Russian Journal of General Chemistry, Vol. 75, No. 2, 2005, pp. 194 199. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005,
pp. 220 225.
Original Russian Text Copyright
2005 by Deryagina, Levanova, Grabel’nykh, Sukhomazova, Russavskaya, Korchevin.
Thiylation of Polyelectrophiles with Sulfur
in Hydrazine Hydrate Amine Systems
E. N. Deryagina, E. P. Levanova, V. A. Grabel’nykh,
E. N. Sukhomazova, N. V. Russavskaya, and N. A. Korchevin
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received May 5, 2003
Abstract Thiylation of polyhaloalkanes and Paraform with elemental sulfur activated in hydrazine hyd-
rate organic amine systems is performed. Monoethanolamine, triethanolamine, and triethylamine were used
as amines. The reactions gave thiocols of various structures. The products were characterized by elemental
analysis and IR spectroscopy. Reductive cleavage of the synthesized thiocols was performed to obtain di- and
polythiols.
Previously we showed that sulfur is easily activated
in hydrazine hydrate alkali (NaOH, KOH) systems to
form polydisulfide anions, which allowed such sys-
tems to be used for fast and complete dissolution of
sulfur [1, 2]. We also found that elemental sulfur is
equally effectively activated in hydrazine hydrate
organic amine systems. As the organic amines we
tried primary, secondary, and tertiary amines, such as
monoethanolamine, morpholine, triethylamine, tri-
ethanolamine, as well as pure hydrazine hydrate [3].
various structures [5]. However, alkalis are hard bases
and may induce dehydrohalogenation of alkyl halides;
at high concentrations, alkalis can cause corrosion of
the reactor material. Therefore, we considered it
promising to replace alkalis with amines which are
free of the above disadvantages and studied sulfur
reactions with polyelectrophilic reagents in hydrazine
hydrate amine systems. As the polyelectrophiles we
used dichloromethane, 1,2-dichloroethane, 1-bromo-3-
chloropropane, 1,2,3-trichloropropane, , -dichloro-
ethyl ether (Chlorex), and Paraform. We also studied
the behavior of mixtures of organochlorine com-
pounds: a fraction containing 78% of 1,2- and 1,3-di-
chloropropanes and a fraction containing 76% of 1,2,3-
trichloropropane. These fractions are epichlorohydrin
production wastes whose utilization is an urgent
ecological problem [6]. As the amine in most experi-
ments we used monoethanolamine. In addition, for
the sake of comparison, the hydrazine hydrate tri-
ethanolamine and hydrazine hydrate triethylamine
systems were tested. The resulting data are shown in
Table 1.
Sulfur reacts with hydrazine hydrate (in the ab-
sence of bases) with heat release and vigorous evolu-
tion of hydrogen sulfide and ammonia, which con-
dense at the outlet of the reactor as ammonium hydro-
sulfide. The reaction of sulfur with hydrazine hydrate
alkali or hydrazine hydrate amine systems begins at
room temperature and occurs with warming-up of re-
action mixture to 60 65 C.
The quantity of dissolved sulfur depends on the
nature of the amine and the concentration of the latter
in hydrazine hydrate, and reaches 700 1300 g per 1 l
of hydrazine hydrate. As the mole fraction of the
amine increases from 5 to 50%, the maximum quan-
tity of dissolved sulfur increases by a factor of about
The example of dichloromethane and monoethanol-
amine was used to study the effect of conditions on
the synthesis of thiocols in hydrazine hydrate amine
systems. For high yields of poly(methylene polysul-
fides), dichloromethane should be reacted with sulfur
in the hydrazine hydrate medium at a low concentra-
tion of monoethanolamine. The S:HOCH CH NH :
1
.5; therewith, primary amines are more active than
secondary, and tertiary amines are the least active.
The best results were obtained with hydrazine hyd-
rate alkali and hydrazine hydrate monoethanolamine
systems [4].
2
2
2
N H OH:CH Cl mole ratio is 8:1:10:4. Therewith,
2
5
2
2
We have thoroughly studied thiylation of polyelec-
trophilic reagent in solutions of sulfur in hydrazine
hydrate alkali systems and developed in the course of
this research new synthetic approaches to thiocols of
the x value in the [CH S ] polymer unit is no more
2 x
than 2.7 (polymer I, yield 75%). Decreased fraction of
sulfur decreases both the yield of polymers and their
sulfur content (polymers II, III, and IIIa). At the
1
070-3632/05/7502-0194 2005 Pleiades Publishing, Inc.