BULLETIN D E L'ACADEMIE

5 7

CHEM1STR Y

On

the

Preparation

of

Caprolactam

and

from

Cyclohexanone

Dinitroethane
by

T. U R B A X S K I

and A . P l O T R O W S K l

Presented by T. URBAtfSKI

C a p r o l a c t a m is u s u a l l y p r e p a r e d

on March 13, 1957

by a c t i n g o n cyclohexanone, w i t h

h y d r o x y l a m i n e , f o l l o w e d by a B e e k m a n n rearrangement of cyclohexanone o x i m e .
K o v o t n y | 1] discovered t h a t the o x i m e f o r m a t i o n c a n occur i n presence of cone, s u l p h u r i c a c i d or o l e u m a t a h i g h t e m p e r a t u r e . S i m u l t a neously, t h e r e a r r a n g e m e n t takes place a n d c a p r o l a c t a m is formed. A s
a further d e v e l o p m e n t of this m e t h o d X o v o t n y suggests [2], [3] t h e use
of p r i m a r y nitroparaffins as a source of h y d r o x y l a m i n e . A c c o r d i n g to
his i n v e n t i o n a p r i m a r y n i t r o p a r a f f i n is a d d e d to cone, s u l p h u r i c a c i d
at 1 2 0 - 1 2 5 . T h e n c y c l o h e x a n o n e is a d d e d to the r e s u l t i n g s o l u t i o n , a n d
the t e m p e r a t u r e k e p t near 120. A f t e r t h e r e a c t i o n is c o m p l e t e d t h e
r e a c t i o n m i x t u r e is n e u t r a l i s e d w i t h a m m o n i a a n d a n u p p e r l a y e r o f
c a p r o l a c t a m is separated a n d t h e n p u r i f i e d b y d i s t i l l a t i o n u n d e r reduced
pressure. Tin* y i e l d of c a p r o l a c t a m is 80 p e r cent of t h e o r e t i c a l , c a l c u l a t e d
o n t h e basis of c y c l o h e x a n o n e .
T h e a u t h o r s of the present p a p e r suggest a further d e v e l o p m e n t
of N o v o t n y ' s m e t h o d , w h i c h consists i n u s i n g 1,2-dinitroethane as the
cheapest of a l l p r i m a r y n i t r o p a r a f f i n s . T h e t r e n d of t h e r e a c t i o n is m u c h
the same as t h a t described b y N o v o t n y . T h e m o d i f i c a t i o n of t h e o r i g i n a l
m e t h o d consisted i n d i s s o l v i n g 1,2-dinitroethane i n acetic a c i d p r i o r
to r e a c t i n g i t . T h i s f a c i l i t a t e d t h e u n i f o r m i t y a n d c o n t r o l of t h e
reaction.
The. s o l u t i o n was i n t r o d u c e d i n t o h o t c o n c e n t r a t e d ( 1 2 0 C . ) s u l p h u r i c a c i d . Isomerisation of 1,2-dinitroethane to o x a l h y d r o x a m i c a c i d
was f o l l o w e d b y h y d r o l y s i s t o h y d r o x y l a m i n e a n d o x a l i c a c i d . T h e l a t t e r
was decomposed i n t o c a r b o n o x i d e , c a r b o n d i o x i d e a n d water. A c e t i c
a c i d w a s distilled off d u r i n g t h e r e a c t i o n a n d c o u l d be recovered.
[543]

T. U r b a n s k i and A . P i o t r o w s k i

544

T h e y i e l d of c a p r o l a c t a m was, in. l a b o r a t o r y c o n d i t i o n s , 7075 per

cent c a l c u l a t e d o n the basis of c y c l o h e x a n o n e .
A n a p p l i c a t i o n for the p a t e n t has been filed at the P o l i s h P a t e n t
Office [4].
Experimental

10 g. of 1,2-dinitroethane were d i s s o l v e d i n a n e q u a l w e i g h t of acetic

a c i d . T h e s o l u t i o n was i n t r o d u c e d dropwise d u r i n g 20 m i n u t e s to 35 g.
of cone, s u l p h u r i c a c i d , the t e m p e r a t u r e b e i n g m a i n t a i n e d w i t h i n the l i m i t s
120125 C . T h e r e a c t i o n flask was k e p t i n a b a t h w i t h c a l c i u m chloride
s o l u t i o n b o i l i n g at 1 2 0 .
N e x t , 12.5 rag. c y c l o h e x a n o n e were a d d e d dropwise d u r i n g 25 m i nutes to the r e a c t i o n m i x t u r e , the t e m p e r a t u r e b e i n g s t i l l k e p t near 1 2 0 .
A c e t i c a c i d , was d i s t i l l e d off t h r o u g h a condenser.
A f t e r the r e a c t i o n was c o m p l e t e d (this was m a r k e d b y a f a l l of t e m p e r a t u r e i n the r e a c t i o n flask), the r e a c t i o n m i x t u r e was carefully neut r a l i s e d b y i n t r o d u c i n g i t i n t o c o l d aqueous 25 per cent s o l u t i o n of a m m o n i a . T h e t e m p e r a t u r e Avas k e p t b y c o o l i n g below 5 0 .
T h e m i x t u r e was separated i n t o t w o l a y e r s : the l o w e r was f o r m e d
b y a n aqueous s o l u t i o n of a m m o n i u m sulphate w i t h crystals of the l a t t e r ,
the u p p e r was f o r m e d of c a p r o l a c t a m . T h e u p p e r l a y e r was d i s s o l v e d
i n ether a n d d r i e d over a n h y d r o u s s o d i u m sulphate.
T h e p r o d u c t was p u r i f i e d b y d i s t i l l i n g u n d e r r e d u c e d pressure at
1389 0 . b y 1 1 - 1 2 m m . H g .
T h e y i e l d was 10.5 g. of c a p r o l a c t a m , i . c , c. 72 per cent ( c a l c u l a t e d
on cyclohexanone).

INSTITUTE OF ORGANIC SYNTHESIS, POLISH A C A D E M Y OF SCIENCES

REFERENCES
[1] A . N o v o t n y , Swiss Pat. 253,953 (1949).
[2] - US Pat. 2,569,114 (1952); Swiss Pat. 237,402 (1952).
[3] A . S t o y , A . N o v o t n y , Nova synthetickd vldkna, Statni Nakl. Techn. Liter.
Praha, 1953.
[4] T. U r b a n s k i , A P i o t r o w s k i . Polish Patent application No. P 83,480 (1956).