1-nitro-2-thio(sulfonyl)alkenes in reactions with thiols

Article abstract of DOI:10.1023/A:1013119318658

Reactions of 1-nitro-2-sulfonylalkenes with arenethiolates result in replacement of the sulfonyl group; the reactions with alkanethiolates are accompanied by subsequent addition of the reagent at the double bond to afford thioacetals. Less reactive α-nitro-β-R-thiostyrenes with thiolates at reduced temperature form addition products which are converted into the corresponding substitution products on storage at room temperature, in keeping with the addition-elimination mechanism of nucleophilic vinyl substitution. Nitro(arylthio)- and nitro(heterylthio)alkenes react with alkanethiolates at room temperature, resulting in replacement of the arylthio (heterylthio) group by alkylthio.

Full text of DOI:10.1023/A:1013119318658

Russian Journal of Organic Chemistry, Vol. 37, No. 9, 2001, pp. 1259 1265. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 9, 2001,
pp. 1327 1333.
Original Russian Text Copyright
2001 by Kuz’mina, Lipina, Kropotova, Berkova, Pavlova.
1-Nitro-2-thio(sulfonyl)alkenes in Reactions with Thiols
N. V. Kuz’mina, E. S. Lipina, T. Yu. Kropotova, G. A. Berkova, and Z. F. Pavlova
Gertsen Russian State Pedagogical University, nab. r. Moiki 48, St. Petersburg, 191186 Russia
Received June 7, 2000
Abstract Reactions of 1-nitro-2-sulfonylalkenes with arenethiolates result in replacement of the sulfonyl
group; the reactions with alkanethiolates are accompanied by subsequent addition of the reagent at the double
bond to afford thioacetals. Less reactive -nitro- -R-thiostyrenes with thiolates at reduced temperature form
addition products which are converted into the corresponding substitution products on storage at room tem-
perature, in keeping with the addition elimination mechanism of nucleophilic vinyl substitution. Nitro(aryl-
thio)- and nitro(heterylthio)alkenes react with alkanethiolates at room temperature, resulting in replacement
of the arylthio (heterylthio) group by alkylthio.
The presence of a readily departing group in the the nitroalkene, and nucleophilicity of the reagent.
-position with respect to conjugated nitro group
is responsible for the high reactivity of such nitro-
alkenes toward nucleophilic reagents and ready forma-
tion of the corresponding substitution products [1].
We previously described reactions of some 2-arylsul-
fonyl-1-nitroalkenes with p-halobenzenethiolates
which resulted in formation of arylthio(nitro)alkenes.
We also showed that 1-arylthio-2-nitroethenes and
-arylthio- -nitrostyrenes react with the same com-
pounds at 60 C to form products of replacement of
the nitro group [2].
The reaction of 1-nitro-2-p-tolylsulfonyl-1,2-diphenyl-
ethene (Ib) with arene- and alkanethiolates leads to
formation of the corresponding substitution products
IIb, IIIe, and IIIf. Less sterically hindered styrene
derivative Ia gives similar products (compounds IIIb
and IIIc) only with arenethiolates. The reaction of Ia
with stronger nucleophiles, sodium alkanethiolates,
does not stop at the stage of formation of the substitu-
tion product; further addition of the reagent at the
double bond (as in the case of alkoxide ions [2]) leads
to formation of nitro-substituted thioacetals Va and
Vb as the major products (Scheme 1, Table 1).
The goal of the present work was to examine reac-
tions of sulfur-containing nitroalkenes with a series
of alkane-, arene-, and hetarenethiolates. The results
showed that these reactions are strongly influenced by
Taking into account that thioacetals were formed
through addition of the second thiolate molecule to
the substitution product (nitrothioalkene), we studied
the nature of the sulfur-containing group, structure of the reactions of nitrothiostyrenes and nitrothiostilbenes
Scheme 1.
IId, R1 = Ph, R2 = C12H25; IIIa, R1 = H, R2 = p-ClC6H4; IIIb, R1 = H, R2 = p-CH3C6H4; IIIe, R1 = Ph, R2 = p-CH3C6H4;
IIIf, R1 = Ph, R2 = p-ClC6H4; Va, R1 = H, R2 = C2H5; Vb, R1 = H, R2 = C12H25.
1070-4280/01/3709-1259$25.00 2001 MAIK Nauka/Interperiodica

1260
KUZ’MINA et al.
Scheme 2.
a. R2
R3
IIIa, IIId, Ve, R2 = Ph; IIIb, IIIe, Vf, R2 = p-CH3C6H4; IIIe, IIIf, Vg, R2 = p-ClC6H4; IVa, IVd, R2 = Ht; IVb, IVe, R2 = HtOEt;
IVc, IVf, R2 = HtNO2; IIa, IIc, R3 = C8H17; IIb, IId, Ve, Vg, Vf, R3 = C12H25.
b. R2 = R3 = R
Va, R = C2H5; IIb, Vb, R = C12H25; IIIb, Vc, R = p-CH3C6H4; IIIc, Vd, R = p-ClC6H4.
with thiolates under various conditions. Nitrothio-
stilbenes failed to react with thiolates at low
temperature, while nitrothiostyrenes IIb and IIIa IIIc
with alkane- and arenethiolates gave rise to addition
The reaction of nitrothiostyrenes with alkane-
thiolates at room temperature is governed by the
nature of the RS group (Table 2). In the reactions
of arylthionitrostyrenes IIIa IIIc with sodium
products Vb Vg. The latter were converted into the dodecanethiolate both thioacetals Ve Vg and substitu-
corresponding substitution products on raising the
temperature or by the action of bases. Scheme 2
shows the results of the reaction, depending on the
temperature and nitroalkene structure.
tion products IIa and IIb were isolated, whereas the
latter were the only final products of the reactions of
heterylthionitrostyrenes IVa IVc with the same
thiolate (Scheme 2a). Under similar conditions nitro-
thiostilbenes IIId IIIf and IVd IVf reacted with
alkanethiolates to give 80 90% of substitution prod-
ucts IIc and IId, no thioacetals being detected during
the process (Scheme 2a).
The observed formation of nitrothioacetals is the
first example of nucleophilic addition reactions of
nitroalkenes having a readily departing group in the
-position. The subsequent transformation of the
adducts into substitution products can be regarded
as an experimental proof of the addition elimination
mechanism of nucleophilic vinyl substitution. When
It should be noted that only thioacetals with similar
RS groups were reported previously; they were syn-
thesized from -nitroketones [3, 4]. The reaction
under study can be regarded as a method for prepara-
tion of both symmetric (Vb Vd) and mixed nitrothio-
acetals (Ve Vg). The structure of compounds Vb Vd
was proved by independent synthesis from , -di-
nitrostyrene and 2 equiv of appropriate sodium
thiolate without isolation of intermediate nitrothio-
styrene (Scheme 2b). Table 1 contains spectral param-
eters of the newly synthesized nitrothioacetals Va Vg.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1-NITRO-2-THIO(SULFONYL)ALKENES IN REACTIONS WITH THIOLS
1261
Table 1. Yields, melting points, and spectral parameters of 1-nitro-2,2-di-R-thioethanes (nitrothioacetals) Va Vg
1
1H NMR spectrum (CDCl3), , ppm
R1
IR spectrum,a cm
Comp.
no.
Yield,
%
mp, C
Ph
HA
HB
R2
s NO2
as NO2
Va
Vb
Vc
Vd
30b
41b
49c
11b
33b
38c
10c
25 27
27 28
39 40
37 39
7.28 7.45 m
7.12 7.29 m
7.23 7.34 m
7.26 7.32 m
5.32 d 4.54 d
5.37 d 4.59 d
5.37 d 4.93 d
5.30 d 4.93 d
1.16 t, 2.67 q
1375
1375
1355
1360
1580
1560
1550
1560
0.81, 1.19, 2.56 m
2.23 s, 7.50 7.00 m
6.95 7.03 m
Ve
Vf
28 29
35 37
7.10 7.31 m
7.09 7.30 m
4.80 d 4.18 d 7.09 7.30 m
4.80 d 4.18 d 7.09 7.30 m, 0.97 1.20 m
1.37 s
0.80 1.19 m
1365
1380
1560
1570
Vg
44c
36 37
7.18 7.24 m
5.36 d 4.56 d 6.88, 6.95 m 0.80 1.18 m
1365
1560
a
b
c
In CHCl3.
From dinitroalkene.
From nitrothioalkene.
Table 2. Exchange of the RS group
Initial alkene
Reaction time,
R1
R2
R3
Yield, % (product)
no.
min
IIIc
IIIa
IIIb
IVc
IVa
IVb
IIIf
IIId
IIIe
IVf
H
H
H
H
H
H
Ph
Ph
Ph
Ph
Ph
Ph
H
p-ClC6H4
Ph
p-CH3C6H4
6-NO2Ht
Ht
6-EtOHt
p-ClC6H4
Ph
p-CH3C6H4
6-NO2Ht
Ht
C12H25
C12H25
C12H25
C12H25
C12H25
C12H25
C12H25
C12H25
C12H25
C12H25
C12H25
C12H25
C8H17
5
10
20
<5
10
30
65
75
95
5
33a (IIb)
25b (IIb)
18c (IIb)
15 (IIb)
35 (IIb)
68 (IIb)
81 (IId)
91 (IId)
80 (IId)
10 (IId)
67 (IId)
31 (IId)
50 (IIa)
68 (IIc)
IVd
IVe
IVb
IIIe
60
25 h
60
6-EtOHt
6-EtOHt
p-CH3C6H4
Ph
C8H17
120
a
b
c
Yield of Vg 44%.
Yield of Ve 38%.
Yield of Vf 10%.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

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KUZ’MINA et al.
Table 3. Yields, melting points, and spectral parameters of 1-nitro-2-R-thioethenes IIa IId and IVa IVf
1
1H NMR spectrum (CDCl3), , ppm
IR spectrum,b , cm
NO2 C C
1305, 1540 1610
Comp.
no.
Yield,
%
R1
R2 a
mp,
C
Ph
R1
R2
IIa
IIb
IVa
H
H
H
C8H17
C12H25
Ht
39 40
48 49
168 170
50c
67c
7.35 7.45 m
7.35 7.45 m
0.82, 1.45, 2.19 m
0.83 t, 1.48 m, 2.22 m 1305, 1540 1610
70d 7.49 m, 7.72 s 7.44 d, 7.95 d, 8.00 d 1310, 1505 1580, 1605
7.53 m
IVb
IVc
H
H
6-EtOHt
172 173
69d 7.52 m 8.64 s 7.43 t, 4.08, 4.10 q,
7.04, 7.49 m, 7.81 d
1310, 1500 1600
6-NO2Ht 195 197
40d 7.51,
9.12 s 8.10 d, 7.34 d, 8.75 s 1355, 1535, 1570
1545
7.54 m
7.10 7.40 m
IIc
IId
IVd
Ph C8H17
Ph C12H25
Ph Ht
69 70
57 59
169 170
68c
90c
75
0.83 t, 1.46 m, 2.21 m 1305, 1545 1605
0.85 t, 1.44 m, 2.22 m 1300, 1545 1605
7.30 7.51 m, 7.95,
8.01 m
7.11 7.40 m
7.30 7.51 m
1315, 1540 1610, 1580
IVe
IVf
Ph 6-EtOHt
162 164
61
47
6.95 7.35, 7.7 m 7.43 t, 3.95, 4.10 q,
6.95 7.35, 7.7 m
1310, 1500 1595, 1560,
1470
Ph 6-NO2Ht 109 110
7.10 7.29 m
7.94 d, 8.26 d, 8.59 s 1355, 1535 1560
a
Ht is 2-benzothiazolyl.
In CHCl3.
b
c
d
Nitrothioethenes IIa IId were obtained by RS-exchange reaction.
According to the 1H NMR data, compounds IIa and IIb are Z isomers, and IVa IVc, E isomers.
nitrothioacetals Vc and Vd were kept in methanol
at room temperature, 30% of the corresponding sub-
stitution products (IIIb and IIIc) was formed via
elimination of thiol (Scheme 2b).
aryl- and heterylthionitroalkenes; this procedure is
superior to direct sulfurization of 1,2-dinitroalkenes,
for it ensures preparation of purer products.
According to the final result, i.e., replacement of
one R-thio group by another, the above reaction of
nitrothioalkenes with thiolates can be regarded as
RS-exchange (by analogy with transamination
reported in [5] for nitroenamines). The data obtained
for -alkyl-, -aryl-, and -heterylthio- -nitroalkenes
allowed us to formulate some general relations
holding therein (Table 2):
(1) Alkanethiolate ions replace heteryl- and aryl-
thio groups in nitrothioalkenes. Benzothiazole-2-
thiolate and arenethiolate ions do not replace alkyl-
and arylthio groups in the corresponding nitroalkenes.
(2) The presence of an acceptor substituent in the
aryl(heteryl)thio group facilitates its replacement by
more nucleophilic RS group; by contrast, donor sub-
stituents hinder the substitution.
We can recommend to use the reaction under study
as a method of synthesis of alkylthionitroalkenes from
EXPERIMENTAL
The IR spectra were recorded on a UR-20 instru-
ment. The H NMR spectra were obtained on a Tesla
1
BS-487C spectrometer at 80 MHz. The progress of
reactions was monitored by TLC on Silufol UV-254
plates using hexane acetone (2:1) as eluent. Some
products were isolated and purified by column
chromatography on silica gel (L 100/400 m) using
the Trappe eluotropic series. Table 3 contains the
melting points and spectral parameters of the newly
synthesized 1-nitro-2-alkylthioethenes (IIa IId) and
1-nitro-2-benzothiazolylthioethenes (IVa IVf);
the elemental analyses of new compounds IIa IId,
IVa IVf, and Va Vg are given in Table 4.
1-Nitro-2-p-tolylsulfonylethenes Ia and Ib were
synthesized from the corresponding 1,2-dinitroethenes
and p-toluenesulfinic acid by the procedure reported
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1-NITRO-2-THIO(SULFONYL)ALKENES IN REACTIONS WITH THIOLS
1263
Table 4. Elemental analyses of 1-nitro-2-R-thioethenes IIa, IIb, and IVa IVf and nitrothioacetals Va Vg
Found, %
H
Calculated, %
H
Comp.
no.
Formula
C
N
C
N
IIa
IIb
IIc
65.21
68.79
71.44
73.11
55.23
56.68
50.03
57.27
63.05
57.81
53.09
69.87
65.98
55.00
68.29
68.41
63.44
7.92
8.92
7.27
8.45
4.13
3.98
2.55
3.24
4.74
3.17
6.08
10.52
5.55
4.01
7.24
8.17
7.41
5.05
4.05
3.89
3.20
9.15
7.75
11.60
8.87
6.25
9.57
5.43
2.63
3.37
3.08
3.08
3.21
2.75
C16H23NO2S
C20H31NO2S
C22H27NO2S
C26H35NO2S
65.53
68.77
71.54
73.41
55.25
56.98
50.14
53.32
63.30
57.93
53.14
69.69
66.84
55.04
68.12
68.50
63.22
7.85
8.88
7.31
8.24
3.94
3.91
2.51
3.18
4.59
2.99
6.27
10.34
5.32
3.44
6.99
8.25
7.29
4.78
4.01
3.79
3.29
4.21
7.82
11.69
8.91
6.42
9.66
5.17
2.54
3.54
3.21
3.06
2.96
2.83
IId
IVa
IVb
IVc
IVd
IVe
IVf
Va
Vb
Vc
Vd
Ve
C15H10N2O2S2
C17H14N2O3S2
C15H9N3O4S2
C15H10N2O2S2
C22H18N2O3S2
C21H13N3O4S2
C12H17NO2S2
C32H57NO2S2
C22H21NO2S2
C20H15Cl2NO2S2
C26H32NO2S2
C27H39NO2S2
C26H37ClNO2S2
Vf
Vg
in [6]. 1-Nitro-2-R-thioethenes IIIa IIIf were syn-
thesized by the procedure described in [7] from the
corresponding dinitroethenes and sodium thiolates.
2-(2-Benzothiazolylthio)-1-nitro-1-phenylethene
(IVa). A solution of 0.4 g (0.002 mol) of 1,2-dinitro-
1-phenylethene in 7 ml of methanol was added to
a solution of 0.4 g (0.002 mol) of benzothiazole-2-
thiol in 5 ml of chloroform. The bright yellow precip-
itate was filtered off and recrystallized from ethanol.
Yield of IVa 0.44 g.
3 drops of triethylamine. When the mixture became
homogeneous, it was cooled to 0 C. The yellow
precipitate of nitrothioethene IVd was filtered off
and recrystallized from ethanol.
2-(6-Ethoxy-2-benzothiazolylthio)-1-nitro-1,2-di-
phenylethene (IVe) was synthesized in a similar way.
The product (bright yellow crystalline substance) was
recrystallized from ethanol.
2-(6-Nitro-2-benzothiazolylthio)-1-nitro-1,2-di-
phenylethene (IVf) was synthesized by the procedure
described above for compound IVc.
2-(6-Ethoxy-2-benzothiazolylthio)-1-nitro-1-
phenylethene (IVb) was synthesized in a similar way.
2-(6-Nitro-2-benzothiazolylthio)-1-nitro-1-
phenylethene (IVc). To a suspension of 0.212 g
Reaction of 1-nitro-2-p-tolylsulfonylethenes Ia
and Ib with sodium thiolates. To a suspension of
0.3 g (0.001 mol) of 1-nitro-2-p-tolylsulfonyl-1-
(0.001 mol) of 5-nitrobenzothiazole-2-thiol in 5 ml of phenylethene (Ia) in 5 ml of methanol we added at
methanol we added at room temperature an equimolar
amount of sodium methoxide in 3 ml of methanol.
When the mixture became homogeneous, it was
cooled to 0 C and was added to a solution of 0.2 g
(0.001 mol) of 1,2-dinitro-1-phenylethene in 5 ml
of methanol. The precipitate was filtered off and
recrystallized from MeOH CHCl3 (2:1). Yield of IVc
0.22 g, yellow crystalline substance.
2-(2-Benzothiazolylthio)-1-nitro-1,2-diphenyl-
ethene (IVd). To a suspension of 0.5 g (1.9 mmol) of
1,2-dinitro-1,2-diphenylethene in 10 ml of methanol
we added a suspension of 0.309 g (1.9 mmol) of
benzothiazole-2-thiol in 10 ml chloroform and then
5 to 0 C a solution of 0.001 mol of sodium ethane-
thiolate prepared from equimolar amounts of sodium
methoxide and ethanethiol in methanol. After 1 h,
the mixture was concentrated, the residue was treated
with acetone, and 0.12 g of sodium p-toluenesulfinate
was filtered off. The filtrate was subjected to column
chromatography on silica gel using first cyclohexane
as eluent. The eluate contained 0.08 g of 2,2-bis(ethyl-
thio)-1-nitro-1-phenylethene (Va); colorless crystalline
substance, mp 25 27 C. The subsequent elution with
1
CCl4 and CHCl3 gave (according to the TLC and H
NMR data) a mixture of 2-ethylthio-1-nitro-1-phenyl-
ethene and nitrothioacetal Va.
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KUZ’MINA et al.
Following the above procedure, the reaction with
evaporated by half and frozen to isolate didodecyl
disulfide (yield 40 and 25%, respectively), mp 32
33 C; published data [8]: mp 34 C.
sodium dodecanethiolate was carried out at room
temperature. The mixture was kept for 1 h at room
temperature, evaporated by half, and frozen. The
product, 2,2-bis(dodecylthio)-1-nitro-1-phenylethene
(Vb), was filtered off. Colorless crystalline substance,
mp 27 28 C.
The reactions with sodium p-toluenethiolate and
sodium p-chlorobenzenethiolate were performed in
a similar way. The products, 1-nitro-1-phenyl-2-p-
tolylthioethene (IIIb), mp 83 C (published data [7]:
mp 85 C), yield 61%, and 2-p-chlorophenylthio-1-
nitro-1-phenylethene (IIIc), mp 112 C (published
data [7]: mp 114 C [7]), yield 58%, were isolated as
yellow crystalline substances.
Reactions of 1-nitro-2-R-thioethenes with
sodium thiolates at room temperature. To a suspen-
sion of 0.2 g (0.69 mmol) of nitrothiostyrene IIIc in
10 ml of methanol we added at room temperature
a solution of sodium dodecanethiolate, prepared from
equimolar amounts of dodecanethiol and sodium
methoxide in 5 ml of methanol. The colorless flaky
precipitate (0.15 g, nitrothioacetal Vg) was filtered
off, the filtrate was evaporated by half, and the light
yellow crystals of 2-dodecylthio-1-nitro-1-phenyl-
ethene (IIb), 0.08 g (33%), were filtered off. Freezing
of the filtrate gave 0.02 g (7%) of didodecyl disulfide.
The reaction of 1-nitro-2-p-tolylsulfonyl-1,2-di-
phenylethene (Ib) with an equimolar amount of
sodium dodecanesulfonate was carried out in methanol
at room temperature (see above). The mixture was
kept for 1 h at room temperature and frozen. 1,2-Di-
phenyl-2-dodecylthio-1-nitroethene (IId) was isolated
as a yellow crystalline substance. Yield 0.13 g (76%),
mp 57 59 C.
The reaction with sodium p-chlorobenzenethiolate
was carried out in a similar way. 2-p-Chlorophenyl-
thio-1-nitro-1,2-diphenylethene (IIIf) was isolated in
60% yield; yellow crystalline substance, mp 132 C;
published data [7]: mp 135 C.
Reactions of 1-nitro-2-R-thioethenes with
sodium thiolates at reduced temperature. To a sus-
pension of 0.22 g (0.9 mmol) of 2-p-chlorophenylthio-
1-nitro-1-phenylethene (IIIc) in 7 ml of methanol
we added at 10 to 0 C a solution of 0.9 mmol of
sodium p-chlorobenzenethiolate prepared from equi-
molar amounts of sodium methoxide and p-chloro-
benzenethiol in methanol. After 0.2 h, the solution
was frozen to isolate 0.14 g of 2,2-bis(p-chlorophenyl-
thio)-1-nitro-1-phenylethane (Vd) as a colorless crys-
talline substance.
The reaction of 1-nitro-1-phenyl-2-p-tolylthio-
ethene (IIIb) with sodium p-toluenethiolate was
carried out in a similar way. The product, 1-nitro-1-
phenyl-2,2-bis(p-tolylthio)ethane (Vc) was isolated as
a colorless crystalline substance with mp 39 40 C.
Following the same procedure, we performed reac-
tions of sodium dodecanethiolate with styrenes IIIa,
IIIb and IVa IVc and stilbenes IIId IIIf and IVd
IVf, as well as of sodium octanethiolate with styrene
IVc and stilbene IIIe. The products were 1-nitro-2-
octylthio-1-phenylethene (IIa), light yellow crystals,
mp 38 40 C; styrene IIb, mp 48 49 C; 1-nitro-2-
octylthio-1,2-diphenylethene (IIc), yellow crystals,
mp 69 70 C; and stylbene IId, mp 57 59 C. For
details, see Table 3.
In the reactions of IVd with sodium p-toluene-
thiolate and sodium p-chlorobenzenethiolate only the
initial nitrothioalkene was isolated in 90% yield
(reaction time 48 h). Likewise, the initial thiol was
isolated in 91% yield in the reaction of 2-ethylthio-1-
nitro-1-phenylethene with sodium benzothiazole-2-
thiolate (reaction time 48 h).
Transformation of nitrothioacetals Vc and Vd
into nitrothioethenes. Compound Vc, 0.18 g
(0.14 mmol), was dissolved in 3 ml of methanol, and
the solution was kept at room temperature. The initial
compound dissolved, and the solution gradually
turned yellow. After 30 min (TLC), the solvent was
removed, the residue was treated with 2 ml of ethanol
cooled to 0 C, p-toluenethiol was filtered off, and
the filtrate was concentrated and frozen to isolate
0.1 g (33%) of nitrothioethene IIIb, mp 84 C. The
reaction with compound Vd was carried out in
a similar way; after 40 min, nitrothioethene IIIc was
isolated in 21% yield, mp 112 C.
Independent synthesis of nitrothioacetals from
1,2-dinitro-1-phenylethene. 2,2-Bis(p-chlorophenyl-
thio)-1-nitro-1-phenylethane (Vd). To a solution of
0.3 g (1.54 mmol) of 1,2-dinitro-1-phenylethene in
5 ml of methanol we added at 0 C a solution of
sodium p-chlorobenzenethiolate in 10 ml of methanol,
prepared from 0.0708 g (3.8 mmol) of sodium and
The reactions of 2-p-chlorophenylthio-1-nitro-1-
phenylethene (IIIc) and 1-nitro-1-phenyl-2-p-tolyl-
thioethene (IIIb) with sodium dodecanethiolate were
carried out in a similar way. The mixture was kept for
1 h, and 2-p-chlorophenylthio-2-dodecylthio-1-nitro-
1-phenylethane (Vg) and 2-dodecylthio-1-nitro-1-
phenyl-2-p-tolylthioethane (Vf) were isolated in
50 and 25% yield, respectively. The filtrate was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

1-NITRO-2-THIO(SULFONYL)ALKENES IN REACTIONS WITH THIOLS
0.445 g (3.8 mmol) of p-chlorobenzenethiol. After REFERENCES
1265
10 min, the colorless precipitate of thioacetal Vd
was filtered off. Yield 0.27 g (30%), mp 37 39 C.
Nitrothioacetals Vb and Vc were obtained in
a similar way; Vb: yield 42%, mp 27 28 C; Vc: yield
31%, mp 39 40 C.
1. Perekalin, V.V., Lipina, E.S., Berestovitskaya, V.M.,
and Efremov, D.A., Nitroalkenes, Chichester: Wiley,
1994.
2. Pavlova, Z.F., Lipina, E.S., Kasem, Ya.A., and Kuz’-
mina, N.V., Russ. J. Org. Chem., 1999, vol. 35, no. 9,
pp. 1321 1325.
2,2-Bis(ethylthio)-1-nitro-1-phenylethane (Va). To
a solution of 1 g (0.005 mol) of 1,2-dinitro-1-phenyl-
ethene in 5 ml of methanol we added at 10 C a solu-
tion of 0.01 mol of sodium ethanethiolate, prepared
from equimolar amounts of ethanethiol and sodium
methoxide in methanol. After 2 h, the mixture was
concentrated, the residue was treated with acetone,
the precipitate of sodium nitrite was filtered off, and
the filtrate was subjected to column chromatography
on silica gel. Using cyclohexane as eluent we isolated
0.43 g of 2,2-bis(ethylthio)-1-nitro-1-phenylethane
(Va) as a colorless crystalline substance. The column
was then eluted with CCl4 and CHCl3; according to
3. Node, M., Kawabata, T., Fujimoto, M., and Fuji, K.,
Synthesis, 1984, p. 234.
4. Jung, M. and Grove, D., J. Chem. Soc., Chem. Com-
mun., 1987, vol. 49, pp. 753 756.
5. Fetell, A. and Feuer, H., J. Org. Chem., 1978, vol. 43,
no. 6, pp. 1238 1241.
6. Mukhina, E.S., Pavlova, Z.F., Berkova, G.A., Lipi-
na, E.S., Mostyaeva, L.V., Perekalin, V.V., and
Kasem, Ya.A., Zh. Org. Khim., 1991, vol. 27, no. 5,
pp. 910 918.
7. Mukhina, E.S., Berkova, G.A., Pavlova, Z.F., Lipi-
na, E.S., and Perekalin, V.V., Zh. Org. Khim., 1990,
vol. 26, no. 7, pp. 1447 1452.
1
the TLC and H NMR data, the eluates contained
a mixture of 2-ethylthio-1-nitro-1-phenylethene and
nitrothioacetal Va. The yields and melting points
of compounds V are given in Table 1.
8. Beilsteins Handbuch der organischen Chemie, EIII,
vol. 1, p. 1792.
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