B U L L E T I N DE L ' A C A D E M I E
POLONAISE DES SCIENCES
CI. Ill - Vol. IV, NO. 6, !956
CHEMISTR Y
Reactions of Aromatic Amines with Cyanguanidine.
Reactions of Phenylamidineurea and T h e i r Derivatives
with N-methylaniline
by
T. U R B A N S K I
and B .
Communicated by T. URBAjYSKI
SKOWRONSKA-SERAFIN
at the meeting of November 28, 1955
C o n t i n u i n g the former e x p e r i m e n t s o n the p r e p a r a t i o n a n d c h e m i c a l
properties of a r y l - a m i d f n e u r e a s , reactions of N - p h e n y l - N - a m i d i n e u r e a
and Nj^p-nitrophenyl^No-amidineurea with N-methylaniline have now
been s t u d i e d . P h e n y l a m i d i n e u r e a (I) n i t r a t e , w h e n b o i l e d w i t h N - m e t h y l a n i l i n e , gave g u a n i d i n e a n d N - m e t h y l c a r b a n i l i d e (II) w i t h t h e y i e l d
of 6 5 ° / . O n p r o l o n g e d b o i l i n g the y i e l d of (II) was c o n s i d e r a b l y r e d u c e d
a n d c a r b a n i l i d e ( I I I ) a n d a n i l i n e c o u l d be isolated f r o m the r e a c t i o n mixture.
t
2
0
T h e r e a c t i o n of N j ^ p - n i t r o p h e n y l ) - N - a m i d i n e u r e a (TV) h y d r o c h l o r i d e w i t h N - m e t h y l a n i l i n e gave g u a n i d i n e , p - n i t r o - X - m e t h y l c a r b a n i l ide ( V ) ( y i e l d c. 2 6 % ) a n d a s m a l l a m o u n t of p, p ' - d i n i t r o c a r b a n i l i d e ( V I ) :
2
R—/
\
V N H - C O - N H - C - N H . H X + CH NH-Y
J
/
\
NH
(I) B
U
(IV) R = N 0
\*~r-/r
3
II
2
R—/
\\
/
~\ V N H C O N - /
//
I
i= ii
(1
1= NO
(
VNH-CO-NH-(
(III)
(VI)
(Tl
\
\
/
3
I:
R=II
R=N0
3
These e x p e r i m e n t s i n d i c a t e a c e r t a i n difference between the behav i o u r of p h e n y l a m i d i n e u r e a s a n d its d e r i v a t i v e s w i t h p r i m a r y a n d sec o n d a r y a r o m a t i c amines, r e s p e c t i v e l y .
T h e first stage of the reaction y i e l d e d i n b o t h instances u r e a der i v a t i v e s , w h i c h c o n t a i n the a r y l f r o m the s t a r t i n g a m i d i n e u r e a , a t t a c h e d
t o one of the n i t r o g e n a t o m s of u r e a , a n d the r a d i c a l s f r o m the a m i n e ,
[3631
T. U r b a n s k i and B . S k o w r o n s k a - S e r a f i n
364
a t t a c h e d to a n o t h e r n i t r o g e n a t o m of u r e a . T h u s , compounds ( I I ) a n d ( V )
are analogous
with
R - /
w h i c h resulted
from
VNHCONH-/
\
p- K - p h e n y l - a m i d i n e - u r e a s o n b o i l i n g w i t h
ani-
line [1], [2].
I n the second stage (prolonged b o i l i n g ) t h e p r o d u c t s are different:
w h e n p r i m a r y amines were used, s y m . d i a r y l u r e a s d e r i v i n g f r o m t h e
a m i n e resulted (hence c a r b a n i l i d e i n t h e case of a n i l i n e w a s formed) [1], [2];
w h e n secondary a m i n e w a s used, s y m . d i a r y l u r e a , d e r i v i n g f r o m a r y l a m i d i n e u r e a resulted (compounds ( I I I ) a n d ( V I ) ) .
T h e m e c h a n i s m of these reactions appears t o be c o m p l i c a t e d ; a c h a i n
r e a c t i o n of free r a d i c a l s s i m i l a r t o t h i s , p o s t u l a t e d p r e v i o u s l y b y t h e
a u t h o r s [3], appears to be p r o b a b l e .
ried o u t .
Kurt her e x p e r i m e n t s
w i l l be car-
Experimental
3 g. of p h e n y l a n i i d i n e i i r e a (I) nitrate were m i x e d w i t h 8 n i l . ol
N - m e t h y l a n i l i n e a n d h e a t e d for a short t i m e i n a n o p e n flask to o b t a i n
a clear s o l u t i o n . T h e m i x t u r e was cooled a n d a c i d i f i e d w i t h 1 5 % H C l .
T h e colourless p r e c i p i t a t e was filtered or (better) e x t r a c t e d w i t h benzene
or ether. A f t e r d r y i n g w i t h N a S H ) the solvent w a s e v a p o r a t e d a n d the
X - m e t h y l c a r b a n i l i d e ( I I ) c r y s t a l l i s e d i n t h e f o r m of colourless plates,
m . p . 1 0 4 - 1 0 5 ° , y i e l d 1.8 g . (c. 6r>% of theoretical).
2
4
N - m e t h y l c a r b a l i n i d e ( I I ) b o i l e d f o r 30 m i n u t e s w i t h a n i l i n e y i e l d e d
c a r b a n i l i d e of m . p . 2 3 0 - 2 4 2 ° ( I I ) . B o i l e d w i t h N - m e t h y l a n i l i u e for 4 hours,
it r e m a i n e d u n c h a n g e d .
D E P A R T M E N T OF ORGANIC T E C H N O L O G Y . INSTITUTE OF T E C H N O L O G Y . WARSAW.
INSTITUTE OF TUBERCULOSIS. WARSAW
REFERENCES
[1] T. U r b a n s k i , B . S k o w r o n s k a - S e r a f i n . It. D a b r o w s k a . .1. J a n k o w s k a ,
On reactions of aromatic amines with cyamiuanidine. Formation of aryl-derivatives of
amidineurea and their transformation into carbanilides. Bull. Acad. Polon. Sci. CI. I l l
1 (1953), 74.
[2] T. U r b a n s k i , B . S k o w r o n s k a - S e r a f i n . II. D a b r o w s k a , Reactions of
aromatic amines with cyamiuanidine. Formation of derivatives of amidineurea and their
reactions with aniline, Bull. Acad. 1'olon. Sci. CI. I l l 2 (1954), 453.
[3] T . U r b a n s k i , B . S k o w r o n s k a - S e r a f i n . II. D a b r o w s k a , Roczniki Chein.
28 (1954). 423.