Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 10, pp. 1769−1775.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
V.N. Kizhnyaev, F.A. Pokatilov, L.I. Vereshchagin, O.N. Verkhozina, T.L. Petrova, A.G. Prodaikov, G.V. Ratovskii, O.V. Tyukalova, 2009,
published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 10, pp. 1616−1622.
STUDIES IN THE FIELD OF CHEMISTRY OF NITRO COMPOUNDS
(TO 100TH BIRTHDAY ANNIVERSARY OF S. S. NOVIKOV)
Synthesis of Energetic Polynuclear
and Polymeric Nitroazole Systems
V. N. Kizhnyaev, F. A. Pokatilov, L. I. Vereshchagin, O. N. Verkhozina, T. L. Petrova,
A. G. Prodaikov, G. V. Ratovskii, and O. V. Tyukalova
Irkutsk State University, Irkutsk, Russia
Received April 29, 2009
Abstract—Interaction of cyanuric chloride and its mono and dichloro derivatives with ammonium or sodium
4-nitro-1,2,3-triazolates and polymer-analogous transformations of tetrazole-containing polymers were used to
synthesize polynuclear systems and macromolecular compounds with heterocyclic structures bearing explosophoric
In development of high-efficiency formulations
of solid-propellant, explosive, and gas-generating
formulations, particular attention is to be given to
polynitrous heterocyclic compounds, whose application
promise is determined by their high enthalpies of
formation, thermal stability, resistance to mechanical
shocks, and comparatively large content of nitrogen.
The increase in the energetic characteristics of these
compounds is favored by introduction of nitro groups
and other explosophoric substituents into heterocyclic
fragments [1–3]. Fairly promising energetic products
are polynuclear heterocyclic systems containing in their
structure nitro groups in addition to triazole, tetrazole, and
1,3,5-triazine rings. The results of syntheses of substances
of this kind are reﬂ ected in our communication.
Commercial cyanuric chloride of 99.5% purity was
used in the study. Its derivatives, 2,4-dichloro-6-methoxy,
, 2-chloro-4,6-diaethylamino-, and 2-chloro-4,6-
dimorpholino-1,3,5-triazines, were synthesized using the
procedures reported in [4, 5]; 4(5)-nitro-1,2,3-triazole,
3-nitro- and 3-azido-1,2,4-triazoles, their N-chloromethyl
derivatives, and chloromethyl methylnitramine were
synthesized by the methods described in [6–8]. Poly-
5-vinyltetrazole (PVT) (M = 5 10
) was produced by
radical polymerization of the corresponding monomer as
it was done in .
We synthesized 2,4,6-tri(4-nitro-1,2,3-triazol-
1-yl)-1,3,5-triazine as follows. To a solution of
a triethylammonium salt produced from 1.14 g (10 mmol)
of 4-nitro-1,2,3-triaziole and 1.02 g (10mmol) of
triethylamine in 10 ml of acetone was added dropwise at
room temperature 0.61 g (3mmol) of cyanuric chloride in
15 ml of acetone. The reaction mixture was agitated for
1 h and poured into 100 ml of cold water. The precipitate
was ﬁ ltered off and dried in air. Yield 1.5 g, mp > 350°C.
IR spectrum, ν, cm
: 1560 (NO
C NMR spectrum, δ,
ppm, DMSO: 160.5 (3C-2,4,6 of triazine), 153.6 (3C-4
of triazole), 124.7 (3C-5 of triazole).
Similarly, we obtained 2-(4-nitro-1,2,3-triazol-1-yl)-
4,6-dimethoxytriazine from 1.4 g (8 mmol) of 2-chloro-
4,6-dimethoxytriazine, 1 g (8.8 mmol) of triethylamine in
10 ml of acetone. Yield 0.6 g (30%), mp 122–124°C. IR
spectrum, ν, cm
: 1219 (–O–), 1565 (NO
), 1603 (C=N
C NMR spectrum, δ, ppm, DMSO: 173.2
(C-6 of triazine), 160.5 (2C-2,4 of triazine), 153.6 (2C-
4 of triazole), 124.7 (2C-5 of triazole), 56.6 (C, CH
Found: C 28.95, H 1.03, N 46.24. С
C 28.66, H 1.49, N 45.97.
We synthesized 2-(4-nitro-5-phenyl-1,2,3-triazol-1-
yl)-4,6-dimethoxy-1,3,5-triazine from 0.87 g (5 mmol)
of 2-chloro-4,6-dimethoxytriazine, 1 g (5.3 mmol) of