Thiolene 1,1-dioxides. Synthesis of azido- and aminonitrosulfodienes [3]

Full text of DOI:10.1023/A:1021706202702

Chemistry of Heterocyclic Compounds, Vol. 38, No. 10, 2002
THIOLENE 1,1-DIOXIDES. SYNTHESIS OF
AZIDO- AND AMINONITROSULFODIENES
I. E. Efremova, S. V. Bortnikov, and B. M. Berestovitskaya
Keywords: azide group, heterocycles, nitro group, nitrothiolene dioxides, amination.
Dinitrothiolene 1,1-dioxides [1] containing the s-trans-fixed 1,4-dinitro-1,3-diene system hold interest
as key synthones for the preparation of functionally substituted heterocyclic nitrosulfodienes. Dinitrodienes are
capable of reacting with nucleophiles through an electron transfer pathway as well as AdN and SNVin reactions
[2, 3].
Me
NO2
NO2
Me
C
NaN3
NH2R
– HN3
Ph
N3
Ph
– HNO2
SO2
C
SO2
O2N
2
1
Me
C
NO2
Ph
SO2
RHN
3, 4
3 R = Ph, 4 R = NHPh
We have shown that the reaction of dinitrosulfodiene 1 with sodium azide in acetic acid at room
temperature proceeds chemo-, regio-, and stereoselectively to give the product of nucleophilic vinyl substitution
of the exocyclic nitro group, namely, Z,E-2-(1-azido-1-phenyl)methylene-3-methyl-4-nitro-3-thiolene
1,1-dioxide (2) in yields above 50%. The reaction of 2 with aniline and phenylhydrazine proceed through an
analogous SNVin pathway to give nitroenamines 3 and 4.
We note that 3 and 4 could not be obtained directly from dinitrothiolene 1,1-dioxide 1. This failure is
probably related to the high oxidizing capacity of this dioxide and its high tendency to oxidize amines.
Azido- and aminonitrosulfodienes 2-4 are stable crystalline compounds, which are colorless in the
crystalline state but appear yellow in polar solvents. The structure of 2-4 was assigned by analyzing their
spectral data in comparison with the indices of 1 [1] and a model analog, namely, 4-anilino-1-nitro-2,3-diphenyl-
1,3-butadiene [4]
Heterocyclic nitroenamines 3 and 4 hold interest as compounds with potential biological activity [5, 6].
1
The IR spectra were taken on a Specord IR-75 spectrometer. The H NMR spectra were taken for
solutions in CDCl3 on a Bruker AC-200 spectrometer at 200 MHz with HMDS as the internal standard.
__________________________________________________________________________________________
A. Hertzen Russian State Pedagogical University, St. Petersburg 191186, Russia, e-mail:
chemis@herzen.spb.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1464-1465,
October, 2002. Original article submitted August 14, 2002.
0009-3122/02/3810-1293$27.00©2002 Plenum Publishing Corporation
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2-(1-Azido-1-phenyl)methylene-3-methyl-4-nitro-3-thiolene 1,1-Dioxide (2) was obtained in 51%
yield; mp 162-165°C (dec., from acetic acid). IR spectrum, ν, cm-1: 1635 (C=C), 1520, 1330 (NO2), 1330, 1130
1
(SO2), 2130 (N3). H NMR spectrum, δ, ppm: 2.02 (3H, s, CH3); 4.52 (2H, s, CH2); 7.40-8.05 (5H, m, Ph).
Found, %: C 47.14, 47.14; H 3.51, 3.54; N 18.35, 18.30. C12H10N4O4S. Calculated, %: C 47.06; H 3.27; N 18.30.
2-(1-Anilino-1-phenyl)methylene-3-methyl-4-nitro-3-thiolene 1,1-Dioxide (3) was obtained in 25%
yield; mp 157-158°C (ethanol). IR spectrum, ν, cm-1: 1610 (C=C), 1550, 1320 (NO2), 1320, 1140 (SO2), 3330
(NH). 1H NMR spectrum, δ, ppm: 1.90 (3H, s, CH3); 4.75 (2H, s, CH2); 6.90, 7.20, 7.93, 7.80, 8.15 (11H, m, Ph,
NH). Found, %: C 60.80, 60.78; H 4.67, 4.65; N 7.99, 8.02. C18H16N2O4S. Calculated, %: C 60.67; H 4.49;
N 7.87.
3-Methyl-4-nitro-2-(1-phenyl-1-phenylhydrazino)methylene-3-thiolene 1,1-Dioxide (40 was
obtained in 24% yield; mp 110-111°C (ethanol). IR spectrum, ν, cm-1: 1600 (C=C), 1555, 1320 (NO2), 1320,
1140 (SO2), 3330 (NH). 1H NMR spectrum, δ, ppm: 2.00 (3H, s, CH3); 4.48 (2H, s, CH2); 6.80, 7.00, 7.25, 7.48,
7.70, 8.00 (12H, m, Ph, NH). Found, %: C 58.20, 58.24; H 4.51, 4.54; N 11.35, 11.30. C18H17N3O4S.
Calculated, %: C 58.22; H 4.58; N 11.32.
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