Thiylation of functionalized electrophiles with sulfur in basic reductive systems

Article abstract of DOI:10.1023/B:RUGC.0000030389.52415.6c

Functionalized electrophiles, specifically acetyl chloride, benzoyl chloride, chloroacetylchloride, benzenesulfonyl chloride, and N,N,4-trichlorobenzenesulfonamide, were brought into reaction with sulfur in the systems hydrazine hydrate-NaOH and sodium sulfide-water-ethanol. The efficiencies of these systems were compared. The reaction of chloroacetyl chloride with sulfur in the system hydrazine hydrate-base afforded new types of polymeric compounds, poly[(diacylhydrazine)polysulfides]. The reaction mechanisms were discussed.

Full text of DOI:10.1023/B:RUGC.0000030389.52415.6c

Russian Journal of General Chemistry, Vol. 74, No. 3, 2004, pp. 346 349. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 3, 2004,
pp. 384 387.
Original Russian Text Copyright
2004 by Deryagina, Russavskaya, Grabel’nykh.
Thiylation of Functionalized Electrophiles with Sulfur
in Basic Reductive Systems
E. N. Deryagina, N. V. Russavskaya, and V. A. Grabel’nykh
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received March 22, 2002
Abstract Functionalized electrophiles, specifically acetyl chloride, benzoyl chloride, chloroacetylchloride,
benzenesulfonyl chloride, and N,N,4-trichlorobenzenesulfonamide, were brought into reaction with sulfur in
the systems hydrazine hydrate NaOH and sodium sulfide water ethanol. The efficiencies of these systems
were compared. The reaction of chloroacetyl chloride with sulfur in the system hydrazine hydrate base
afforded new types of polymeric compounds, poly[(diacylhydrazine)polysulfides]. The reaction mechanisms
were discussed.
In continuation of our studies on reactions of sulfur
with mono- and difunctional electrophiles in the
system hydrazine hydrate alkali [1 3], we extended
the series of electrophilic reagents by including such
compounds as acetyl chloride, benzoyl chloride,
chloroacetyl chloride, benzenesulfonyl chloride, and
N,N,4-trichlorobenzenesulfonamide. The same sub-
strates were also involved in reaction with sodium
disulfide generated from sulfur and sodium sulfide in
aqueous alcohol in the absence of hydrazine hydrate
with a view to elucidate the effect of the latter on the
reaction direction.
S8 + 8NaOH + 2NH2NH2 H2O
4Na2S2 + 2N2 + 10H2O,
Na2Sn + 2C6H5COCl
C6H5COS3(4)COC6H5 + 2NaCl,
(1)
(2)
I
H2O, C2H5OH
Na2S + S
Na2S2
2C6H5COCl
C6H5COS2COC6H5.
II
The nature of the polysulfide anions formed upon
dissolution of sulfur in hydrazine hydrate aqueous
alkali depends on the ratio MOH:S:N2H4 and condi-
tions. Presumably, reaction (1) gives rise to an equi-
librium between polysulfide ions [scheme (3)] [4].
Sodium disulfide was generated in two ways:
(1) from sulfur in the system hydrazine hydrate
aqueous NaOH and (2) from sodium sulfide and sulfur
in aqueous alcohol. In both cases, the reactions of
sodium disulfide with the above electrophiles were
carried out at room temperature, and the reactions
were accompanied by heat evolution. The reaction
conditions and the yields and properties of the pro-
ducts are summarized in Tables 1 and 2. Among the
examined electrophiles, only acetyl chloride failed to
react with sodium disulfide, regardless of the method
of its generation; as a result, acetyl chloride was
reduced to acetic acid. The reaction of benzoyl
chloride with sodium disulfide generated from sulfur
in the system hydrazine hydrate NaOH gave a mix-
ture of dibenzoyl polysulfides [scheme (1)], the major
components of which were tri- and tetrasulfides I.
Sodium disulfide obtained from sodium sulfide and
sulfur in aqueous alcohol reacted with benzoyl chlo-
ride according to scheme (2) to afford dibenzoyl di-
sulfide (II).
S2
S22
S32
S2n .
(3)
In all cases, the ratio MOH:S was 1:1 which
should favor predominant formation of disulfides
M2S2. However, in the presence of a strictly stoichio-
metric amount of hydrazine hydrate, tri- and tetrasul-
fide ions were mainly generated. We succeeded in ob-
taining disulide ions only when used a 4 5-fold
excess of hydrazine hydrate. In the presence of excess
hydrazine hydrate, benzoyl chloride reacted only with
hydrazine to give N,N -dibenzoylhydrazine (III) ac-
cording to scheme (4). Likewise, the same product
was formed at a high rate in the reactions of benzoyl
chloride with pure hydrazine hydrate or the system
hydrazine hydrate alkali.
1070-3632/04/7403-0346 2004 MAIK Nauka/Interperiodica

THIYLATION OF FUNCTIONALIZED ELECTROPHILES WITH SULFUR
347
Table 1. Reactions of functionalized electrophiles with sulfur in the system hydrazine hydrate NaOH water (NaOH,
0.1 mol; S, 0.1 mol, hydrazine hydrate, 5 ml; water, 30 ml)
Reagent
Product
yield, g (%)
Temperature,
C
mp,
C
formula
C6H5COCl
g
mol
no.
appearance
14a
14b
6.8
6.8b
17.7
0.1a
0.1b
0.06
0.06b
0.1
54
70
60
65
84
50
I
7.5 (45.5)
8 (66.2)
3.4 (56.6)
4.2 (45.8)
7.2 (38.1)
1.5 (78.9)
White powder
White prisms
Yellow powder
Yellowish green
112 117
205 206
105 135
95
125
135 138
C6H5COCl
III
VI
VII
IX
X
ClCH2COCl
ClCH2COCl
C6H5SO2Cl
4-ClC6H4SO2NCl2
2.6
0.01
White powder
Calculated, %
Found, %
Formula
C
H
Cl
N
O
S
C
H
Cl
N
O
S
49.52
68.47
23.52
23.24
38.32
37.55
3.40
5.37
3.39
3.22
2.65
3.51
9.74 37.12 C14H8O2S3.8
14.45 C14H14N2O2
4.38 12.41 15.84 40.46 C4H6Cl0.25N2O2S2.5 23.65
3.14 14.64 19.79 35.97 C4H6Cl0.17N2O2S2
18.00 41.40 C12H10O4S5
50.97
69.4
2.42
5.78
2.96
3.04
2.65
3.13
9.70 36.89
11.57 13.22
4.37 13.80 15.77 39.43
3.15 14.20 16.26 32.50
16.93 42.33
11.0
24.39
38.69
37.5
19.65
7.36
14.39 17.54 C6H6NClO2S
18.25 7.29 17.16 16.67
a
b
Amount of hydrazine hydrate 1.2 ml.
Amount of hydrazine hydrate 10 ml.
Table 2. Reactions of functionalized electrophiles with sulfur in the system Na2S H2O S water ethanol (0.05 mol:
0.05 mol: 2.5 ml : 1 ml)
Reagent
Product
yield, g (%)
Temperature,
C
mp,
C
formula
g
mol
no.
appearance
C6H5COCl
ClCH2COCl
C6H5SO2Cl
14
0.1
0.1a
0.1
60
82
70
II
VIII
IXa
4.5 (33)
2.9 (47.5)
4.6 (23.4)
White plates
Brown rubber
White prisms
131 132
115 120
180 183
11.3a
17.7
Found, %
Calculated, %
Formula
C
H
O
S
C
H
O
S
61.18
19.40
36.69
3.05
2.70
2.65
12.27
12.47
16.42
23.35
65.11
44.47
C14H8O2S2
C2H2OS2.5
C12H10O4S5.5
61.31
19.67
36.65
3.05
1.64
2.54
11.68
13.11
16.26
23.36
65.57
44.57
a
Found Cl, %: 0.58.
S8 + 8NaOH + 2NH2NH2 H2O
4Na2S2 + 2N2 + 10H2O,
2C6H5COCl + NH2NH2
Presumably, excess hydrazine solvates disulfide
ions formed in the system. Disulfide ions are strongly
activated via complex IV formation.
Complex IV is known to effectively react with al-
dehydes, yielding the corresponding aldehyde azines
[5]. It was assumed that aldehydes are initially con-
C6H5CONH NHCOC6H5 + 2NaCl.
(4)
III
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 3 2004

348
DERYAGINA et al.
5 ml of hydrazine hydrate; molecules VI include al-
Na+---S Na
H
_
n
.
ternating di- and trisulfide bridges. Presumably, under
these conditions sulfide ions disproportionate accord-
ing to scheme (3), and the equilibrium therein is dis-
placed to the right. Excess hydrazine hydrate sta-
bilizes disulfide ions and favors formation of polymer
VII having only disulfide bridges (compound VII was
obtained in the presence of 10 ml of hydrazine hyd-
rate). The molecular weight of VII is higher than that
of VI (1131 and 810 au, respectively; calculated
from the concentration of terminal chlorine atoms).
Polymers VI and VII were isolated as yellow and
yellowish green powders, respectively.
.
.
.
.
H N
N H
.
.
..
_
H
...
NaSn---Na+
IV
verted into thioaldehydes which then react with
hydrazine at a high rate. Probably, in our case benzoyl
chloride initially reacts with complex IV to give
sodium benzothioate which quickly reacts with hyd-
razine according to scheme (5). It is also possible that
hydrazine is a stronger nucleophile than polysulfide
ions with respect to benzoyl chloride.
The reaction of chloroacetyl chloride with sodium
disulfide generated from sodium sulfide and sulfur in
aqueous alcoholic medium gave thiocol-like poly-
sulfide polymer VIII according to scheme (7).
C6H5COCl + Na2S2
C6H5COSNa + NaCl,
2C6H5COSNa + NH2NH2
H2O, C2H5OH
Na2S2,
C6H5CONH NHCOC6H5 + 2NaSH.
(5)
Na2S + S
III
Cl
CH2CS2.5
O
nClCH2COCl + nNa2S2
(7)
The reaction of chloroacetyl chloride with sulfur in
the system hydrazine hydrate NaOH in water led to
formation of mixed S,N,O-containing polymers. The
sulfur concentration in the product decreases as the
fraction of hydrazine hydrate in the system increases.
The data of elemental analysis and IR spectroscopy
suggest that chloracetyl chloride initially reacts with
hydrazine to give N,N -bis(chloroacetyl)hydrazine (V)
which then undergoes polycondensation with sodium
polysulfides according to scheme (6).
n
VIII
Polymer VIII is a typical rubber-like thiocol which
melts over a wide temperature range (115 126 C).
Judging by its elemental composition, its structure
involves alternating di- and trisulfide units (Table 2).
The molecular weight of VIII (calculated from the
residual chlorine concentration) is 6120 au, i.e., it is
considerably higher that the molecular weights of
polymers VI and VII. Polymers VI, VII and VIII are
characterized by different IR spectra. The IR spectra
of VI and VII are consistent with the assumed
S8 + 8NaOH + 2NH2NH2 H2O 4Na2S2 + 2N2 + 10H2O,
NH2NH2 + 2ClCH2COCl
1
structure, cm : 3219 [ (NHN)]; 2991, 2930, 2855
ClCH2CONH NHCOCH2Cl,
(6)
[ (CH2)]; 1702 [ (NHCO)]; 1490, 1403 [ (CH2)];
1291, 1202, 1127, 880 [ (CN)]; 763, 639 [ (CS)];
544, 453, 427 [ (SS)]. In the IR spectrum of VIII we
observed absorption bands typical of poly(methylene-
2HCl
V
nClCH2CONH NHCOCH2Cl + nNa2Sm
Cl [ CH2CONH NHCOCH2Sm ]n + 2nNaCl,
1
polysulfide) polymers, cm : 2963, 2919 [ (CH2)];
VI, VII
1685 [ (CO)]; 1374, 1299, 1267, 1164 [ (CH2)]; 1067,
998 [ (CC)]; 786, 754, 734, 652 [ (CS)]; 587, 467
[ (SS)] [6].
VI, m = 2.5, n = 4; VII, m = 2, n = 6.
Probably, initial thiylation of chloroacetyl chloride
with complex IV gives sodium chloro(thioacetate)
which then quickly reacts with hydrazine following
scheme (5). This assumption is supported by the fact
that in the absence of sulfur chloroacetyl chloride
reacts with hydrazine very difficultly, presumably
because of its decomposition to the corresponding
ketene.
Thus, by the reaction of chloroacetyl chloride with
sulfur in the system hydrazine hydrate alkali we ob-
tained polymeric products of new types, namely poly-
[(diacylhydrazine) polysulfides].
The reaction of benzenesulfonyl chloride with
sulfur in the system hydrazine hydrate NaOH, as well
as with the system sodium sulfide sulfur, aforded bis-
(phenylsulfonyl)
[scheme (8)].
polysulfides
IX
and
IXa
Polymer VI is formed when the system contains
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THIYLATION OF FUNCTIONALIZED ELECTROPHILES WITH SULFUR
349
S8 + 8NaOH + 2NH2NH2 H2O
4Na2S2 + 2N2 + 10H2O,
amount of sulfur was added in portions to a solution
containing required amounts of alkali, hydrazine
hydrate, and water, heated to 40 50 C. The mixture
was heated for 1 2 h at 85 90 C and cooled to room
temperature, and the corresponding electrophile was
added. All reactions were accompanied by heat evolu-
tion and precipitation of products. The reaction
conditions and the yields and properties of the pro-
ducts are given in Table 1.
Na2S + S H O, C H OH Na2S2,
2
2 5
(8)
C6H5SO2Cl + Na2Sn
C6H5SO2SnSO2C6H5,
IX, IXa
IX, n = 5; IXa, n = 5.5.
Reactions of electrophilic reagents with the
system Na2S H2O S water ethanol. A mixture of
Na2S H2O, water, and ethanol was heated to 45 C
until it became homogeneous. Required amount of
sulfur was added in portions, the mixture was heated
for 1 2 h at 85 90 C and cooled to 25 C, and the
corresponding electrophile was added at 25 C. All
reactions were accompanied by heat evolution and
precipitation of products. The reaction conditions
and the yields and properties of the products are given
in Table 2.
Despite the fact that the amount of sulfur was
sufficient to generate only sodium disulfide, polysul-
fides IX and IXa fromed by reaction (8) contained
both tri- and tetrasulfide bridges. This means that
sulfide ions disproportionate in basic reducing me-
dium according to scheme (3). Presumably, sodium
sulfide is partially oxidized to sodium sulfite or sul-
fate. Therefore, the remaining sodium sulfide reacts
with sulfur to give sodium tri- and tetrasulfides. The
IR spectra of products IX and IXa are consistent with
1
the proposed structures, cm : 3190 [ (CH Ar)]; 1930,
1685 [ (C=C)]; 1411, 1400, 1160, 1130 [ (SO2)];
1060 [ (S=O)]; 765, 720, 670 [ (CS)]; 580, 520, 510
[ (SS)].
ACKNOWLEDGMENTS
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 00-03-32810a).
N,N,4-Trichlorobenzenesulfonamide reacted with
sulfur in the system hydrazine hydrate alkali to afford
4-chlorobenzenesulfonamide (X) [scheme (9)]. Pre-
sumably, the reaction also involves intermediate thiyla-
tion of the dichloro amide.
REFERENCES
1. Korchevin, N.A., Turchaninova, L.P., Deryagina, E.N.,
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S8 + 8NaOH + 3NH2NH2#f
+ 4ClC6H4SO2NCl2
H2O
4Na2S2 + 3N2 + 11H2O
2. Russavskaya, N.V., Alekminskaya, O.V., Korche-
vin, N.A., and Deryagina, E.N., Zh. Obshch. Khim.,
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+ 4ClC6H4SO2NH2 + 2HCl.
(9)
X
On the whole, the yields of sulfur-containing
products in the system hydrazine hydrate alkali are
higher than in the system sodium sulfide sulfur
(Tables 1, 2).
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EXPERIMENTAL
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ionizing electrons 57 eV, 25-m SB-5 capillary
column.
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Reactions of electrophilic reagents with sulfur in
the system hydrazine hydrate NaOH. Required
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 3 2004