LEZINA et al.
1250
equal amounts of the corresponding thiol sulfonate and
sulfonyl chloride. The oxidation of diphenyl disulfide
with chlorine dioxide in hexane did not occur even at
the use of the 8-fold excess of the oxidant whereas in
the acetonitrile the 3-fold excess of the oxidant led to the
practically complete conversion of the initial compound.
Reaction products were separated by vacuum distillation.
Yield 73%, bp 90–91°C (15 mm Hg).
p-Toluenesulfonyl chloride (Vb). Reaction time 3 h.
Yield 45%, mp 68–70°C (EtOH).
Benzenesulfonyl chloride (VIb). Through a solu-
tion of 0.1 g (0.46 mmol) of disulfide (VI) and 0.012 g
(0.046 mmol) of VO(acac)2 in 15 ml of acetonitrile was
bubbled 0.15 g (2.3 mmol) of chlorine dioxide mixed with
argon passed through a washer with concn. sulfuric acid
for 3 h at continuous stirring (method a). The solvent was
evaporated in a vacuum, the reaction product was chro-
matographed on a column packed with silica gel (eluent
chloroform–petroleum ether, 3 : 5). Yield 0.14 g (85%).
The yield of arylsulfonyl chlorides notably grows
at the use of catalysts. For instance, at the addition of
10 mol % of VO(acac)2 the yield of the corresponding
sulfonyl chloride increased from 40 to 85% after passing
5 mol of chlorine dioxide.
The deciding factor determining the yield of sulfonyl
chlorides proved to be the way of charging the reagents
into the reaction mixture. We tried two ways: In the first
one in the solution of the organosulfur compounds was
measured out gaseous chlorine dioxide or its solution
(method a); in the second procedure into the solution
of chlorine dioxide was measured out thiol or disulfide
(method b). For the quantitative preparation of sulfonyl
chlorides method b is optimal since the thiol (disulfide)
here occurs in the excess of oxidant. The yield of hexa-
decanesulfonyl chloride (IIb) along the method a was
11%, whereas by the method b 79% was obtained.
IR spectra were recorded on a Fourier spectrophotom-
eter Schimadzu IR Prestige 21 from thin film or pellets
with KBr. Melting points were measured on an instrument
Gallenkamp-Sanyo. 1H and 13C NMR spectra were reg-
istered on a spectrometer BrukerAvance-II-300 (300.17,
75.42 MHz respectively). Elemental analysis was carried
out on an automatic analyzer EA 1110 CHNS-O. GLC
analysis was performed on a chromatograph Chrom-5
equipped with the flame-ionization detector, column
2 m × 4 mm, stationary phase 5% Carbowax-20 on
Chromaton-N-AW-DMCS, ramp from 50 to 250°C at
a rate 6 deg/min.
The cooling the reaction mixture to 0°C or its heating
to 50°C resulted in the reduction of the conversion of the
initial compound in the first event due to the decrease in
the reaction rate, in the second case apparently because
of the decomposition of the oxidant.
TLC was performed on Silufol and Sorbfil plates using
as eluents hexane–acetone, 5 : 1 (for sulfonyl chlorides Ib,
IIb, IVb), petroleum ether–ethyl ether, 1:1 (for sulfonyl
chloride IIIb), ethanol (for sulfonyl chloride Vb), chlo-
roform (for sulfonyl chloride VIb). Spots were visualized
with 0.2% solution of bromocresol green in ethanol.
The characteristics of the compounds synthesized
were in agreement with the published data: Ib [7]; IIb
[8]; IIIb [9]; IVb [7]; Vb [10]; VIb [11].
Commercially available compounds Ia–VIa were
used without additional purification. The concentration
of industrial water solution of chlorine dioxide was
measured by titration along procedure [12]. The chlorine
dioxide was transferred into the organic solvent by extrac-
tion or bubbling with air.
Hexanesulfonyl chloride (Ib). A solution of 0.5 g
(4.2 mmol) of hexanethiol in 5 ml of dichloromethane
was added dropwise to a solution of 0.55 g (8.4 mmol) of
chlorine dioxide in 120 ml of dichloromethane (method
b). The reaction mixture was stirred for 3 h at 20°C. The
solvent was evaporated in a vacuum, the reaction product
was chromatographed on a column packed with silica gel
(eluent heptane–acetone, 10:1). Yield 0.64 g (82%), bp
92–94°C (5 mm Hg).
The study was carried out under the financial support
of the Department of Chemistry and Material Science of
the RussianAcademy of Sciences (project 09-Т-3-1015).
Compounds IIb–Vb were obtained similarly.
REFERENCES
Hexadecanesulfonyl chloride (IIb). Reaction time
1 h. Yield 79%, mp 49°C (EtOH).
1. Comprehensive Organic Chemistry, Barton, D. and Ol-
lis, W.D., Eds., Oxford: Pergamon, 1979, vol. 5.
2. Kuchin, A.V., Rubtsova, S.A., Karmanova, L.P., Subboti-
na, S.N., and Loginova, I.V., Izv. Akad. Nauk, Ser. Khim.,
1998, p. 2110.
Phenylmethanesulfonyl chloride (IIIb). Yield 70%,
mp 92–93°C (EtOH).
Butanesulfonyl chloride (IVb). Reaction time 3 h.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011