Reactions of diorganyl disulfides with dihaloalkanes in basic reductive media. Synthesis of bis(organylthio)alkanes

Article abstract of DOI:10.1023/A:1015397313038

A convenient preparative synthesis of bis(organylthio)alkanes was developed. It is based on alkylation with dihaloalkanes of solutions of diorganyl disulfides in the basic reductive system hydrazine hydrate-alkali. The generation of organylthiolate anions

Full text of DOI:10.1023/A:1015397313038

Russian Journal of General Chemistry, Vol. 72, No. 1, 2002, pp. 75 78. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 1, 2002,
pp. 82 85.
Original Russian Text Copyright
2002 by Alekminskaya, Russavskaya, Korchevin, Deryagina.
Reactions of Diorganyl Disulfides with Dihaloalkanes
in Basic Reductive Media. Synthesis of Bis(organylthio)alkanes
O. V. Alekminskaya, N. V. Russavskaya, N. A. Korchevin, and E. N. Deryagina
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received May 10, 2000
Abstract A convenient preparative synthesis of bis(organylthio)alkanes was developed. It is based on
alkylation with dihaloalkanes of solutions of diorganyl disulfides in the basic reductive system hydrazine
hydrate alkali. The generation of organylthiolate anions from disulfides and the subsequent reaction of the
anions with dihaloalkanes are performed in one reaction vessel without isolation of intermediate alkali metal
thiolates. At the same time, the reactions of diphenyl or dithienyl disulfides with dihaloalkanes result in
substitution with the thiolate anions of only one halogen atom to give the corresponding unsymmetrical
sulfides. In certain cases in the presence of excess alkali the latter sulfides are dehalogenated to form alkyl
vinyl sulfides.
Bis(organylthio)alkanes of the general formula
RS(CH2)nSR (I), which comprise two sulfide sulfur
atoms, can serve as complex-forming and flotation
agents, as well as metal corrosion inhibitors. By
varying n in these compounds, thus varying the
distance between the ligand centers, one can attain
geometric characteristics ideal for coordination or
adsorption. Quite recently Smith et al. [1, 2] showed
that compounds I effectively catalyze selective chlori-
nation of certain aromatic compounds [1, 2].
react with dielectrophiles (previously we used this
approach to synthesize unsymmetrical sulfides from
disulfides [4]).
2R2S2 + N2H4 H2O + 4MOH
+ 5H2O,
4RSM + N2
2RSM + X(CH2)nX
RS(CH2)nSR,
Ia Ik
(1)
For R, M, X, Y, and n, see Table 1.
The known methods of synthesis of compounds I
are based either on the reaction of thiols with for-
maldehyde (only for n = 1) or on the reaction of thiols
or dithiols with organyl halides [3]. The potential of
these methods is much restricted by the use of thiols
and dithiols as starting materials, since they are
hardly accessible and, moreover, highly volatile and
unpleasantly odored compounds. Thiols and dithiols
are readily oxidized to disulfides, and the latter are
inactive in the above reactions.
The generation from disulfides of organylthiolate
anions and their subsequent reaction with dihaloal-
kanes by scheme (1) are accomplished in one reaction
vessel without isolation of intermediate alkali metal
thiolates. The conditions of synthesis and the yields
of bis-sulfides I are listed in Table 1. As seen from
the table, to improve the yields of compounds I
requires that the basic reductive activity of the
medium be sufficiently high (large excesses of alkali
and hydrazine hydrate).
However, thiols or the corresponding thiolates are
easy to generate in situ by reductive cleavage of the
S S bond in disulfides [4]. Diorganyl disulfides are
less volatile than thiols and more stable in handling
and use. Moreover, they are fairly accessible reagents.
They are synthesized by alkylation of sulfur in basic
reductive media [5].
The example of the reaction of 1,2-dichloroethane
with diethyl disulfide was used to show that even with
a tenfold excess of dichloride the reaction involves no
substitution of one of the chlorine atoms by the thio-
late anion to give an unsymmetrical sulfide (1-ethyl-
thio-2-chloroethane). The GC MS data rule out
formation of unsymmetrical sulfides in reactions (1)
with dialkyl disulfides (R = Me, Et, Pr).
We found that bis(organylthio)alkanes (I) are
formed by alkylation with dihaloalkanes of solutions
of diorganyl disulfides in the basic reductive system
hydrazine hydrate alkali. Therewith, the S S bond is
reduced to give organylthiolate anions which then
At the same time, unsymmetrical sulfides II are
readily formed on the reactions of diphenyl or di-
thienyl disulfides with dihaloalkanes by scheme (2):
1070-3632/02/7201-0075$27.00 2002 MAIK Nauka/Interperiodica

76
ALEKMINSKAYA et al.
Table 1. Conditions of synthesis and yields of bis(organylthio)alkanes I
Comp.
no.
R2S2 : MOH: N2H4 H2O: X(CH2)nY
R
M
n
X, Y
Yield, %
molar ratio
Ia
Ib
Ic
Ic
Ic
Ic
Id
Id
Id
Id
Id
Ie
If
If
If
Ig
Ih
Ii
Ii
Ii
Ij
Ij
Et
Pr
Na
Na
Na
Na
Na
K
Na
Na
Na
K
Na
Na
Na
Na
Na
Na
K
Na
Na
Na
Na
Na
Na
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
4
4
5
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Br
Cl
Cl
0.05: 0.2: 0.7: 0.05
0.05: 0.12: 0.4: 0.05
0.05: 0.2: 0.5: 0.1
0.05: 0.6: 0.5: 0.1
0.05: 0.1: 0.5: 0.1
0.05: 0.15: 0.5: 0.1
0.05: 0.22: 0.8: 0.05
0.05: 0.22: 0.4: 0.05
0.05: 0.1: 0.5: 0.05
0.05: 0.1: 0.5: 0.05
0.05: 0.2: 0.8: 0.5
77
58
85
70a
38
82
74
52b
40
52
78
70
66
73
25c
6d
Me
Me
Me
Me
Et
Et
Et
Et
Et
Pr
0.1: 0.22: 0.8: 0.1
Ph
Ph
Ph
0.009: 0.018: 0.1: 0.009
0.009: 0.018: 0.1: 0.009
0.014: 0.028: 0.2: 0.018
0.006: 0.012: 0.2: 0.006
0.01: 0.022: 0.3: 0.01
0.05: 0.22: 0.5: 0.05
0.05: 1.0: 0.8: 0.1
0.05: 0.1: 0.5: 0.05
0.05: 0.22: 0.7: 0.1
0.05: 0.22: 0.3: 0.1
0.05: 0.23: 0.8: 0.1
C4H3S
8-Quinolyl
Cl
20e
84
80
41
76
48b
68
Et
Et
Et
Et
Et
Et
Cl, Br
Cl, Br
Cl, Br
Br
Br
Br
Ik
a
c
b
Simultaneously CH SCH=CH (IIIa) is formed (yield 8%). Hydrazine hydrate was diluted with water (1:1 by volume).
3
2
d
-Chloroethyl phenyl sulfide (IIa) is formed (yield 68%). The major reaction product is -chloroethyl 2-thienyl sulfide (IIb)
(yield 85%). 8-Quinolyl vinyl sulfide (IIIb) is formed (yield 31%). With sodium 8-quinolylthiolate, the yields of compounds Ih
e
and IIIb are 32 and 18%.
II + RSM
I.
MX
2R2S2 + N2H4 H2O + 4MOH
+ 5H2O,
4RSM +N2
Sulfides IIa and IIb are worse soluble in water,
and, therefore, they quickly pass into the organic phase.
It is not also excluded that the reason for the different
reactivities of dialkyl and diaryl(hetaryl) disulfides in
reactions (1) and (2) may lie in the reduced nucleo-
philicity of aryl- and thienylthiolate anions.
(2)
RSM + ClCH2CH2Cl
RSCH2CH2Cl,
MCl
IIa, IIb
R = Ph (a),
(b).
S
Diphenyl disulfide already with a double excess of
dichloroethane gives primarily sulfide IIa. With di-
thienyl disulfide even at equimolar reagent amounts,
the major product of reaction (2) is unsymmetrical
sulfide IIb. The different reactivities of dialkyl and
diaryl(hetaryl) disulfides in their reactions with di-
haloalkanes by schemes (1) and (2) are apparently
explained by different solubilities of sulfides II in
the aqueous system hydrazine hydrate alkali. Sulfides
like II formed from dialkyl disulfides in the first stage
of reaction (1) are readily soluble in the aqueous
system, and, therefore, they convert into bis-sulfides I
without passing into the organic phase.
Reactions (1) and (2) with excess alkali sometimes
involve dehalogenation of sulfides II to form un-
saturated sulfides III by scheme (3).
(3)
RS(CH2)nCl
RSCH=CH2,
HCl
IIIa, IIIb
n = 2, R = Me (a), 8-quinolyl (b).
Sulfides III are formed with a sixfold or greater
excess of alkali, as shown with the reaction with
dimethyl disulfide by scheme (1) as example. At the
same time, reaction (1) with di(8-quinolyl) disulfide
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 1 2002

REACTIONS OF DIORGANYL DISULFIDES WITH DIHALOALKANES
Table 2. Physicochemical characteristics of compounds I III
77
bp,
(p, mm)
(mp, C)
C
Comp.
no.
1H NMR spectrum, , ppm
Reference
Ia
Ib
Ic
95 (40)
132 (54)
77 (20)
1.25 t (CH3), 2.65 q (CCH2S), 3.81 s (SCH2S)
0.98 t (CH3), 1.61 m (CCH2C), 2.61 t (CCH2S), 3.64 s (SCH2S)
2.08 s (CH3), 2.65 s (CH2)
[6]
[7]
[8]
Id
Ie
If
Ig
Ih
Ii
134 (45)
102 (40)
1.25 t (CH3), 2.52 q (CH3CH2S), 2.72 s (SCH2CH2S)
0.97 t (CH3), 1.61 m (CCH2C), 2.52 t (CCCH2S), 3.70 s (SCH2CH2S)
3.06 s (CH2S), 7.26 (HAr)
2.92 s (CH2S), 6.90 7.38 m (thienyl H)
3.45 s (CH2S), 7.10 8.94 m (quinolyl H)
1.25 t (CH3), 2.59 m (CH2S), 1.88 m (CCH2C)
1.24 t (CH3), 2.51 m (CH2S), 1.68 m (CCH2C)
1.24 t (CH3), 2.51 m (CH2S), 1.53 m (CCH2C)
3.20 s (CH2S), 3.57 t (CCH2Cl), 7.26 m (HAr)
3.01 s (CH2S), 3.61 t (CH2Cl), 6.90 7.38 m (thienyl H)
5.57 d (trans-C=CH), 5.71 d (cis-C=CH), 6.75 d. d (SCH=) (Jcis 9, Jtrans 17 Hz),
6.92 8.78 m (quinolyl H)
[9]
[10]
[11]
(65 66)
a
b
125 (35)
125 (35)
106 (2)
180 (5)
110 (5)
(35 39)
[12]
[12]
[12]
[13]
Ij
Ik
IIa
IIbc
IIIb
[14]
a
1
b
1
Identified by the H NMR spectrum in mixture with sulfide IIb (not isolated individual). Identified by the H NMR spectrum in
c
mixture with vinyl sulfide IIIb (not isolated individual). Found, %: Cl 19.76; S 35.92. C H ClS . Calculated, %: Cl 19.89,
6
7
2
S 35.83.
even at an equimolar amount of alkali results in ex-
clusive formation of sulfide IIIb in a moderate yield.
Such reaction result can be explained by the effect of
the quinoline nitrogen which acts as a basic center
located in the immediate vicinity of the leaving group.
Actually, the diquinolyl disulfide is fairly difficultly
reduced by the hydrazine hydrate alkali system. As a
result, for preparing an equimolar mixture we used
sodium 8-mercaptoquinolinate.
tra were measured on a Bruker DPX-400 spectrometer
(400 MHz) in CDCl3 solutions, internal reference
HMDS.
The reaction progress was followed and the purity
of the reaction products was determined by GLC on
an LKhM-80MD chromatograph (column 2000
3 mm, packing 5% XE-60 on Chromaton N-AW-
HMDS), carrier gas helium, linear temperature
programming at a rate of 12 deg/min.
Thus, we proposed a convenient preparative syn-
thetic procedure for bis(organylthio)alkanes I. They
are formed by alkylation with dihaloalkanes of solu-
tions of diorganyl disulfides in the basic reductive
system hydrazine hydrate alkali. The generation of
organylthiolate anions from disulfides and the sub-
sequent reaction of the anions with dihaloalkanes are
accomplished in one reaction vessel without isolation
of intermediate alkali metal thiolates. At the same
time, the reactions of diphenyl or dithienyl disulfides
with dihaloalkanes involve substitution by the thiolate
anions of only one halogen atom, yielding unsym-
metrical sulfides II. When excess alkali is used, some
sulfides II undergo dehalogenation to give alkyl vinyl
sulfides III.
Gas chromatography mass spectrometry was per-
formed on an AHP 5972 GC MS system (capillary
column 50000 0.2 mm 0.5 m, liquid phase PONA,
carrier gas helium, linear temperature programming at
a rate of 12 deg/min).
The physicochemical characteristics of the syn-
thesized compounds are listed in Table 2.
Synthesis of bis(organylthio)alkanes I. A four-
neck flask equipped with a stirrer, a reflux condenser,
a thermometer, and a charging device was charged with
required amouns of alkali, hydrazine hydrate, and
diorganyl disulfide (Table 1). The mixture was vi-
gorously stirred with heating (90 C) until homo-
geneous (2 3 h), cooled to room temperature, and,
after addition of dihalide, heated at 50 C for 2 h and
cooled. The organic layer was separated and dried
over CaCl2. The yields of the reaction products,
calculated from GLC data, are listed in Table 1. The
EXPERIMENTAL
The IR spectra were obtained on an IFS-25 in-
strument in thin films or KBr pellets. The NMR spec-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 1 2002

78
ALEKMINSKAYA et al.
target products were isolated by vacuum distillation
of the reaction mixtures. Compound If was recrystal-
lized from ethanol after distillation. The IR spectra of
compounds I all showed strong bands due to stretch-
3. Comprehensive Organic Chemistry, Barton, D.H. and
Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 3.
Translated under the title Obshchaya organicheskaya
khimiya, Moscow: Khimiya, 1983, vol. 5.
4. Deryagina, E.N., Korchevin, N.A., and Paper-
naya, L.K., Zh. Obshch. Khim., 1997, vol. 67, no. 5,
pp. 866 869.
1
ing (2850 2970 cm ) and deformation (1410
1
1350 cm ) vibrations characteristic of methylene and
methyl C H bonds.
5. Korchevin, N.A., Turchaninova, L.P., Deryagina, E.N.,
and Voronkov, M.G., Zh. Obshch. Khim., 1989,
vol. 59, no. 8, pp. 1785 1787.
6. Fecher, F. and Vogelbruch, K., Chem. Ber., 1966,
vol. 99, no. 4, pp. 1393 1413.
Organyl chloromethyl sulfides II were obtained in
a similar way under the conditions given in Table 1
and isolated by vacuum distillation of the reaction
mixtures.
8-Quinolyl vinyl sulfide (IIIb) was isolated by
recrystallization from ethanol.
7. Mostagli, P. and Langlois, Y., C. R. Acad. Sci., 1964,
vol. 258, no. 7, pp. 2092 2093.
Methyl vinyl sulfide (IIIa) was identified by GC
MS. Mass spectrum, m/z (Irel, %): 74 (10) (M+), 72
8. Derygina, E.N., Russavskaya, N.V., Alekmin-
skaya, O.V., Korchevin, N.A., and Trofimov, B.A.,
Sulfur Lett., 1999, vol. 22, no. 3, pp. 85 88.
(100) (M
H2)+, 59 (8) (M
CH3)+, 57 (97)
(HC CS)+, 46 (10) (CH2S)+, 39 (75) (M H2S H)+.
9. Simao, M., Quimica, 1942, no. 1, pp. 75 410; Chem.
Abstr., 1946, vol. 40, no. 2798.
ACKNOWLEDGMENTS
10. Shostakovskii, M.F., Prilezhaeva, E.N., and Ivano-
va, N.I., Izv. Akad. Nauk SSSR, Ser. Khim., 1955,
no. 4, pp. 906 912.
The work was financially supported by the Russian
Foundation for Basic Research (project no. 00-03-
32810a).
11. Tarbell, D.S. and Herz, A.H., J. Am. Chem. Soc., 1953,
vol. 75, no. 7, pp. 1668 1672.
12. Anklam, E., Synthesis, 1987, no. 9, pp. 841 843.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 1 2002