Synthesis of 4-aryl-5-nitro-1,2,3-triazoles

Full text of DOI:10.1023/B:RUJO.0000036090.61432.18

Russian Journal of Organic Chemistry, Vol. 40, No. 4, 2004, pp. 594–595. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 4, 2004,
pp. 620–621.
Original Russian Text Copyright © 2004 by Sheremet, Tomanov, Trukhin, Berestovitskaya.
SHORT
COMMUNICATIONS
Synthesis of 4-Aryl-5-nitro-1,2,3-triazoles
E. A. Sheremet, R. I. Tomanov, E. V. Trukhin, and V. M. Berestovitskaya
Hertzen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received November 4, 2003
It is known that some 1,2,3-triazole derivatives
possess practically important properties. For example,
4-(4-methoxyphenyl)-5-nitro-1,2,3-triazole exhibits
antifungal activity, and 4-(4-bromophenyl)- and 4-(4-
nitrophenyl)-5-nitro-1,2,3-triazoles are tuberculostatic
and fungicide agents [1]. Some 1,2,3-triazoles can be
used as photostabilizers and optical bleaching agents
[2, 3], and they may be regarded as precursors of
azapurines which are potential carcinostatic agents [2].
[1]. 1,2,3-Triazoles VIII and IX were previously
unknown. It should be noted that 2-aryl-1-bromo-1-
nitroethenes failed to react with sodium azide in aceto-
nitrile. Presumably, the reaction of sodium azide with
β,β-dinitrostyrenes I–III, as well as with geminal
bromonitrostyrenes IV–VI [1], formally follows
1,3-cycloaddition pattern [3].
The structure of aryl-substituted nitro-1,2,3-tri-
azoles was confirmed by elemental analysis and
1
1H and IR spectroscopy. The H NMR spectra of
The synthesis of nitro-1,2,3-triazoles having aryl
substituents at the ring carbon atoms was described
by Khisamutdinov and co-workers [1, 4]. It is based
on the reaction of 2-aryl-1-bromo-1-nitroethenes or
2-aryl-1,2-dibromo-2-nitroethanes with sodium azide
in aprotic (DMF, DMSO) or protic (ethanol) solvents.
4-aryl-5-nitro-1,2,3-triazoles VII-IX contain signals
from protons of the aromatic ring at δ 7.31–7.78 ppm.
In the IR spectra, absorption bands arising from vibra-
tions of multiple bonds (1610–1615 cm–1), conjugated
nitro group (1510–1530 and 1374–1380 cm–1), and
1,2,3-triazole ring (990–1022 cm–1) were present.
1,1-Dinitroethene derivatives, specifically β,β-di-
nitrostyrenes, are highly reactive compounds [5–8]
which can be used in the synthesis of nitro-1,2,3-
triazoles. We have shown that β,β-dinitrostyrenes I–III
react with 2 equiv of sodium azide under fairly mild
conditions, in anhydrous acetonitrile at room tempera-
ture. The reaction takes 2.5–4.5 h, and the products
are 4-aryl-5-nitro-1,2,3-triazoles VII–IX which are
formed in 59–77% yield. Compounds VII–IX were
also synthesized by independent method from the
corresponding β-bromo-β-nitrostyrenes and sodium
azide in DMF, following a slightly modified procedure
Initial 2-aryl-1,1-dinitroethenes I–III were synthe-
sized by the procedures described in [9, 10].
5-Nitro-4-phenyl-1,2,3-triazole (VII). a. A solu-
tion of 0.29 g (1.5 mmol) of 1,1-dinitro-2-phenyl-
ethene (I) in 12.5 ml of anhydrous acetonitrile was
added to a suspension of 0.20 g (3 mmol) of sodium
azide in 12.5 ml of anhydrous acetonitrile. The mixture
was stirred for 2.5 h at room temperature, the precip-
itate was filtered off, and the filtrate was poured onto
finely crushed ice and acidified with acetic acid. The
aqueous phase was extracted with diethyl ether, the
organic layer was separated and dried over magnesium
sulfate, and the solvent was evaporated. Yield 0.17 g
(59%). Colorless crystals, mp 196–198°C (from
chloroform); published data [1]: mp 199–201°C (from
CH3COOH–CCl4).
NO2
ArCH
C
Ar
NO2
NO2
NaN3
I–III
N
NH
N
NO2
Br
ArCH
C
VII–IX
b. A mixture of 0.46 g (2 mmol) of 1-bromo-1-
nitro-2-phenylethene (IV) and 0.26 g (4 mmol) of
sodium azide in 15 ml of DMF was stirred for 2.5 h at
room temperature. The mixture was poured onto finely
crushed ice and acidified with hydrochloric acid to
IV–VI
I, IV, VII, Ar = Ph; II, V, VIII, Ar = 4-MeC6H4;
III, VI, IX, Ar = 4-ClC6H4.
1070-4280/04/4004-0594 © 2004 MAIK “Nauka/Interperiodica”

SYNTHESIS OF 4-ARYL-5-NITRO-1,2,3-TRIAZOLES
595
pH ~1, and the precipitate was filtered off. Yield 0.22 g
(52%), mp 195–196°C. The product showed no de-
pression of the melting point on mixing with a sample
prepared as described in a.
spectra were measured on an InfraLYuM FT-02 spec-
trometer from samples dispersed in mineral oil.
This study was performed under financial support
by the Ministry of Education of the Russian Federation
(project nos. E02-5.0-138 and A03-2.11-517).
5-Nitro-4-(p-tolyl)-1,2,3-triazole (VIII). a. Com-
pound VIII was synthesized from 1,1-dinitro-2-
(p-tolyl)ethene (II) in a way similar to the synthesis of
VII. Yield 65%. Colorless crystals, mp 207–209°C
(from chloroform). Found, %: C 53.00, 53.07; H 4.09,
4.08; N 27.47, 27.50. C9H8N4O2. Calculated, %:
C 52.94; H 3.92; N 27.45.
REFERENCES
1. Khisamutdinov, G.Kh., Bondarenko, O.A., Kupriyano-
va, L.A., Klimenko, V.G., and Demina, L.A., Zh. Org.
Khim., 1979, vol. 15, p. 1307.
2 Comprehensive Organic Chemistry, Barton, D. and
Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 4.
Translated under the title Obshchaya organicheskaya
khimiya, Moscow: Khimiya, 1985, vol. 8, p. 430.
3. Gilchrist, T.L., Heterocyclic Chemistry, Harlow, Essex,
England: Longman Scientific & Technical, 1992,
2nd ed. Translated under the title Khimiya getero-
tsiklicheskikh soedinenii, Moscow: Mir, 1996, p. 351.
4. Khisamutdinov, G.Kh., Bondarenko, O.A., and Kupriya-
nova, L.A., Zh. Org. Khim., 1975, vol. 11, p. 2445.
5. Berestovitskaya, V.M., Trukhin, E.V., and Kornee-
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8. Benhaoua, H., Piet, J.-C., Danion-Bougot, R., and
Carrie, R., Bull. Soc. Chim. Fr., 1987, vol. 2, p. 325.
9. Novikov, S.S., Belikov, V.M., Dem’yanenko, V.F., and
Lapshina, L.V., Izv. Akad. Nauk SSSR. Ser. Khim., 1960,
p. 1295.
b. Compound VIII was obtained from 1-bromo-1-
nitro-2-(p-tolyl)ethene (V) by the procedure described
above for the synthesis of triazole VII (method b).
Yield 51%, mp 205–207°C (from chloroform). No de-
pression of the melting point was observed on mixing
with a sample prepared as described in a.
4-(4-Chlorophenyl)-5-nitro-1,2,3-triazole (IX).
a. Compound IX was synthesized from 2-(4-chloro-
phenyl)-1,1-dinitroethene (III) as described above for
VII (method a). Reaction time 4.5 h. Yield 77%.
Colorless crystals, mp 198–199°C (from chloroform).
b. Compound IX was obtained from 1-bromo-2-(4-
chlorophenyl)-1-nitroethene (VI) by the procedure
described above for the synthesis of triazole VII
(method b). Yield 52%. mp 197–198°C. No depression
of the melting point was observed on mixing with
a sample prepared as described in a. Found, %:
C 42.75, 42.78; H 2.38, 2.37; N 24.97, 24.91.
C8H5ClN4O2. Calculated, %: C 42.76; H 2.22; N 24.94.
1
The H NMR spectra were recorded on a Bruker
10. Kim, T.R., Lee, Y.H., and Chai, W.S., Igong Nonjip.,
AC-200 instrument (200 MHz) in DMSO-d6. The IR
1985, vol. 26, p. 195.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 4 2004