MIKOVA et al.
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on a water bath to 60°C for 48 h. Yield 81%, mp 134–
136°C (ether). IR spectrum (KBr), ν, cm–1: 1590, 1560
(C=C), 1550, 1324 (NO2). UV spectrum, λ, nm (ε): 240
h the orange-red precipitate was filtered off and subjected
to purification by column chromatography. From the
fraction eluted with ether we isolated 0.22 g (53%) of
compound Va, mp 182–184°C. IR spectrum, ν, cm–1: 1595,
1567 (C=C, C=N), 1362, 1333 (NOO–). UV spectrum,
λ, nm (ε): 304 (13000), 387 (19000). 1H NMR spectrum
(CDCl3), δ, ppm: 7.74 s (=C–H), 7.30–7.16 m (Ph, Ht),
11.55 s (NH), 6.72 s (CH). Found, %: N 13.78.
C15H11N3O2C. Calculated, %: N 14.14.
1
(7000), 332 (10000). H NMR spectrum, δ, ppm: 7.91 s
(=C–H), 7.84–7.56 m (Ph), 9.50 s (NH). Found, %:
C 48.32; H 4.26; N 18.72. C9H9N3O2C. Calculated, %:
C 48.43; H 4.03; N 18.83.
2-Nitro-1-phenyl-1-ethenylsulfanyl(phenyl-
imino)methyl(phenyl)amine (IVa). To a solution of
0.275 g (1 mmol) of compound I in 3 ml of anhydrous
ethanol was poured a suspension of 0.228 g (1 mmol) of
N,N'-diphenylthiourea in 3 ml of anhydrous ethanol.After
5 min the precipitate was filtered off. Yield 0.257 g (68%),
yellow crystals, mp 117–119°C (ether). IR spectrum, ν,
cm–1: 1628, 1589 (C=C), 1500, 1312 (NO2). UV
spectrum, λ, nm (ε): 232 (1670), 340 (4700). 1H NMR
spectrum (CDCl3), δ, ppm: 7.01 s (=CH), 7.31–7.27 m
(Ph). Found, %: N 10.85. C21H17N3O2S. Calculated, %:
N 11.19.
2-(2-Nitro-1-phenyl-1-ethenylsulfanyl)-1,3-
benzothiazol-6-amine (Vb). To a suspension of
0.182 g (1 mmol) of 5-aminobenzothiazolyl-2-thiol in
3 ml of anhydrous methanol was poured 0.6 ml (1 mmol)
of triethylamine. The obtained thiolate was slowly added
dropwise to a solution of 0.275 g (1 mmol) of compound
I in 2 ml of anhydrous methanol. After 10 min the dirty-
yellow precipitate was filtered off and subjected to
purification by column chromatography. From the fraction
eluted with benzene we separated 0.16 g (46%) of yellow
precipitate of compound Vb, mp 124–127°C, then elution
was continued with ether, and 0.08 g (23%) of orange
precipitate of compound Va was additionally isolated, mp
180–184°C. Nitrothioethene Vb was obtained in the
similar way from compound II.After 30 min the reaction
mixture was concentrated on a rotary evaporator in
a vacuum, and the yellow precipitate of compound Vb
was filtered off. Yield 20%, mp 124–127°C. IR spectrum,
ν, cm–1: 1619, 1600 (C=C), 1510, 1332 (NO2). UV
Anilino-2-nitro-1-phenyl-1-ethenylanilino-
methanethione (IVb). To a solution of 0.12 g (0.4 mmol)
of compound II in 3 ml of anhydrous ethanol was poured
a suspension of 0.091 g (0.4 mmol) of N,N'-diphenyl-
thiourea in 3 ml of anhydrous ethanol. The reaction mixture
was heated at 60°C for 60 h, then cooled to 0°C and the
precipitate was filtered off. Yield 0.05 g (45%), yellow
crystals, mp 193–195°C (ether). IR spectrum, ν, cm–1:
1611, 1594 (C=C, C=N), 1367, 1326, 1255 (NOO–). UV
spectrum, λ, nm (ε): 235 (7200), 293 (5000), 378 (12000).
1H NMR spectrum (CDCl3), δ, ppm: 7.63 s (=CH), 7.42–
7.30 m (Ph), 8.01 s (NH). Found, %: C 67.02; H 4.78;
N 10.77. C21H17N3O2C. Calculated, %: C 67.18; H 4.53;
N 11.19.
1
spectrum, λ, nm (ε): 263 (6600), 325 (8700). H NMR
spectrum (CDCl3), δ, ppm: 7.85 s (=CH), 7.38–7.24 m
(Ph, Ht), 5.58 s (NH2). Found, %: C 60.52; H 3.59.
C15H11N3O2C. Calculated, %: C 60.60; H 3.70.
5-(2-Nitro-2-phenyl-1-ethenylamino)-1,3-benzo-
thiazole-2-thiol (VIII). To a suspension of 0.146 g
(0.5 mmol) of 1-nitro-2-p-chlorophenylsulfanyl-1-
phenylethene (VI) in 5 ml of methanol was poured a sus-
pension of 0.091 g (0.5 mmol) of 5-aminobenzothiazolyl-
2-thiol in 10 ml of methanol. After 24 h the dirty-yellow
precipitate was filtered off and subjected to purification
by column chromatography. From the fraction eluted with
ether was isolated 0.16 g (90%) of bright-yellow
precipitate of compound VIII, mp 228–229°C (ethanol).
IR spectrum, ν, cm–1: 1640, 1590 (C=C), 1377, 1136
(NOO–). UV spectrum, λ, nm (ε): 336 (9800), 419
Isomerization of S-substitution product IVa into
N-substitution product IVb. In 20 ml of chloroform
was dissolved 0.01 g of compound IVa. After 48 h the
reaction mixture was concentrated on a rotary evaporator
in a vacuum, and the yellow precipitate of compound IVb
was filtered off. Yield 0.0056 g (56%), mp 195–197°C
(ether). Similar result was obtained at heating compound
IVa in ethanol solution at 50°C for 60 min. The mixed
sample of compound IVb obtained by isomerization and
by direct synthesis from iodonitroethene I melted without
depression of the melting point.
1
(17700). H NMR spectrum (CDCl3), δ, ppm: 7.63 s
(=CH), 7.54–7.24 m (Ph, Ht), 11.13 s (NH). Found, %:
C 54.69; H 3.37; N 12.76. C15H11N3O2C2. Calculated,
%: C 54.71; H 3.34; N 12.76.
6-(2-Nitro-1-phenyl-1-ethenylamino)-1,3-benzo-
thiazole-2-thione (Va). To a solution of 0.275 g (1 mmol)
of compound I in 2 ml of anhydrous ethanol was poured
a suspension of 0.182 g (1 mmol) of 5-aminobenzo-
thiazolyl-2-thiol in 3 ml of anhydrous methanol.After 48
Imino(2-nitro-1,2-diphenyl-1-ethenylsulfanyl)-
methylamine (XI). To a suspension of 0.17 g (0.5 mmol)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 2 2009