New Routes to Poly(Alkylene Sulfidoselenides)

Article abstract of DOI:10.1023/A:1013934206501

A procedure was developed for preparing mixed poly(alkylene sulfidoselenides) by simultaneous dissolution of sulfur and selenium in basic reducing systems NaOH (KOH)-N2H4 * H2O-H2O, followed by alkylation of the resulting solutions with bielectrophilic agents.

Full text of DOI:10.1023/A:1013934206501

Russian Journal of General Chemistry, Vol. 71, No. 11, 2001, pp. 1729 1733. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 11, 2001,
pp. 1825 1829.
Original Russian Text Copyright
2001 by Deryagina, Grabel’nykh, Russavskaya, Alekminskaya.
New Routes to Poly(Alkylene Sulfidoselenides)
E. N. Deryagina, V. A. Grabel’nykh, N. V. Russavskaya, and O. V. Alekminskaya
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received April 26, 2000
Abstract A procedure was developed for preparing mixed poly(alkylene sulfidoselenides) by simultaneous
dissolution of sulfur and selenium in basic reducing systems NaOH (KOH) N2H4 H2O H2O, followed by
alkylation of the resulting solutions with bielectrophilic agents.
Mixed chalcogen-containing compounds and poly-
mers are used as photoconductors [1] and plastics for
electrophotography [2].
alkylation of the systems S Se NaOH (KOH) N2H4
H2O H2O with ethyl bromide [scheme (1)] (Table 1).
S + Se + NaOH + N2H4 H2O
Na2S + Na2Se + Na2S2
Poly(alkylene sulfidoselenides) are prepared by
alkylation with dihaloalkanes of mixed alkali metal
sulfidoselenides [2]. The latter species are generated
by reaction of selenium with solutions of sodium
mono-, di-, and trisulfide or of sulfur with solutions
of sodium polyselenide. The reaction yields Na2SSe2.
Fusion of a mixture of sodium sulfide and selenium
yields mainly Na2SSe3 [3]. Cyclic sulfides of the
+ Na2SSe + Na2Se2 + Na2S3 + Na2SSe2 + Na2Se3
EtBr
Et2S + Et2Se + Et2S2 + EtSSeEt + Et2Se2 + Et2S3
+ EtSSeSeEt + Et2Se3. (1)
The composition of the mixture of diethyl chalco-
genides was determined by GLC and GC MS. For
each compound in scheme (1) we detected the molec-
ular ion. This fact shows that at equimolar ratio of
sulfur and selenium the major species generated by
reaction (1) are the anions S22 , SSe2 , and Se22 ,
which are formed in approximately equal amounts.
A twofold excess of selenium favors predominant for-
mation of SSe2 and Se22 , and insignificant amounts
of Se2 , S22 , Se2S2 , S32 , and Se23 are also formed.
At a twofold molar excess of sulfur, the content of
mixed sulfidoselenide anions decreases, and the S2
and Se2 anions appear.
general formula SenS8 were prepared by reaction of
n
a mixture of Se2Cl2 and SCl2 with KI [4].
We have shown previously that elemental chalco-
gens are activated with such basic reducing system as
hydrazine hydrate alkali, with alkali metal mono- and
polychalcogenides being generated under mild condi-
tions [5, 6].
Proceeding with these studies, we added (succes-
sively or simultaneously) sulfur and selenium to the
basic reducing system. We found that on dissolution
of first sulfur and then selenium, or of a mixture of
sulfur and selenium in the system NaOH (KOH)
N2H4 H2O H2O, mixed alkali metal sulfidoselenides
are generated along with monosulfides, polysulfides,
and polyselenides. Their formation was detected in
Alkylation of the system S Se NaOH N2H4 H2O
H2O with such bielectrophilic agents as dichloro-
methane, 1,2-dichloroethane, or paraform was tested
as a route to poly(alkylene sulfidoselenides). Hydra-
Table 1. Synthesis of diethyl sulfidoselenidesa
Molar
ratio
S : Se
Content in reaction products, % (yield, mol %)
Et2S2 Et2SSe Et2Se2 Et2S3 EtS2Se
Et2S
Et2Se
Et2SSe2 Et2Se3
1 : 1
1 : 2
2 : 1
2.25(2.2) 4.5 (5.5) 21.35(29.7) 25.8 (25.9) 46.1 (36.2)
1.1 (2.2) 2.5 (2.9) 6.7 (9.5) 23.7 (24.8) 44.8 (36.1) 1.3 (1.4) 1.3 (1.1) 0.6 (0.4) 0.5 (0.3)
3.3 (6.0) 4.6 (5.4) 21.0 (27.9) 15.0 (15.4) 36.5 (29.6)
a
In all the experiments we took 0.1 mol of NaOH, 5 ml of hydrazine hydrate, 30 ml of water, and 0.1 mol of ethyl bromide.
1070-3632/01/7111-1729$25.00 2001 MAIK Nauka/Interperiodica

1730
DERYAGINA et al.
Table 2. Conditions for synthesis of poly(alkylene sulfidoselenides) I IX (30 ml of water, unless otherwise stated) and
properties of the polymers
Comp.
no.
S,
mol
Se,
mol
NaOH,
mol
N2H4 H2O,
mol
Temperature,
(time, h)
C
Polymer
yield, g
Reagent, mol
I
II
0.05
0.1
0.225
0.2
0.05
0.005
0.01
0.005
0.01
KOH, 0.1
0.1
0.03
CH2Cl2, 0.2
CH2Cl2, 0.2
CH2Cl2, 0.09
CH2Cl2, 0.2
CH2Cl2, 0.2
CH2Cl2, 0.02
[ CH2O ]n , 0.3
ClCH2CH2Cl, 0.05
ClCH2CH2Cl, 0.05
35 (8)
35 37 (5)
35 38 (5)
38 (7)
38 (7)
35 38 (5)
90 (2.5)
5.4
3.0
3.7
6.5
3.7
1.2
5.0
4.9
3.5
0.025
III
IV
V
VI
VII
VIII
IX
0.01
0.1
0.01
0.01
0.1
0.2a
0.025
0.025
0.0025b
0.025
0.14
0.1
SeS3 alloy, 0.01
0.05
0.05
0.005
0.05
0.1
0.1
65 70 (1.5)
70 (1)
Mixture S, 0.05 + Se, 0.05
0.14
Found, %c
Calculated, %
Comp.
no.
mp, C (appearance, color)
Formula
C
H
S
Se
C
H
S
Se
I
II
95 180 (solid, claret-colored)
55 100 (powder, yellow)
(Sticky, orange)
110 120 (viscous, orange)
(Viscous, claret-colored)
(Solid, dark green)
55 59 (solid, orange)
(Sticky, claret-colored)
(Friable, claret-colored)
7.8 2.0 23.5 67.0
CH2SSe
9.6 1.6 25.6 63.2
14.7 2.8 77.4
78.0
8.0 2.3 86.5
2.45
2.2
1.9
CH2S2Se0.03
CH2S2Se0.03
CH2S3Se0.02
CH3S2Se0.2
CH3S3Se
C3H8S4Se0.1O0.1 20.0 4.1 71.0
C2H4S2Se1.4
14.9 2.5 79.6
79.6
10.7 1.8 86.0
2.9
2.9
1.4
III
IV
V
VI
VII
VIII
IX
11.5 3.0 64.0 19.4
6.5 1.8 50.2 40.0
12.1 3.0 65.2 19.7
6.3 1.5 50.5 41.5
18.2 4.0 62.0
3.9
1.9
10.5 2.7 30.0 56.3
23.0 56.5
11.4 1.9 30.0 56.4
C2H4S1.4Se1.4
24.0 61.2
a
b
c
No water added.
3 ml of water.
Polymers I VI, VIII, and IX also contain 0.7 2.0% Cl.
zine hydrate was used as reductant, and water, as
solvent. Sulfur and selenium were added to the basic
reducing system in equimolar amounts, or sulfur was
taken in a large excess. The reaction conditions and
polymer yields are listed in Table 2. Alkylation of
S Se solutions with dichloromethane or paraform
yields polymers I VI and VII [scheme (2)]. Based
on the results of alkylation of the system S Se
(2)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 11 2001

NEW ROUTES TO POLY(ALKYLENE SULFIDOSELENIDES)
1731
NaOH (KOH) N2H4 H2O H2O with ethyl bromide
(Table 1), and also on the molecular formulas, we
can ascribe to these polymers the structure shown in
scheme (2). The polymers differ in the ratio of the
of alkali to the sum of sulfur and selenium (polymers
II, VII). These polymers are mainly poly(methylene
disulfides) promoted with methylene diselenide and
methylene sulfidoselenide units. As judged by ele-
similar monomeric units, governed by the ratio of mental analysis, polymer VII based on paraform also
the initial reactants.
contains methylene oxide units. With an excess of
hydrazine hydrate or alkali, sticky or viscous poly-
mers III and IV are formed, in which methylene
disulfide and trisulfide units prevail. The difference
in the appearance of polymers II and III having
the same molecular formula is due to the fact that
polymer III was prepared in hydrazine hydrate
with no water added and therefore it has a lower mo-
lecular weight (in the more basic medium the poly-
mer partially degrades).
At equimolar ratio of sulfur and selenium, disul-
fide, diselenide, and sulfidoselenide units prevail
in the polymers. Polymer I is a rubbery, almost
solid claret-colored compound. Polymer VI formed
from the sulfur selenium alloy SeS3 has a similar
composition, but it is a solid dark green substance
which can be crushed. In polymers formed when re-
action (2) is carried out with excess sulfur, methyl-
ene disulfide and trisulfide units prevail. Forma-
tion of powdered yellow or orange polymers from
both dichloromethane and paraform is favored by
Poly(ethylene sulfidoselenides) VIII and IX are
formed by alkylation of the system S Se NaOH
deficiency of hydrazine hydrate and equimolar ratio N2H4 H2O H2O with 1,2-dichloroethane [scheme (3)].
(3)
The elemental analysis of polymers VIII and IX,
which were prepared with the equimolar ratio of sul-
fur and selenium, is better consistent with the compo-
sition of the unit [CH2CH2SSe]. However, the poly-
mer chain. However, their assignment to the C=S
vibrations seems more likely. Such fragments were
detected in the other related polymers [8]. In the IR
spectra of poly(methylene diselenides), the strongest
1
meric chain, in accordance with scheme (1), actually bands are those at 1102 1030 cm . In the IR spectra
contains also approximately equal amounts of ethyl-
ene disulfide and ethylene diselenide units. Dissolu-
tion of first sulfur and then selenium in the system
S Se NaOH N2H4 H2O H2O, followed by alkyla-
tion with 1,2-dichloroethane, yields sticky claret-
colored polymer VIII. When a mixture of sulfur and
selenium is dissolved, friable claret-colored poly-
mer IX is formed. All the polymers can also con-
tain minor amounts of methylene monochalcogenide
units.
of mixed poly(methylene sulfidoselenides) with equal
or comparable content of sulfur and selenium, the
1
strongest bands are those at 1445 and 1123 cm
(polymer I). These frequencies are apparently charac-
teristic of such mixed polymers. The IR spectra of
the polymers in which the sulfur content considerably
exceeds that of selenium contain bands characteristic
of both poly(methylene disulfides) and poly(methyl-
ene diselenides). The IR spectra of III V contain
1
strong bands at about 1510 cm . These polymers
were prepared with an excess of hydrazine hydrate or
alkali, which often favors elimination of sulfur or
selenium atoms from the polymer chain. As a result,
C C bonds are formed, whose vibrations can give rise
to such bands.
The IR spectra of the polymers confirm their struc-
ture and indicate the presence of C S and C Se
bonds (Table 3). The strongest bands are observed
1
in the range 1170 1179 cm . They are present in the
spectra of pure poly(methylene polysulfides) [7] but
absent in the spectrum of poly(methylene diselenide).
Initially they were assigned to vibrations of the poly-
Thus, we have developed a new route to practically
important poly(alkylene sulfidoselenides). Its advan-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 11 2001

1732
DERYAGINA et al.
1
Table 3. IR spectra of polymers I VIII, cm
Comp.
no.
Se Se, S S,
S Se
(CH2)
(CH2)
C=S
C S
C Se
I
II
III
IV
V
2980, 2922, 2848 1445, 1124, 1023
2950, 2892, 2858 1359, 947, 859, 850
2960, 2919, 2851 1510, 1461, 1376, 1113
787, 750
700, 666, 615 512, 490, 453
1171 808, 776, 756 730, 702, 543 486, 467
1172 812, 782 734, 701, 635 488, 467
1179 849, 812, 782 732, 699, 634 469, 434
1172 849, 812, 782, 732, 699, 634 469, 434
765
2963, 2902
2963, 2903
1510, 1379, 1162, 1114
1510, 1119, 1375
VI
VII
2955, 2920, 2858 1374, 1143
2955, 2922, 2858 1361, 1086
1173 849, 812, 780 731, 704, 563 482, 465
1170 861, 804, 776 731, 702, 668, 469
586
VIII
X
2906, 2858
2950, 2902, 2855 1457, 1362
1407, 1246, 1187, 1164, 1104
836, 813
1173 881, 846, 806,
775
717, 675, 607 471
487, 468
XI
2983, 2919, 2854 1538, 1454, 1356, 1259,
1102, 1130
753, 731, 615, 467
572, 534
tages over the known routes are the use of commer-
cially available chemicals and a simple synthesis
procedure.
analyzed by GC MS. The yields of reaction products
were determined by GLC.
Poly(alkylene sulfidoselenides) I IX. Sulfur and
selenium were added in portions, simultaneously or
successively, to a solution of the calculated amounts
of alkali and hydrazine hydrate. The mixture was
stirred for 1 h. In the process, it became red-orange
and spontaneously warmed up to 60 C. Then the mix-
ture was heated for 1 h at 85 C and cooled to room
temperature, after which the calculated amount of the
alkylating agent was added in portions over a period
of 0.5 h. The mixture warmed up to 35 46 C and was
kept at this temperature for several hours. The precipi-
tated polymers were washed with water and vacuum-
dried.
EXPERIMENTAL
The IR spectra of polymers were taken on an IFS-
25, Sample Scant:250 spectrometer from KBr pellets
or thin films.
The mass spectra of the alkylation products were
recorded with an LKB-2091 gas chromatograph mass
spectrometer. Samples were introduced through a
25-m capillary column coated with SB-5; the ionizing
electron energy was 57 eV.
The products of alkylation of sulfur and selenium
solutions with ethyl bromide were analyzed by GLC
with an LKhM-8MD-2 chromatograph in the linear
heating mode (12 deg min ); a 1000 3-mm stain-
less steel column was used; liquid phase XE-60, 5%
on Chromaton N-AW-HMDS; carrier gas helium.
The IR data for poly(methylene disulfide) X are
taken from [7].
For comparison, we also prepared, following the
procedure in [6], poly(methylene diselenide) XI. Its
IR spectrum is given in Table 3.
1
ACKNOWLEDGMENTS
Mixed diethyl sulfidoselenides. A mixture of
powdered sulfur and selenium was added in portions
to a mixture of 0.105 mol of NaOH, 0.025 mol of
hydrazine hydrate, and 30 ml of water. The red-orange
mixture was heated for 2 h at 90 C and cooled to
room temperature, after which 0.1 mol of ethyl bro-
mide was added. The mixture spontaneously warmed
up to 52 56 C and decolorized. The organic layer was
separated, washed with water, dried over CaCl2, and
The study was financially supported by the Russian
Foundation for Basic Research (project no. 00-03-
32810a).
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 11 2001

NEW ROUTES TO POLY(ALKYLENE SULFIDOSELENIDES)
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