Russian Journal of Applied Chemistry, Vol. 77, No. 5, 2004, pp. 853 854. Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 5,
2004, pp. 858 859.
Original Russian Text Copyright
2004 by Klyuchnikov, Starovoitov, Khairutdinov, Golovin.
BRIEF
COMMUNICATIONS
Synthesis of Condensed Nitrofuroxanes Using Hydroxylamine
O. R. Klyuchnikov, V. I. Starovoitov, F. G. Khairutdinov, and V. V. Golovin
Kazan State Technological University, Kazan, Tatarstan, Russia
Received January 13, 2004
Abstract The possibility of preparing condensed nitrofuroxanes using hydroxylamine was examined.
Benzofuroxanes exhibit biological activity and are
intermediates in synthesis of a number of effective
NH OH HCl + CH COONa
2
3
antimicrobial agents; 4,6-dinitrobenzofuroxane in the
form of salts is used in priming charges [1]. In this
connection, it is interesting to develop relatively safe
methods for preparing nitrofuroxanes without using
azides.
O
O2 N
NO2
OH
O2 N
N
O +
N
(H2 N)
(H2 N)
.
NO2
NO2
EXPERIMENTAL
Previous studies concerning formation of the furox-
ane ring in synthesis of 4,6-dinitrobenzofuroxane by
reaction of picryl chloride, hydroxylamine hydrochlo-
ride, and sodium acetate showed that the intermediate
in this procedure is picrylhydroxylamine [2]. This
finding allowed preparation of 3-nitro[4,5-c]pyrido-
furoxane by the reaction of 4-hydroxylamino-3,5-di-
nitropyridine with picryl chloride [3]. Similarly, the
reaction of 2,4- or 2,6-dinitrophenylhydroxylamine or
its potassium salt with picryl chloride also yielded, re-
spectively, 4- or 6-nitrobenzofuroxane and picric acid:
4- and 6-Nitrobenzofuroxanes were prepared by
adding 2.48 g (0.01 mol) of picryl chloride to a
suspension of 2.37 g (0.01 mol) of potassium salt of,
respectively, 2,6- and 2,4-dinitrophenylhydroxylamine
in 30 ml of MeOH at room temperature with stirring.
The mixture was left for 0.5 h and poured into 60 ml
of water. The precipitate of 4- or 6-nitrobenzofuroxane
was filtered off, washed with water, and dried. Yield
of 4-nitrobenzofuroxane 1.67 g (92%), mp 112 C
(from EtOH); yield of 6-nitrobenzofuroxane 1.59 g
(88%), mp 74 76 C (from EtOH).
NHOH(K)
NO2
Cl
O2 N
NO2
(O2 N)
+
4,6-Dinitrobenzofuroxane was prepared by gradual
addition of 5.16 g (0.02 mol) of 1,2,3,5-tetranitroben-
zene to a suspension of 1.39 g (0.02 mol) of hydroxyl-
amine hydrochloride and 3.28 g (0.04 mol) of sodium
acetate in 50 ml of MeOH at 45 50 C with stirring.
The mixture was stirred at this temperature for an
additional 1 h, after which it was cooled and diluted
with water; the precipitate was filtered off, washed
with water, and dried. Yield 2.1 g (93%), mp 172 C
(from MeOH).
(NO2)
NO2
O
OH
N
O
O2 N
NO2.
(O2 N)
N
Base
(K)HCl
+
NO2
(NO2)
From compounds containing a labile nitro group,
4,6-dinitrobenzofuroxane derivatives are formed
also:
5-Amino-4,6-dinitrobenzofuroxane was prepared
similarly by adding 5.46 g (0.02 mol) of 2,3,4,6-tetra-
nitroaniline to a suspension of 1.39 g (0.02 mol) of
hydroxylamine hydrochloride and 3.28 g (0.04 mol)
of sodium acetate in 50 ml of MeOH at 45 50 C. The
reaction mixture was kept at this temperature for an
additional 2 h, after which it was cooled, and the pre-
NO2
NO2
O2 N
2
(H2 N)
NO2
1070-4272/04/7705-0853 2004 MAIK Nauka/Interperiodica