Reaction of Mono- and Dihaloalkanes with Mixed Solutions of Chalcogens in Alkaline Reductive Systems

Article abstract of DOI:10.1023/A:1026126601555

Sufur-selenium, sulfur-tellurium, selenium-tellurium, and sulfur-selenium-tellurium mixtures readily dissolve in the hydrazine hydrate-alkali system to form chalcogenide anions. Alkylation of the latter with ethyl bromide results in preferential formation

Full text of DOI:10.1023/A:1026126601555

Russian Journal of General Chemistry, Vol. 73, No. 5, 2003, pp. 711 714. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 5, 2003,
pp. 752 755.
Original Russian Text Copyright
2003 by Deryagina, Grabel’nykh, Mamaseva.
Reaction of Mono- and Dihaloalkanes with Mixed Solutions
of Chalcogens in Alkaline Reductive Systems
E. N. Deryagina, V. A. Grabel’nykh, and T. V. Mamaseva
Favorskii Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received April 11, 2001
Abstract Sufur selenium, sulfur tellurium, selenium tellurium, and sulfur selenium tellurium mixtures
readily dissolve in the hydrazine hydrate alkali system to form chalcogenide anions. Alkylation of the latter
with ethyl bromide results in preferential formation of diethyl disulfide, diethyl diselenide, and diethyl ditel-
luride. Tellurium reacts with dichloromethane in the presence of sulfur, yielding poly(methylene ditelluride),
the reaction in the presence of selenium gives rise to poly(methylene selenotellurides), while in the sulfur
selenium tellurium mixture polymers containing all the components are formed.
Polymers with chalcogenide bridges in the chain
are used as photoactive cationic materials for electro-
photography [1 4].
or mixed sulfur and selenium solutions with dihalo-
alkanes affords poly(methylene diselenides) or mixed
poly(alkylene sulfoselenides) [7, 8].
We earlier showed that elemental chalcogens are
activated by such an alkaline reductive system as
hydrazine hydrate alkali; therewith, alkali metal mono-
or polychalcogenides are generated under mild condi-
tions [5, 6]. Moreover, we introduced into the alkaline
reductive system, in succession or simultaneously,
sulfur and selenium. It was found that on dissolution
of sulfur followed by selenium or of a mixture of
sulfur and selenium in the NaOH(KOH) N H H O
Proceeding with these studies, we have explored
the possibility of generation in alkaline reductive
systems of mixed selenotelluride, sulfotelluride, and
sulfoselenotelluride anions and their subsequent
alkylation with mono- and dihaloalkanes.
Into a solution of sodium hydroxide in hydrazine
hydrate we introduced in succession sulfur and tel-
lurium, selenium and tellurium, or sulfur and sele-
nium, and tellurium. The solutions were heated at 85
90 C for 1.5 h, cooled, and treated with ethyl bromide.
The reaction conditions and compositions and the
yields of the resulting compounds are listed in Table 1.
For the sake of comparison, we also give data for reac-
tions of mixtures of sulfur and selenium in similar
2
4
2
H O mixture, mixed alkali metal sulfoselenides are
2
generated along with mono- and polysulfides and
polyselenides. The formation of mixed alkali metal
sulfoselenides was detected in the alkylation of the
S Se NaOH(KOH) N H H O H O system with
2
4
2
2
ethyl bromide. The alkylation of selenium solutions
Table 1. Alkylation with ethyl bromide of chalcogen solutions in the hydrazine hydrate (30 40 ml) NaOH system
35 C)
(
Conver-
sion of
EtBr,
%
Initial reagents, g
chalcogens NaOH EtBr
Reaction
products,
g
Yields of reaction products, %
(per reacted EtBr)
S, 1.6; Se, 4.9
S, 3.2; Te, 12.8
S, 4.2; Te, 9.0
Se, 7.8; Te, 12.8 8.0
S, 2.1; Se, 5.2;
Te, 8.4
4.0
8.0
8.0
10.9a 98.0
6.5
10
6
12
11
2.2 (Et S), 5.5 (Et Se), 29.7 (Et S ), 36.2 (Et Se ), 25.9 (Et SSe)
2
2
2 2
2
2
2
21.8
21.8
21.8
21.8
97.7
98.0
85.0
85.0
3.5 (Et S), 21.3 (Et S ), 4.7 (Et Te), 37.2 (Et Te ), 5.0 (Et STe)
2 2 2 2 2 2 2
2.2 (Et S), 24.9 (Et S ), 2.7 (Et Te), 27.0 (Et2Te2), 2.1 (Et STe)
2 2 2 2 2
5.3 (Et Se), 43.7 (Et Se ), 3.5 (Et Te), 30.3 (Et Te ), 1.03 (Et SeTe)
2 2 2 2 2 2 2
8.0
Traces (Et S), 4.6 (Et Se), 15.5 (Et S ), 24.0 (Et Se ), 7.9 (Et Te),
2
2
2 2
2
2
2
14.4 (Et Te )
2
2
a
The synthesis was performed in water; volume of hydrazine hydrate 3 ml.
070-3632/03/7305-0711$25.00 2003 MAIK Nauka/Interperiodica
1

712
DERYAGINA et al.
conditions [8]. The reaction products were identified
by GLC using authentic samples, as well as by GC
MS. The mass spectra contain the molecular ions of
the resulting diethyl chalcogenides, including mixed
ones whose authentic samples were unavailable.
Thus, mixed anions are best formed from sulfur
and selenium, worse from sulfur and tellurium, and
very bad from selenium and tellurium. The reactions
of mixtures of sulfur and selenium are performed in
water, and hydrazine hydrate is taken in a stoichio-
metric amount as reducer. The other chalcogenides
are activated in hydrazine hydrate only. We took these
results into accout in alkylation of chalcogenides with
dihaloalkanes and preparation of polymers with dif-
ferent chalcogenide bridges.
Unlike the S Se system, the S Te system in the
alkaline reductive system generates little STe (yield
of diethyl sulfotelluride 5%). The major reaction
products here are diethyl disulfide and diethyl ditel-
luride, as well as small amounts of diethyl sulfide and
diethyl telluride.
We studied the synthesis of chalcogenide polymers
by alkylation with dihaloalkanes with selenium or
tellurium in alkaline reductive systems. It was found
that polymers are formed only when the selenium
solution is alkylated with dichloromethane [7] or
S + Te + 2 NaOH + N H4 H O
2
2
2
EtBr
Et S + Et Te + Et S + Et STe + Et Te .
2
2
2 2
2
2
2
3
.5% 4.7%
21.3% 5.0%
37.3%
1-bromo-3-chloropropane. At the same time, 1,2-di-
At the S:Te molar ratio increased to 2, the yields
of the mixed and ditelluride anions decrease.
chloro- and 1,2-dibromomethanes, 1,4-dibromobutane,
and 1,5-dichloropentane do not work in any condi-
tions. Probably, these alkylating agents undergo al-
kaline dehydrohalogenation to give ethylene,
Mixed anions are even worse generated on activa-
tion in the alkaline reductive system of a mixture of
selenium and tellurium.
1,3-butadiene, and 1,4-pentadiene, respectively.
Tellurium fails to react with dielectrophiles in these
Se + Te + 2NaOH + N H H O
2
4
2
systems. At the same time, the S Te, Se Te, and
S Se Te binary and ternary systems are alkylated
with dichloromethane, yielding polymers. The reac-
tion conditions and polymer compositions are given
in Table 2.
2
EtBr
Et Se + Et Te + Et Se + Et SeTe + Et Te .
2
2
2
2
2
2
2
5
.3% 3.5% 43.7%
1.03%
30.3%
With a 1:1:1 mixture of the three chalcogenides
in the hydrazine hydrate alkali system, only one
mixed sulfoselenide anion is formed in a low yield,
whereas the major anions formed are diselenide, as
well as dislfide and ditelluride.
Sulfur and tellurium in an aqueous hydrazine
hydrate NaOH system do not react with dichloro-
methane. However, this reaction occurs in hydrazine
hydrate as medium and reducer and gives a polymer
(black adhesive substance) which, according to its
elemental analysis, contains mostly ditelluride bridges.
S + Se + Te + 3NaOH + N H H O
2
4
2
2
EtBr
Et Se + Et Te + Et S + Et Se + Et SSe + Et Te .
The approximate formula C H S Te may corres-
2
2
2 2
2
2
2
2
2
3 14 0.5 7
4
.6%
7.9%
15.5% 24.0% 2.7%
14.4%
pond to the following polymer.
CH Cl
2
2
S + Te + 2NaOH + Na H H O
Cl [ CH TeTeCH TeTeCH TeTeCH STeCH TeTeCH TeTeCH TeTe ] CH Cl.
2 2 2 2 2 2 2 n 2
2
4
2
A certain excess of hydrogen atoms is presumably
explained by the presence in the polymer chain of
tetravalent tellurium atoms bound by hydrogen atoms.
The directions of alkylation of a mixture of sulfur and
tellurium in alkaline reductive systems with mono-
and dihaloalkanes are much different. Dichloro-
methane, unlike ethyl bromide, prefers to react with
ditelluride anions and, apparently, fully binds sulfo-
telluride anions. Therewith, poly(methylene ditel-
lurides) that have little sulfotelluride bridges acquire
stability in alkaline reductive systems (from tellurium
alone no polymer is formed). Similarly, selenium is
alkylated with 1,2-dichloroethane only in the presence
of sulfur [8].
The reaction of dichloromethane with a mixture of
selenium and tellurium in the hydrazine hydrate
NaOH system takes another pathway. The polymer
formed (black substance) comprises much selenium
and tellurium and has the formula C H Cl Se Te .
3
15 0.2
4
5
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 5 2003

REACTION OF MONO- AND DIHALOALKANES WITH MIXED SOLUTIONS
713
Table 2. Alkylation with dichloromethane of chalcogens in the hydrazine hydrate NaOH system (35 40 C)a
Initial reagents, g
Reac- Poly-
N H
tion mer
time, yield,
2
4
Found, %
Formula
Calculated, %
H O
2
chalcogens NaOH
dihalide
(
H O),
h
g
2
ml
S, 1.6; Te, 6.4 4.0 10 (30) CH Cl , 8.4
5
8
0
5
2
2
S, 1.6; Te, 6.4 4.0 40
CH Cl , 8.4
C 3.14; H 1.41; C H S Te7
S 1.4; Te 91.98
C 3.76; H 1.46;
S 1.67; Te 93.08
Te 100
2
2
3 14 0.5
Te, 12.8
4.0 40
4.0 40
CH Cl , 8.4
6
2
11.1
2
2
(Te)
8.5 C 3.73; H 1.57; C H Cl Se Te
5
Se, 3.9;
Te, 6.38
CH Cl , 8.4
C 3.56; H 1.4;
Cl 0.69; Se 31.28;
Te 62.87
2
2
3
15 0.2
4
Cl 0.88; Se 30.7;
Te 62.69
S, 1.2; Se, 2.73; 4.0 30
Te, 4.48
CH Cl , 8.4
2
2.5 C 5.72; H 0.83; C H Cl S Se2.5Te4 C 7.1; H 0.9;
2
2
5 8 0.1 2
Cl 0.5; S 7.35;
Se 20.2; Te 55.6
C 4.6; H 1.0; C H ClSe
Cl 0.4; S 7.6;
Se 23.48; Te 60.4
C 5.2; H 1.0;
Cl 7.7; Se 85.96
Se, 7.8
Se, 3.9
Se, 2.9
Se, 7.8
Se, 7.8
Se, 7.8
4.0
2.0
1.5
3
CH Cl , 12.8 1.5
8
2
2
2 5 5
(
0.2)
Cl 7.6; Se 86.22
b
ClCH CH Cl, 0.1
2
2
9
.8
b
1.0 12.5
BrCH CH Br, 0.5
2
2
7
.01
4.0
4.0
4.0
1.5
1.5
1.5
ClCH CH
0.1
0.1
0.1
9.4 C 14.16; H 3.24; C H Cl0.1Se3
C 12.74; H 2.81;
Cl 1.23; Se 83.3
2
2
3 8
CH Br, 7.9
Cl 1.09; Se 78.94
2
b
Br(CH ) Br,
2
4
1
0.8
b
Cl(CH ) Cl,
2
5
7
.05
a
All mixed poly(methylene chalcogenides) are black bright adhesive substances, poly(methylene diselenide) is a dark claret rubber-
b
like substance, and poly(propylene diselenide) is a solid dark orange substance.
Polymer is not formed.
This result suggests that the polymer chain contains
mostly diselenide and ditelluride bridges.
more excess hydrogen that sulfoteluride polymers.
This may also result from Te H bond formation in
the polymer chain. Dichloromethane, like ethyl
bromide, effectively binds ditelluride and diselenide
anions.
Se + Te + 2NaOH + Na H H O
2
4
2
CH Cl
2
2
Cl [ CH TeTeCH TeTeCH SeSeCH SeSe ] CH Cl.
A mixture of sulfur, selenium, and tellurim in the
hydrazine hydrate NaOH system, too, is alkylated
with dichloromethane to give a black adhesive
polymer. Its composition C H Cl S Se Te cor-
2
2
2
2
n
2
Mixed selenotelludie bridges are unlikely here,
since selenotelluride anions are scarcely formed
in this system. Selenotelluride polymers contain even
5
8
0.1
2
2.5
4
responds to the following structure.
CH Cl
2
2
S + Se + Te + 2NaOH + Na H H O
Cl [ CH TeTeCH TeTeCH SeSeCH SSCH Se ] CH Cl.
2 2 2 2 2 n 2
2
4
2
Dichloromethane alkylates the S + Se + Te mixture,
preferentially binding ditelluride anions. A few
mixed sulfoselenide bridges, too, may be present in
the polymer chain. The IR spectrum of the resulting
polymer shows the following frequencies, cm : 1445,
1
1376, 1125 [ (CH )], 770 [ (CH )], 630 (C Te), 570
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 5 2003

7
14
DERYAGINA et al.
dissolved completely. The reddish-orange solution
(Se Se), 580 (Te Te), 490 (S S, S Se).
was heated at 85 90 C for 1.5 h, cooled to room
temperature, and ethyl bromide was added. The reac-
tion mixture warmed up to 35 C (this temperature was
further maintained) and decolorized. After cooling, the
lower organic layer was separated, washed with water,
Thus, we found that sulfur selenium, sulfur tel-
lurium, selenium tellurium, and sulfur selen tellu-
rium mixtures in alkaline reductive systems form dif-
ferent chalcogenide anions. These anions are readily
alkylated with monohaloalkanes, such as ethyl
bromide. The major alkylation products are diethyl
disulfide, diethyl diselenide, and diethyl ditelluride.
Mixed diethyl chalcogenides are best formed from
sulfur and selenium, worse from sulfur and tellurium,
and very bad from selenium and tellurium. Individual
chalcogens or their mixtures differently react in with
dihaloalkanes in alkaline reductive systems. Tellurium
in the system hydrazine hydrate alkali fails to react
with dichloromethane but reacts with the latter in the
presence of sulfur. Therewith, sulfur scarcely takes
part in reaction and acts to stabilize poly(methylene
ditelluride) in alkaline reductive systems. In the pre-
sence of selenium, tellurium, too, is alkylated with
dichloromethane, forming mixed poly(methylene
selenotellurides) with alternating ditelluride and di-
selenide bridges. Ditelluride anions, too, prefer to
bind with dichloromethane in the presence of sele-
nium and sulfur. The resulting polymer contains di-
dried with CaCl , and subjected to GLC and GC MS
2
analysis. The yields of the reaction products were
estimated by GLC data.
Poly(alkylene chalcogenides). Chalcogens were
successively added in portions to a solution of NaOH
in hydrazine hydrate at 27 C until they dissolved
completely. The dark claret solution was heated at 85
90 C for 2 h. After cooling, dihaloalkane was added
in protions. The reaction mixture warmed up to 35
46 C and was kept at this temperature for some hours.
The polymers that precipitated were washed with
water and dried in a vacuum.
ACKNOWLEDGMENTS
The work was financially supported by the Rius-
sian Foundation for Basic Research (project no. 00-
03-32810a).
telluride, diselenide, and, apparently,
bridges (sulfoselenide bridges may also be present).
The developed simple procedures for synthesis of poly-
disulfide
REFERENCES
(
methylene chalcogenides) make use of available
1. Kishore, K. and Ganesh, K., Adv. Polym. Sci., 1995,
chalcogens and hydrazine hydrate alkali system.
vol. 121, no. 2, p. 81.
2
3
4
5
. JP Patent 6128527, Chem. Abstr., 1986, vol. 105,
no. 98203c.
EXPERIMENTAL
. US Patent 5376502, Chem. Abstr., 1995, vol. 122,
no. 214892d.
The IR spectra of the polymers were obtained on
an IFS-25, Sample Scant-250 instrument in KBr or
thin films. The mass spectra of the alkylation products
were obtained on an LKB-2091 GC MS system,
ionization energy 57 eV, gas chromatography was
performed on an SB-5 capillary column (25 m).
. US Patent 424496, Chem. Abstr., 1976, vol. 84,
no. 67846h.
. Korchevin, N.A., Podkuiko, P.A., Stankevich, V.K.,
Deryagina, E.N., and Voronkov, M.G., Zh. Obshch.
Khim., 1989, vol. 59, no. 8, p. 1788.
Analysis of the alkylation products of solutions of
sulfur and selenium with ethyl bromide was per-
formed by GLC on an LKhM-8MD-2 chtomatograph
in the linear programming mode (12 deg/min) using a
stainless-steel column (1000 3 mm) packed with 5%
of XE-60 on Chromaton N-AW-HMDS, carrier gas
helium.
6. Korchevin, N.A., Turchaninova, L.P., Deryagina, E.N.,
and Voronkov, M.G., Zh. Obshch. Khim., 1989, vol. 59,
no. 8, p. 1785.
7
. Deryagina, E.N., Russavskaya, N.V., Alekmin-
skaya, O.V., and Grabel’nykh, V.A., Zh. Obshch. Khim.,
2
000, vol. 70, no. 12, p. 2051.
Mixed diethyl chalcogenides (Table 1). Chalco-
gens were successively added in portions to a solu-
tion of NaOH in hydrazine hydrate at 27 C until they
8. Deryagina, E.N., Grabel’nykh, V.A., Russavskaya, N.V.,
and Alekminskaya, O.V., Zh. Obshch. Khim., 2001,
vol. 71, no. 11, p. 1825.
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