1932
BERESTOVITSKAYA et al.
nitro-3-thiolene 1,1-dioxide (I) in 15 ml of carbon
tetrachloride. Compound I gradually dissolved. The
reaction mixture was left to stand for 40 min. After
removal of the solvent and excess N2O4, a white
precipitate formed and was washed with diethyl ether
to obtain 0.68 g (52%) of compound V, mp 105
106 C (decomp.). Found, %: C 40.57, 40.58; H 3.34,
3.33; N 11.92, 11.91. C12H12N3O8S. Calculated, %:
C 40.34; H 3.08; N 11.76.
N 8.26, 8.24. C12H9ClN2O6S. Calculated, %: C 41.80;
H 2.61; N 8.13.
The mixture was separated by fractional crystalliza-
tion from benzene to obtain individual Z,E isomer Xa,
mp 160 162 C (from benzene).
3-Methyl-4-nitro-2-[nitro(p-nitrophenyl)me-
thylene]-3-thiolene 1,1-dioxide (XI). a. Dinitrogen
tetroxide, 6 ml, was added dropwise with stirring at
room temperature to a suspension of 0.3 g of com-
pound IV in 15 ml of carbon tetrachloride. The reac-
tion mixture was left to stand for 90 min, and the
solvent was evaporated to leave an oily substance
which was crystallized with methanol. A mixture of
3-Methyl-4,4-dinitro-2-[nitro(p-tolyl)methyl]-2-
thiolene 1,1-dioxide (VI) was obtained in a similar
way from compound II. Yield 24%, mp 102 105 C
(decomp.). Found, %: C 42.12, 42.10; H 3.63, 3.63;
N 11.31, 11.30. C13H13N3O8S. Calculated, %: C
42.05; H 3.50; N 11.32.
1
Z,E and E,E isomers XIa and XIb (2:3, by H NMR)
was obtained, yield 0.4 g (35%), mp 169 170 C
(from methanol). Found, %: C 40.65, 40.67; H 2.62,
2.64; N 11.88, 11.90. C12H9N3O8S. Calculated, %: C
40.56; H 2.50; N 11.80.
2-[(p-Chlorophenyl)nitromethyl]-3-methyl-4,4-
dinitro-2-thiolene 1,1-dioxide (VII) was obtained in
a similar way from compound III, except that the re-
action mixture was left to stand for 60 min. Yield
50%, mp 100 105 C (decomp.). Found, %: C 36.78,
36.80; H 2.53, 2.60; N 10.72, 10.77. C12H10ClN3O8S.
Calculated, %: C 36.78; H 2.55; N 10.77.
b. Fuming nitric acid, 1 ml, was added dropwise
with stirring at 0 C to a suspension of 0.3 g of com-
pound VIIIa in 10 ml of carbon tetrachloride. The
mixture was left to stand for 15 min and poured into
ice water to isolate 0.3 g (97%) of Z,E isomer XIa as
yellow crystals, mp 172 174 C (from acetone chlo-
roform, 1:1). Found, %: C 41.37, 41.37; H 2.37, 2.35;
N 11.98, 11.92. C12H9N3O8S. Calculated, %: C 40.56;
H 2.50; N 11.80.
3-Methyl-4-nitro-2-[nitro(phenyl)methylene]-3-
thiolene 1,1-dioxide (VIII). A suspendion of 0.3 g
of compound V in 3 ml of methanol was heated for
1 2 min on a sand bath. Nitrogen oxides evolved, the
starting compound dissolved, and yellow crystals
formed. The mixture was cooled to room temperature
and filtered to obtain 0.24 g (92%) of compound VIII
REFERENCES
1
as a 3:2 Z,E: E,E mixture (by H NMR), mp 130
1. Berestovitskaya, V.M., Zh. Obshch. Khim., 2000,
135 C (from methanol). Found, %: C 46.74, 46.73;
H 3.37, 3.45; N 9.05, 9.08. C12H10N2O6S. Calculated,
%: C 46.45; H 3.23; N 9.03.
vol. 70, no. 9, p. 1512.
2. Vasil’eva, M.V., Berestovitskaya, V.M., Berko-
va, G.A., and Pozdnyakov, V.P., Zh. Org. Khim.,
1986, vol. 22, no. 2, p. 428.
The mixture was separated by column chromato-
graphy (eluent benzene) or fractional crystallization
from benzene to obtain individual Z,E isomer VIIIa,
mp 155 158 C (from benzene).
3. Vasil’eva, M.V., Berestovitskaya, V.M., Berko-
va, G.A., and Perekalin, V.V., Zh. Org. Khim., 1988,
vol. 24, no. 2, p. 436.
4. Berestovitskaya, V.M., Yakovleva, O.G., Latypo-
va, V.V., Pozdnyakov, V.P., Vasil’eva, M.V., Zolo-
toi, A.B., and Kargina, N.M., Zh. Obshch. Khim.,
1991, vol. 61, no. 2, p. 351.
3-Methyl-4-nitro-2-[nitro(p-tolyl)methylene]-3-
thiolene 1,1-dioxide (IX) was obtained from com-
pound VI similarly to compound VIII, except that
the reaction mixture was left to stand for 20 min. A
mixture of Z,E and E,E isomers IXa and IXb (3:1, by
1H NMR) was isolated, yield 70%, mp 98 102 C
(from methanol). Found N, %: 8.35, 8.32. C13N12H2
O6S. Calculated N, %: 8.64.
5. Lipina, E.S., Perekalin, V.V., and Bobovich, Ya.S.,
Zh. Obshch. Khim., 1964, vol. 34, no. 11, p. 3640.
6. Lipina, E.S. and Perekalin, V.V., Acta Phys. Chem.,
1973, vol. 19, nos. 1 2, p. 125.
7. Bondi, A., J. Phys. Chem., 1964, vol. 68, no. 6,
2-[(p-Chlorophenyl)nitromethylene]-3-methyl-4-
nitro-3-thiolene 1,1-dioxide (X) was obtained from
compound VII similarly to compound VIII. A mix-
ture of Z,E and E,E isomers Xa and Xb (3:2, by H
NMR) was isolated, yield 90%, mp 135 138 C (from
methanol). Found, %: C 41.74, 41.75; H 2.78, 2.78;
p. 441.
8. Schultz, G., Hargittai, J., Kapovits, J., and Kuc-
sman, A., J. Chem. Soc., Faraday Trans. 2, 1984,
no. 80, p. 1273.
1
9. Borisov, A.V., Bodrikov, I.V., Borisova, G.N.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 12 2002