Reactions of 1,2-dinitro- and 1-nitro-2-sulfonylethenes with some binucleophiles

Full text of DOI:10.1134/S1070428010080221

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 8, pp. 1251–1253. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © T.Yu. Kretser, E.S. Lipina, N.V. Kuz’mina, G.A. Berkova, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 8,
pp. 1249–1251.
SHORT
COMMUNICATIONS
Reactions of 1,2-Dinitro- and 1-Nitro-2-sulfonylethenes
with Some Binucleophiles
T. Yu. Kretser, E. S. Lipina, N. V. Kuz’mina, and G. A. Berkova
Hertzen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
Received June 10, 2009
DOI: 10.1134/S1070428010080221
The presence in dinitroethene and nitrosulfonyl-
ethene molecules of a strong electron-withdrawing and
nucleofugal substituent in the β-position with respect
to the conjugated nitro group determines high reactiv-
ity of these compounds toward nucleophilic reagents
and is responsible for predominant formation of re-
placement products in such reactions [1–3]. We previ-
ously reported on the reactions of dinitro- and nitrosul-
fonylethenes with such difunctional nucleophiles as
hydrazine [4], thiourea, and N,N′-diphenylthiourea [5].
In the present communication we describe reactions of
nitroethenes I–IV with phenylhydrazine, o-aminoben-
zenethiol, and 6-amino-1,3-benzothiazole-2-thiol. The
two latter reagents are interesting due to the presence
in their molecules of two potential reaction centers of
different natures. We have found no published data on
relative nucleophilic reactivity of these reagents.
VIII, the latter being formed as two stereoisomers
(Scheme 1).
Scheme 1.
SC6H4X-4
H
SC6H4X-4
NHNHPh
Ha
Ph
PhNHNH2, 18°C
Ph
Hb
NO2
V, VI
NO2
VII, VIIIa, VIIIb
V, VII, X = H; VI, VIII, X = Cl.
Unlike the reaction with phenylhydrazine, com-
pounds I–IV reacted with N,S-binucleophiles,
o-aminobenzenethiol and 6-amino-1,3-benzothiazole-
2-thiol, following the nucleophilic replacement pattern.
The reactions with nitrostilbene derivatives III and IV
involved the sulfur reaction center of the binucleophile
(Scheme 2). In the reactions with more electrophilic
and less sterically loaded styrene derivatives I and II,
unstable sulfanyl-substituted products XI and XIII
were detected only spectrally as mixtures with isomer-
ic nitro enamines XII and XIV. Compounds XI and
XIII were converted with time or during the isolation
procedure into thermodynamically more stable amino
derivatives XII and XIV (Scheme 3). Compounds XI
and XIII were identified by IR and UV spectroscopy;
their IR and UV spectra were typical of 1-nitro-1-
phenyl-2-arylsulfanylethenes [IR spectrum (CHCl3): ν,
cm–1: 1620, 1595, 1520, 1320, 1310. UV spectrum
(CHCl3): λmax 1360 nm] [6]. The spectral parameters
of compounds XII and XIV were typical of nitro
enamines [3].
X
Ph
R
NO2
I–IV
I, II, R = H; III, IV, R = Ph; I, III, X = O2N;
II, IV, X = 4-ClC6H4SO2.
The reactions of compounds I–IV with phenylhy-
drazine (which is characterized by a fairly low oxida-
tion potential) were accompanied by strong tarring, so
that we failed to isolate and identify products of these
reactions. We succeeded in avoiding side redox proc-
esses only by replacing electron-withdrawing β-substit-
uent in the substrate by electron-donating phenyl- or
4-chlorophenylsulfanyl group; in these cases we ob-
tained the corresponding addition products VII and
1-[2-Nitro-2-phenyl-1-(phenylsulfanyl)ethyl]-2-
phenylhydrazine (VII). A solution of 0.108 g
(1 mmol) of phenylhydrazine in 5 ml of ethanol was
1251

KRETSER et al.
1252
Scheme 2.
NH2
NH2
N
S
N
SH
S
S
X
S
H2N
SH
18°C (III), 60°C (IV)
Et3N
Ph
NH2
Ph
Ph
Ph
Ph
Ph
NO2
IX
NO2
III, IV
NO2
X
III, X = O2N; IV, X = 4-ClC6H4SO2.
Scheme 3.
NH2
S
HN
SH
0°C (I), 18°C (II)
MeOH, 18°C, 1 h
Ph
NH2
Ph
SH
H
N
H
NO2
XI
NO2
XII
X
Ph
H
N
N
NH2
NO2
SH
SH
S
S
I, II
S
S
HN
H2N
Et3N
18°C
Ph
Ph
H
H
NO2
NO2
XIII
XIV
I, X = O2N; II, X = 4-ClC6H4SO2.
added to a suspension of 0.257 g (1 mmol) of com-
pound V in 10 ml of ethanol. The mixture was kept for
3 days at 0°C, and the colorless needle-shaped crystals
were filtered off. Yield 0.1 g (27%), mp 117–119°C
(from ethanol). IR spectrum, ν, cm–1: 1560, 1360
(NO2). 1H NMR spectrum (CDCl3), δ, ppm: 5.10 d (1H,
Hb, Jab = 11 Hz), 5.50 d (1H, Ha), 7.10–7.60 m (15H,
0.133 g (33%), mp 137–140°C. IR spectrum, ν, cm–1:
1
1560, 1358 (NO2). H NMR spectrum (CDCl3), δ,
ppm: 5.00 d (1H, Hb, Jab = 8 Hz), 5.10 d (1H, Ha),
7.42 m (4H, C6H4), 7.55 m (10H, C6H5). Found, %:
C 60.17; H 4.61; N 10.40. C20H18ClN3O2S. Calculated,
%: C 60.07; H 4.54; N 10.51.
2-[(2-Nitro-1,2-diphenylvinyl)sulfanyl]aniline
(IX). A solution of 0.125 g (1 mmol) of o-aminoben-
zenethiol in 10 ml of methanol was added dropwise at
18°C to a suspension of 0.27 g (1 mmol) of nitro-
ethene III in 5 ml of methanol. After 30 min, the bright
yellow crystals were filtered off. Yield 0.154 g (44%),
mp 134–136°C. IR spectrum, ν, cm–1: 1615 (C=C);
1530, 1305 (NO2). UV spectrum (CHCl3), λ, nm (ε,
l mol–1 cm–1): 255 (10000), 290 (7000), 338 (10000).
1H NMR spectrum (CDCl3), δ, ppm: 3.85 s (NH2),
6.40–8.10 m (14H, C6H4, C6H5), Found, %: C 69.00;
H 4.75; N 8.14. C20H16N2O2S. Calculated, %: C 68.96;
H 4.63; N 8.04.
H
arom). Found, %: C 65.10; H 5.21. C20H19N3O2S. Cal-
culated, %: C 65.53; H 5.20.
1-[1-(4-Chlorophenylsulfanyl)-2-nitro-2-phenyl-
ethyl]-2-phenylhydrazines VIIIa and VIIIb were
synthesized in a similar way from nitroethene VI at
20°C. After 30 min, isomer VIIIa separated from the
solution as colorless solid with mp 127–130°C. Yield
0.084 g (21%). IR spectrum, ν, cm–1: 1560, 1360
1
(NO2). H NMR spectrum (CDCl3), δ, ppm: 5.45 d
(1H, Ha), 5.00 d (1H, Hb, Jab = 11.5 Hz), 7.00 d and
7.15 d (4H, C6H4), 7.40 m (10H, C6H5). Found, %:
C 60.10; H 4.70; N 10.41. C20H18ClN3O2S. Calculated,
%: C 60.07; H 4.54; N 10.51.
Compound IX was also synthesized in a similar
way from nitrosulfonylethene (IV). The reaction mix-
ture was heated until it became homogeneous, kept for
The mixture was cooled to 0°C, and the colorless
crystals of isomer VIIIb were filtered off. Yield
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010

REACTIONS OF 1,2-DINITRO- AND 1-NITRO-2-SULFONYLETHENES
1253
3 days at room temperature, and cooled to 0°C. Yield
0.07 g (38%), mp 133–135°C.
and purified by column chromatography. Yield 0.11 g
(67%), bright yellow crystals, mp 202–203°C (from
benzene). IR spectrum (mineral oil), ν, cm–1: 1645,
1600 (C=C, C=N); 1305, 1165 (NOO–). UV spectrum
(CHCl3), λ, nm (ε, l mol–1 cm–1): 336 (7500), 419
2-[(2-Nitro-1,2-diphenylvinyl)sulfanyl]-1,3-ben-
zothiazol-6-amine (X) was synthesized in a similar
way from 0.135 g (0.5 mmol) of dinitroethene III and
0.091 g (0.5 mmol) of 5-amino-1,3-benzothiazole-2-
thiol with addition of one drop of triethylamine. The
mixture was kept for 1 h at 18°C, and the orange pre-
cipitate was filtered off. Yield 0.179 g (87%), mp 142–
144°C (from CCl4). IR spectrum, ν, cm–1: 1600, 1620
(C=C, C=N); 1540, 1305 (NO2). UV spectrum
(CHCl3), λ, nm (ε, l mol–1 cm–1): 242 (16500), 328
1
(15300). H NMR spectrum (DMSO-d6), δ, ppm: 7.90–
8.10 m (8H, Harom), 8.15 s (1H, =CH), 11.26 (NH).
Found, %: C 54.77; H 3.46; N 12.72. C15H11N3O2S2.
Calculated, %: C 54.70; H 3.37; N 12.76.
Compound XIV was also synthesized in a similar
way from nitrosulfonylethene II. Yield 56%.
The reactions of 1,2-dinitro-1-phenylethene (I) with
6-amino-1,3-benzothiazole-2-thiol in the presence of
triethylamine were performed according to an analo-
gous procedure using an equimolar amount of triethyl-
amine. After 10 min, 0.135 g of a brown–red solid was
filtered off and subjected to column chromatography.
Elution with benzene gave bright yellow crystals of
compound XIV. Yield 0.1 g (31%), mp 201–203°C
(from benzene). According to the spectral data, the
chloroform eluate contained 2-[(2-nitro-2-phenylvinyl)-
sulfanyl]-1,3-benzothiazol-6-amine (XIII). IR spec-
trum, ν, cm–1: 1639, 1591 (C=C, C=N); 1517, 1339
(NO2). UV spectrum (CHCl3), λmax, nm: 229, 335.
1
(18700). H NMR spectrum (CDCl3), δ, ppm: 6.70–
7.60 m (13H, Harom), 3.90 s (NH2). Found, %: C 61.82;
H 4.04; N 9.78. C21H15N3O2S2. Calculated, %: C 62.20;
H 3.73; N 10.37.
Compound X was also synthesized in a similar way
from nitrosulfonylethene IV. Yield 0.016 g (57%).
2-{[(E)-2-Nitro-2-phenylvinyl]amino}benzene-
thiol (XII). A solution of 0.388 g (2 mmol) of dinitro-
ethene I in 10 ml of anhydrous ethanol was cooled to
0°C, a solution of 0.25 g (2 mmol) of o-aminobenzene-
thiol in 10 ml of anhydrous ethanol was added, the
mixture was kept for 40 min, and the yellow precip-
itate, 0.08 g (mp 85–150°C), was filtered off. Accord-
ing to the TLC, IR, and UV data, the product was
a mixture of nitrosulfanylethene XI and nitroamino-
ethene XII.
1
The H NMR spectra were recorded on a Bruker
AC-200 spectrometer at 200 MHz. The IR spectra
were measured on a Shimadzu IR Prestige-21 spec-
trometer from solutions in CHCl3 with a concentration
of 40 mg/ml. The UV spectra were recorded on
a Shimadzu UV-2401 PC spectrophotometer. The
progress of reactions and the purity of products were
monitored by TLC on Silufol UV-254 plates using
hexane–acetone (2:1) as eluent.
2-[(2-Nitro-2-phenylvinyl)sulfanyl]aniline (XI).
IR spectrum, ν, cm–1: 1610 (C=C); 1525, 1310 (NO2).
UV spectrum (CHCl3): λmax 360 nm.
The filtrate was cooled to –5°C and kept for 48 h at
that temperature, and red–orange crystals of compound
XII were filtered off. Yield 0.077 g (14%), mp 170–
173°C. IR spectrum (CHCl3), ν, cm–1: 1587, 1634
(C=C, C=N); 1378, 1152 (NOO–). UV spectrum
(CHCl3), λ, nm (ε, l mol–1 cm–1): 250 (10900), 407
REFERENCES
1. Pavlova, Z.F., Lipina, E.S., and Perekalin, V.V., Sulfur
Rep., 1995, vol. 16, p. 149.
2. Kuz’mina, N.V., Lipina, E.S., Berkova, G.A., Kropoto-
va, T.Yu., and Pavlova, Z.F., Russ. J. Org. Chem., 2001,
vol. 37, p. 1259.
3. Kuz’mina, N.V., Lipina, E.S., Kropotova, T.Yu., Berko-
va, G.A., and Pavlova, Z.F., Russ. J. Org. Chem., 2003,
vol. 39, p. 82.
4. Kretser, T.Yu., Lipina, E.S., Kuz’mina, N.V., Berko-
va, G.A., and Berestovitskaya, V.M., Russ. J. Org. Chem.,
2003, vol. 39, p. 1202.
1
(8700). H NMR spectrum (CDCl3), δ, ppm: 7.35–
7.70 m (9H, Harom), 8.10 s (1H, =CH), 11.50 s (NH).
Found, %: C 62.02; H 4.78; N 9.97. C14H12N2O2S. Cal-
culated, %: C 61.75; H 4.44; N 10.29.
According to the UV data, after 5 min the reaction
mixture contained only sulfur derivative XI, and after
40 min, only compound XII.
6-{[(E)-2-Nitro-2-phenylvinyl]amino}-1,3-benzo-
thiazole-2-thiol (XIV). A solution of 0.097 g
(0.5 mmol) of dinitroethene I in 5 ml of methanol was
added dropwise to a suspension of 0.091 g (0.5 mmol)
of 6-amino-1,3-benzothiazole-2-thiol in 5 ml of metha-
nol. After 5 min, the orange precipitate was filtered off
5. Kretser, T.Yu., Lipina, E.S., Kuz’mina, N.V., Berko-
va, G.A., and Berestovitskaya, V.M., Russ. J. Org. Chem.,
2003, vol. 39, p. 1670.
6. Pavlova, Z.F., Lipina, E.S., Kasem, Ya.A., and Kuz’mi-
na, N.V., Russ. J. Org. Chem., 1999, vol. 35, p. 1321.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 8 2010