Synthesis of dinitrosulfodienes of the thiolene 1,1-dioxide series

Full text of DOI:10.1023/A:1012320627045

Russian Journal of General Chemistry, Vol. 71, No. 6, 2001, pp. 985 986. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 6, 2001,
pp. 1047 1048.
Original Russian Text Copyright
2001 by Efremova, Bortnikov, Berestovitskaya.
LETTERS
TO THE EDITOR
Synthesis of Dinitrosulfodienes
of the Thiolene 1,1-Dioxide Series
I. E. Efremova, S. V. Bortnikov, and V. M. Berestovitskaya
Hertzen Russian State Pedagogical University, St. Petersburg, Russia
Received November 30, 2000
Nitrothiolene-1,1-dioxides are convenient synthons
The reaction of 2-benzylidene-3-methyl-4-nitro-3-
thiolene 1,1-dioxide (I) with dinitrogen dioxide
proceeds in carbon tetrachloride for 0.5 h at 16 18 C
to give trinitrothiolene 1,1-dioxide III in 52% yield;
short heating (1 2 min) of the latter in methanol
(50 60 C) is accompanied by 1,4 elimination of
nitrous acid to provide a dinitrosulfodiene as a mix-
ture of geometric isomers IVa and IVb.
for constructing new types of functionalized thiolene-
and thiophene-1,1-dioxides [1 5]. Thus, the s-trans-
fixed diene system of 2-benzylidene-3-methyl-4-nitro-
3-thiolene 1,1-dioxides I, II, which was earlier widely
used for preparing nucleophilic addition products
[6, 7], proved highly effective in nitration reactions.
This finding opened the way to the synthesis of ori-
ginal dinitrosulfodienes of the thiolene dioxide series.
R = H (I), NO2 (II); Z,E (a), E,E (b).
The reaction of 3-methyl-4-nitro-2-(p-nitrobenzyl-
idene)-3-thiolene 1,1-dioxide (II) with N2O4 proceeds
slower (1.5 h) with a larger excess of the nitrating
agent (1:30) and produces compound Va, Vb in 35%
yield (method a). Compound Va, Vb was obtained
by independent synthesis via nitration of dinitrosul-
fodiene IVa, IVb with fuming nitric acid (method b).
(2.06 ppm), methylene (4.68 ppm), phenyl (7.46 ppm),
and nitromethine (7.04 ppm) protons. The spectrun
also contains bands due to the multiple bonds
1
1
(1610 cm ) and geminal nitro (1570, 1390 cm ) and
1
sulfonyl (1345, 1160 cm ) groups.
The dinitrosulfodienes are yellow crystalline sub-
stances. They are formed as mixtures of Z,E (IVa,
Va) and E,E (IVb, Vb) isomers, whose crystallization
or column chromatography gave individual Z,E
isomers IVa, Va.
The structure of the products was established on
1
the basis of spectral data. The H NMR spectrum of
trinitro derivative III contains signals of the methyl
1070-3632/01/7106-0985$25.00 2001 MAIK Nauka/Interperiodica

986
EFREMOVA et al.
1
The geometric isomers were identified by H NMR
spectroscopy. Because of the strong through-space
deshielding effect of the nitro group proximate to CH3
the methyl proton signals of E,E isomers
IVb, Vb are shifted downfield (2.45, 2.50 ppm)
compared with those in the Z,E isomers (1.85,
1.95 ppm), while the methylene proton signals the Z,E
form (4.55 ppm) are downfield from those of the E,E
form (4.45 ppm). The aromatic proton signals of IVa,
Vb, Va, and Vb appear at 7.30 8.45 ppm.
acetone chloroform, 1:1). Found, %: C 40.65; H 2.62;
N 11.88. C12H9N3O8S. Calculated, %: C 40.56; H
2.50; N 11.80.
The IR spectra were recorded on an IR-75 spec-
trometer in KBr. The H NMR spectra were recorded
on a Tesla BS-487C spectrometer (80 MHz), internal
reference HMDS, solvent CDCl3 (III, IVa, IVb) and
CD3CN (Va, Vb).
1
REFERENCES
The IR spectra of compounds IVa, IVb, Va, and
Vb contain bands of the multiple bonds (1610
1. Berestovitskaya, V.M., Zh. Obshch. Khim., 2000,
1
1590 cm ) and sulfonyl (1345 1310, 1170
vol. 70. no. 9, pp. 1512 1529.
1
1140 cm ) and conjugated nitro groups (1540 1520,
2. Khlytin, A.L., Efremova, I.E., Berestovitskaya, V.M.,
Gamazin, D.A., and Lapshina, L.V., Zh. Org. Khim.,
1997, vol. 33, no. 10, pp. 1596 1597.
1
1380 1340 cm ).
2-Benzylidene-3-methyl-4-nitro-3-thiolene 1,1-
dioxides I, II were prepared as described in [5].
3. Efremova, I.E., Berestovitskaya, V.M., and Pereka-
lin, V.V., Zh. Org. Khim., 1984, vol. 20, no. 4,
pp. 890 891.
3-Methyl-4,4-dinitro-2-[nitro(phenyl)methyl]-2-
thiolene 1,1-dioxide (III). Yield 52%, 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.
4. Efremova, I.E., Abzianidze, V.V., Berkova, G.A., and
Berestovitskaya, V.M., Zh. Obshch. Khim., 2000,
vol. 70, no. 6, pp. 1037 1038.
5. Vasil’eva, M.V., Berestovitskaya, V.M., Berkova, G.A.,
and Pozdnyakov, V.P., Zh. Org. Khim., 1986, vol. 22,
no. 2, pp. 428 434.
3-Methyl-4-nitro-2-[nitro(phenyl)methylene]-3-
thiolene 1,1-dioxide IVa, IVb. Yield 92%, mp 130
135 C (for a 1:2 Z,E:E,E mixture). Z,E isomer IVa:
mp 155 158 C (from benzene). 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.
6. Vasil’eva, M.V., Berestovitskaya, V.M., Berkova, G.A.,
and Perekalin, V.V., Zh. Org. Khim., 1988, vol. 24,
no. 2, pp. 436 442.
3-Methyl-4-nitro-2-[nitro(phenyl)methylene]-3-
thiolene 1,1-dioxide Va, Vb. Yield 35 (method a)
and 97% (method b), mp 169 170 C (for a 2:3 Z,E:
E,E mixture). Z,E isomer Va: mp 172 174 C (from
7. 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,
no. 2, pp. 351 358.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 6 2001