SYNTHESIS OF 6(5)-METHYL-5,7(4,6)-DINITRO-1H-BENZO[1.2.3]TRIAZOLE
137
20.4 s (1C, CH3), 124.1 s (1C, C3), 128.9 s (1C, C5),
132.8 s (1C, C6), 135.3 s (2C, C2, C4), 144.1 s (1C,
mixture was poured into 50 ml of ice water. A pre-
cipitate formed and was filtered off, washed to neutral
washings, and dried in a thermostat at 70 C. Yield
150 mg (66.3%), light yellow substance, mp 194
207 C. Recrystallization gave white needle crystals,
mp 222 C. The NMR, IR, and UV spectra of the ob-
tained compound were fully identical to those of the
dinitro derivative prepared by procedure A.
1
C1). IR spectrum, cm : as(N O) 1535, s(N O)
1335, (N N, nitro) 835, (N N, imide) 1000 1300,
(N H) 1630, (C H, methyl) 1405. UV spectrum,
max, nm (log ): 240.8 (3.42), 310.9 (3.97).
6(5)-Methyl-5,7(4,6)-dinitro-1H-benzo[1.2.3]tri-
azole (III). Procedure A. Benzotriazole II, 41.3 mg
(0.23 mmol), was dissolved in 0.6 ml of sulfuric acid
at room temperature under stirring in a 5-ml flack and
then 0.2 ml of 99.6% nitric acid was added in one
portion. The reaction mixture was heated at 60 70 C
for 5 h, two 0.1-ml portions of nitric acid were then
added to at that temperature at an interval of 3 h, and
heating was continued for 4 h. After that the reaction
mixture was poured into 10 ml of ice water, and the
precipitate formed after its conglomeration (12 h) was
filtered off, washed with water to neutral washings,
and dried in a thermostat at 70 C. Yield of crude
product 34.2 mg (66%), yellow solid, mp 194 207 C
(decomp). Recrystallization from chloroform followed
by double crystallization from 50% aqueous 2-pro-
panol gave 23.4 mg (30.6%) of light yellow needle
crystals, mp 219 220 C. Found, %: C 37.55, H 2.16,
N 30.65. C7H5N5O4. Calculated, %: C 37.67, H 2.22,
N 31.38, O 28.73. 1H NMR spectrum, , ppm
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(DMSO-d6): 2.83
s (3H, CH3), 9.04 s (1H,
Harom), 14.0 s (1H, NH); CDCl3: 2.91 s (3H, CH3),
8.8 s (1H, Harom), 13.9 s (1H, NH). 13C NMR spec-
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,
max
nm (log ): 243.2 nm (4.10), 205.3 nm (4.42), 290
(3.92) (shoulder).
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perature in a 10-ml flask, and then 0.7 ml of 99.6%
nitric acid was added. The flask was placed into a
microwave oven and exposed to microwave radiation
at 750 W (7 10 s). Then the reaction vessel was
cooled in air at room temperature for 0.5 h and ex-
posed again (6 10 s). After cooling, the reaction
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007