Dinitrosulfodienes of the thiolene 1,1-dioxide series in electron-transfer reactions [3]

Full text of DOI:10.1023/B:COHC.0000003535.20077.8d

Chemistry of Heterocyclic Compounds, Vol. 39, No. 8, 2003
DINITROSULFODIENES OF THE
THIOLENE 1,1-DIOXIDE SERIES IN
ELECTRON-TRANSFER REACTIONS
I. E. Efremova, S. V. Bortnikov, and V. M. Berestovitskaya
Keywords: 1,4-dinitro-1,3-dienes, thiolene 1,1-dioxides, electron transfer.
Conjugated aliphatic 1,4-dinitrodiene structures are active oxidants, and in the presence of 2 equivalents
2-
of an electron donor (Na/Hg, C10H8 2K+, KI) are converted to stable dinitro anions [1, 2]. The structure of
dinitro dienes of the thiolene 1,1-dioxide series [3, 4] of the 1a-d type is characterized by the fact that their
diene system is constructed from endocyclic and exocyclic conjugated multiple bonds of a five-membered
heterocycle, and the molecule has an additional electron-acceptor substituent: the SO2 group, which affects the
characteristic features of reactions with electron donors.
In contrast to open-chain analogs, dinitrosulfodienes 1a,c react via an electron-transfer route with such
representatives of donor reagents as N,N-dimethylaniline. These reactions are carried out at room temperature in
alcoholic solution, and lead to formation of stable crystalline molecular complexes 2a,b in which the role of the
donor component is played by N,N-dimethylaniline and the role of the acceptor component is played by the
electron-deficient structure of the heterocyclic dinitrosulfodiene. Evidence that 4a,b are complex compounds
comes from the presence in their electronic spectra of a charge-transfer band at λmax ~450 nm (ε 2000-4000),
close to the position of such a band (λmax 443 nm, ε ~33000) in molecular complexes formed by 3-methyl-2,4-
dinitrothiophene dioxide and pyridine [5, 6]. The binary composition of complexes 2a,b is also confirmed by
1H NMR spectra and elemental analysis.
In the presence of MeONa dinitrosulfodienes 1a-d, like the linear analogs [1, 2], are converted to
disodium salts 3a-d which are stable in solutions and unstable in the crystalline state. Formation of salts 3a-d is
confirmed by electronic spectra taken in 0.1 N NaOH solution, in which the bands at λ1 310-320 (ε 6000-16000)
and λ2 360 nm (ε 2500-8600) correspond to the conjugated dinitro anions.
As preparative proof of the structure, the salts 3a-d were subjected to oxidation and protonation under
conditions described earlier for conjugated dinitronates [2, 7]. Thus bromine treatment of a solution of nitronate
3a in absolute MeOH at room temperature leads to formation of dinitrosulfodiene 1a, and when a solution of
salt 3a is acidified with AcOH or HCl, the 3-methyl-4-nitro-2-(α-nitrobenzyl)-2-thiolene-1,1-dioxide (4) is
isolated.
The starting 3-methyl-4-nitro-2-(1-nitro-1-arylmethylene) 3-thiolene-1,1-dioxides 1a-d were synthesized
by the procedure in [4].
3-Methyl-4-nitro-2-(α-nitrobenzyl)-2-thiolene 1,1-Dioxide (4). Mp 189-191°C (MeOH). Mass
1
spectrum, m/z 312 [M]+. H NMR spectrum (CD3CN), δ, ppm (J, Hz): 2.00 (3H, s, CH3); 3.92-4.30 (2H, m,
2JAB = 15, CH2); 5.30 (1H, s, CH); 5.63 (1H, m, 3JAX = 6, 3JBX = 2, C(4)HNO2); 7.52, 7.91 (5H, m, CH arom.). IR
__________________________________________________________________________________________
A. I. Herzen Russian State Pedagogical University, St. Petersburg 191186; e-mail:
chemis@herzen.spb.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1267-1268,
August, 2003. Original article submitted May 7, 2003.
0009-3122/03/3908-1111$25.00©2003 Plenum Publishing Corporation
1111

_
NO2
NO2
p-
XH4C6
MeONa
p-
XH4C6
+
_
2Na
O2N
Br2
–2NaBr
SO2
1a–d
O2N
SO2
3a–d
(for 1a,c)
PhNMe2
(for 3a)
–2Na
+
+
H
NMe2
NO2
NO2
H
p-
XH4C6
O2N
Ph
H
O2N
SO2
2a,b
SO2
4
1a, 2a, 3 X = H, 1b, 3b R = Me, 1c, 2b, 3c R = Cl, 1d, 3d R = NO2
spectrum (nujol), λ, cm-1: 1620 (C=C, Ar); 1570, 1350 (NO2), 1350, 1140 (SO2). Found, %: C 46.28, 46.31;
H 3.49, 3.50; N 9.24, 9.28. C12H12N2O6S. Calculated, %: C 46.15; H 3.85; N 8.97. M 312.
Molecular Complex of 3-Methyl-4-nitro-2-(α-nitrobenzylidene)-3-thiolene 1,1-Dioxide with
1
N,N-Dimethylaniline (3a). Mp 299-300°C (with decomposition). H NMR spectrum (CDCl3), δ, ppm: 1.90
(3H, s, CH3); 3.00 (6H, s, N(CH3)2); 4.50 (2H, s, CH2); 6.60, 6.80, 7.40, 7.55, 7.68, 7.75 (10H, m, CH arom.).
Found, %: C 55.58, 55.57; H 4.74, 4.78; N 9.92, 9.66. C20H21N3O6S. Calculated, %: C 55.68; H 4.87; N 9.74.
p
Molecular Complex of 3-Methyl-4-nitro-2-[α-nitro-1-( -chlorophenyl)methylene]-3-thiolene
1
1,1-Dioxide with N,N-Dimethylaniline (3b). Mp 297-299°C (with decomposition). H NMR spectrum
(CDCl3), δ, ppm: 1.95 (3H, s, CH3); 3.00 (6H, s, N(CH3)2); 4.55 (2H, s, CH2); 6.65, 6.80, 7.45, 7.50, 7.70, 7.80
(9H, m, CH arom.). Found, %: N 9.00, 9.02. C20H20ClN3O6S. Calculated, %: N 9.02.
REFERENCES
1.
2.
3.
4.
E. S. Lipina and V. V. Perekalin, Acta Phys. Chem., 19, 125 (1973).
E. S. Lipina and V. V. Perekalin, Zh. Obshch. Khim., 34, 3644 (1965).
I. E. Efremova, S. V. Bortnikov, and V. M. Berestovitskaya, Zh. Obshch. Khim., 71, 1047 (2001).
V. M. Berestovitskaya, I. E. Efremova, S. V. Bortnikov, I. A. Litvinov, and O. N. Kataeva, Zh. Obshch.
Khim., 72, 2035 (2002).
5.
6.
7.
V. M. Berestovitskaya, I. E. Efremova, A. L. Khlytin, G. A. Berkova, V. P. Pozdnyakov, and
D. A. Gamazin, Zh. Org. Khim., 32, 152 (1996).
I. E. Efremova, L. V. Lapshina, and V. M. Berestovitskaya, Izv. RGPU, Estestvennye i Tochnye Nauki,
No. 2 (4), 104 (2002).
V. M. Berestovitskaya, M. V. Titova, and V. V. Perekalin, Zh. Org. Khim., 18, 1783 (1982).
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