and R1 and R2 t o g e t h e r w i t h

i the car bo n a t o m to w h i c h they ar e bo t h b o n d e d f o r m a

r i n g , by r e a c t i n g a n a l i p h a t i c o r a r o m a t i c k e t o n e h a v i n g

t h e f o r m u l a :

wherein R1 and R2 a r e a s d e f i n e d a b o v e , with a m m o n i a

and a p e r o x i d e c o m p o u n d o r compounds, a t a tempera

t u r e o f f r o m 0 ° t o 1 2 0 ° C . , i n l i q u i d p h a s e , t h e i m p r o v e

m e n t wherein s i l i c a , a t l e a s t one p a l l a d i u m c o m p o u n d

or a mi x t u re thereof i s u s e d a s a c a t a l y s t .

2 . A r o c e s s a s claimed i n c l a i m 1 , wherein s a i d k e ~

t o n e i s s e l e c t e d f r o m a c e t o n e , m e t h y l e t h y l k e t o n e ,

m e t h y l i s o b u t y l k e t o n e , c y c l o h e x an o n e a n d a c e t o p h e

none.

3 . A r o c e s s a s claimed i n c l a i m 1 , wherein s a i d p e r

o x i d e c o m p o u n d i s h y d r o g e n p e r o x i d e .4 . A r o c e s s a s c l a i m e d i n c l a i m 1 , wherein s a i d p e r

o x i d e compound i s s e l e c t e d f r o m a l i q u i d p h a s e o x i d a

t i o n r e a c t i o n p r o d u c t o f s e c o n d a r y a l c o h o l w i t h ox yg e n , a r e a c t i o n p r o d u c t o f s a i d k e t o n e R1COR2 and

hydrogen p e r o x i d e , and a r e a c t i o n p r o d u c t o f s a i d k e

t o n e R1COR2, h y d r o g e n p e r o x i d e a n d a m m o n i a .

5 . A r o c e s s a s c l a i m e d i n c l a i m 4 , wherein s a i d p e r

o x i d e compound h a s t h e f o r m u l a

1 5

2 0

2 5

3 0

3 5

40

4 5

5 5

60

6 5

1 6

R1 OOH

l

OHHOO R2

h e r e i n R1 and R2 a r e a s de?ned above and Y e p r e s e n t s

OH r NH2.

6 . Ar o c e s s a s c l a i m e d i n c l a i m

1 ,wherein s a i d c a t a

l y s t i s a m o r p h o u s s i l i c a .7 . A r o c e s s a s claimed i n c l a i m 6 , wherein t h e

a m o un t o f t h e c a t a l y s t i s w i t h i n t h e r a n g e o f from 2 t o

5 0 % by w e i g h t b a s e d upon t h e t o t a l w e i g h t o f t h e r e a c

t i o n m i x t u r e .

8 . A r o c e s s a s claimed i n c l a i m 1 , wherein s a i d c a t a

l y s t i s a t l e a s t o n e p a l l a d i u m ( I I ) compound.

9 . A p r o c e s s a s c l a i m e d i n c l a i m 8 , wherein t h e

a mou nt o f t h e c a t a l y s t i s w i t h i n t h e r a n g e o f from 0 . 0 0 1

t o 5 . 0 m i l l i m o l b a s e d u p o n 1 g o f t h e r e a c t i o n m i x t u r e .

1 0 . A r o c e s s a s c l a i m e d i n c l a i m 8 , wherein t h e p a l l a

d i u m ( I I ) compound i s s e l e c t e d f r o m p a l l a d i u m c h l o

r i d e , p a l l a d i u m ? u o r i d e , p a l l a d i u m b r o m i d e , p a l l a d i u mn i t r a t e , p a l l a d i u m s u l f a t e , p a l l a d i u m c y a n i d e , p a l l a d i u mo x y c h l o r i d e , p a l l a d i u m a c e t a t e , p a l l a d i u m p r o p i o n a t e ,p a l l a d i u m o x a l a t e , p a l l a d i u m d i p y r i d y l c h l o r i d e , p a l l ad i u m d i p y r i d y l n i t r a t e , s o d i u m p a l l a d i u m c h l o r i d e , p o

t a s s i u m p a l l a d i u m c h l o r i d e , p a l l a d i u m a c e t y l a c e t o n a t ea n d p a l l a d i u m ( I I ) - 1 : 4 - n a p h t h o q u i n o - 5 - o l e a t e .

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US4233242_1980_KETAZINE PRODUCTION.pdf