LETTERS TO THE EDITOR

REACTION OF 5-NITROANTHRANILIC ACID WITH

p-TOLUENESULFONYL CHLORIDE IN PYRIDINE

M. V. Loseva, B. M. Bolotin, UDC 547.867.5'856.7:543.422.4'51

and Yu. S. Ryabokobylko

We have p r e v i o u s l y [1] d e m o n s t r a t e d that 2 - ( 2 - t o s y l a m i n o p h e n y l ) - 4 H - 3 , 1 - b e n z o x a z i n - 4 - o n e is f o r m e d

in the r e a c t i o n of anthranilic acid with p-toluenesulfonyl chloride in refluxing pyridine. In an investigation
of the reaction of 5 - n i t r o a n t h r a n i l i c acid with p-toluenesulfonyl chloride, we i s o l a t e d I (rap 298 ~ and II (rap
256.5~ which differed s h a r p l y in composition and p r o p e r t i e s f r o m the expected 2 - ( 2 - t o s y l a m i n o - 5 - n i t r o -
p h e n y l ) - 6 - n i t r o - 4 H - 3 , I - b e n z o x a z i n - 4 - o n e . At r o o m t e m p e r a t u r e the yields of I and II w e r e 26 and 72%,
r e s p e c t i v e l y , c o m p a r e d with 59 and 29% at 114 ~.
Substance I is 2- ( 2 - a m i n o - 5 - n i t r o p h e n y l ) - 6 - n i t r o - 4 H - 3 , 1 - b e n z o x a z i n - 4 - o n e . IR s p e c t r u m : 1765
(VC ----O in benzoxazinones [2]), 3296, and 3443 c m -1 (PNH2). Found: C 51.2; H 2.7; N 17.2~c. CI4HaN406.
Calculated: C 51.2; H 2.5; N 17.1%.
Substance II [Found: C 60.2; H 2.8; N 17.2%; tool. wt. 241 (mass s p e c t r o s c o p y ) . C12HTN303. C a l c u -
l a t e d : C 59.8; H 2.9; N 17.4%] differs m a r k e d l y in its optical and c h e m i c a l p r o p e r t i e s f r o m I. Solutions of
II l u m i n e s c e intensely at r o o m t e m p e r a t u r e , which is not c h a r a c t e r i s t i c for n i t r o - s u b s t i t u t e d benzoxazinones.
Compound II f o r m s a stable h y d r o c h l o r i d e . Absorption bands in the region of the s t r e t c h i n g v i b r a t i o n s of
NH bonds a r e not o b s e r v e d in the IR s p e c t r u m of II. The band at 1710 c m -1 is c l o s e s t to V c = O of N -
p h e n y l - s u b s t i t u t e d t e r t i a r y amides [3]. In the IR s p e c t r u m of the hydrochloride, v c = O is shifted m a r k e d l y
to the h i g h e r - w a v e - n u m b e r region (1750 c m -1) as c o m p a r e d with II. This s o r t of shift m e a n s that a n i t r o -
gen that is capable of salt f o r m a t i o n is in d i r e c t p r o x i m i t y to the c a r b o n y l group. The p r e s e n c e of a CsH4N 2+
f r a g m e n t with m / e 78 was e s t a b l i s h e d in the m a s s s p e c t r u m of II. The II m o l e c u l e consequently includes a
pyridine r i n g . On the b a s i s of these data, we assigned the 2 - n i t r o - l l H - p y r i d o [ 2 , 1 - b ] - l l - q u i n a z o l i n o n e
s t r u c t u r e to II.
O 0
o~N~f"-o o ~N, , . ~ : - ~ . / \ ,v~.%,"

I II

Using the method in [4] for the s y n t h e s i s of unsubstituted 1 1 H - p y r i d o [ 2 , 1 - b ] - l l - q u i n a z o l i n o n e , we ob-

tained a s u b s t a n c e f r o m 5 - n i t r o a n t h r a n i l i c acid and 2 - c h l o r o p y r i d i n e that was identical to II with r e s p e c t to
the IR and UV s p e c t r a and melting points.

LITERATURE CITED
1. M. V. L o s e v a , B. M. Bolotin, and I. P. Shepilov, C h e m i c a l Reagents and P r e p a r a t i o n s [in Russian],
T r u d y IREA, Moscow (1971), No. 33.
2o K. L e m p e r t and G. Doleshall, T e t . L e t t e r s , 781 (1963).
3. L. B e l l a m y , I n f r a - R e d Spectra of Complex Molecules, Methuen (1958).
4. O. A. Zaide and G. V. C h e l i n t s e v , Zh. Obshch. Khim., 7, 2314 (1937).

All-Union S c i e n t i f i c - R e s e a r c h Institute of C h e m i c a l Reagents and E s p e c i a l l y P u r e C h e m i c a l Sub-

s t a n c e s , Moscow. T r a n s l a t e d f r o m Khimiya G e t e r o t s i k l i c h e s k i k h Soedinenii, No. 7, p. 1003, July, 1972.
Original a r t i c l e submitted S e p t e m b e r 17, 1971.

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