Synthesis of sulfides by reactions of 1,1-dichloro-2-chloro- methylcyclopropane with S-nucleophiles

Article abstract of DOI:10.1007/s11178-005-0172-4

1,1-Dichloro-2-chloromethylcyclopropane reacts with thiolates to give 2,2-dichlorocyclopropylmethyl sulfides via replacement of the side-chain chlorine atom. The resulting sulfides are readily oxidized to the corresponding sulfones.

Full text of DOI:10.1007/s11178-005-0172-4

Russian Journal of Organic Chemistry, Vol. 41, No. 3, 2005, pp. 370–375. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 3, 2005,
pp. 381–386.
Original Russian Text Copyright © 2005 by Mikhed’kina, Nedel’ko, Prezhdo.
Synthesis of Sulfides by Reactions of 1,1-Dichloro-2-chloro-
methylcyclopropane with S-Nucleophiles
E. I. Mikhed’kina1, P. V. Nedel’ko1, and V. V. Prezhdo2
1 “Khar’kovskii politekhnicheskii institut” National Technical University, ul. Frunze 21, Khar’kov, 61002 Ukraine
e-mail: nedelko@kpi.kharkov.ua
2 Institute of Chemistry, J. Kochanowski Higher Pedagogical School, Kielce, Poland
Received October 15, 2003
Abstract—1,1-Dichloro-2-chloromethylcyclopropane reacts with thiolates to give 2,2-dichlorocyclopropyl-
methyl sulfides via replacement of the side-chain chlorine atom. The resulting sulfides are readily oxidized to
the corresponding sulfones.
As shown in [1–4], 1,1-dichloro-2-chloro(bromo)-
methylcyclopropanes react with O- and C-nucleophiles
to give both products of substitution of the halogen
atom in the side chain and 1,1- or 1,2-disubstituted
methylenecyclopropanes according to the elimination–
addition pattern. As concerns S-nucleophiles, only the
reaction of such compounds with benzenethiol has
been reported [1, 2].
In the present work we examined reactions of
1,1-dichloro-2-chloromethylcyclopropane with various
S-nucleophiles with the goal of synthesizing sulfides
which may be useful from the viewpoint of searching
for new biologically active compounds. It is known [5]
that the 2,2-dichlorocyclopropyl group is a structural
fragment of the drug Ciprofibrate and that a number of
sulfides possessing the above group exhibit herbicide
and fungicide activity [6].
The reactions of 1,1-dichloro-2-chloromethylcyclo-
propane (I) with benzenethiol, p-methylbenzenethiol,
and 1H-1,2,4-triazole-5-thiol in anhydrous ethanol in
the presence of sodium ethoxide afforded sulfides IIa–
IIc (Scheme 1). These results are consistent with the
data of Jonczyk and Kmiotek-Skarzynska [2] who
studied the reaction of chloride I with benzenethiol,
depending on the basicity of the medium and solvent
nature. In all cases the authors isolated 2,2-dichloro-
cyclopropylmethyl phenyl sulfide (IIa) as the only
product. The poor solubility of 1H-1,2,4-triazole-5-
thiol in anhydrous ethanol makes it difficult to obtain
sulfide IIc in a preparative yield. We have found that
the reaction of 1H-1,2,4-triazole-5-thiole with chloride
I successfully occurs in DMF in the presence of
anhydrous potassium carbonate.
In the reaction of I with thiourea, followed by
treatment of the reaction mixture with aqueous sodium
hydroxide, we isolated two products. One of these was
identified as 2,2-dichlorocyclopropylmethanethiol
(III), and the other, as symmetric sulfide IId. The
latter was identical to the product described in [7] and
to that obtained from 2-bromomethyl-1,1-dichloro-
cyclopropane by heating in boiling ethanol. Sulfide IId
can also be prepared by phase-transfer reaction using
an aqueous solution of sodium sulfide and benzyltri-
ethylammonium chloride (BTEAC) as catalyst. Under
these conditions, the yield of IId was greater (~80%)
than that reported in [7] (70%). According to the
1H NMR data, sulfide IId is formed as a 1:1 mixture
of two possible diastereoisomers.
Treatment of chloride I with sodium thiosulfate in
aqueous ethanol gave 85% of thiol III which was
identical to a sample obtained from compound I and
thiourea. The structure of III was confirmed by the
1
spectral data. Its H NMR spectrum (DMSO-d6) con-
tained a multiplet at δ 2.61 ppm from the SH proton. In
the IR spectrum of III, an absorption band correspond-
ing to stretching vibrations of the S–H bond was ob-
served at 2576 cm–1. Thiol III is readily oxidized to
disulfide IV by the action of iodine in alkaline
solution.
Unsymmetrical dialkyl sulfides IIe–IIj containing
a dichlorocyclopropyl fragment were synthesized from
chloride I or thiol III in two ways. In the first case,
chloride I was brought into reaction with the corre-
sponding S-alkylisothiuronium salt under conditions
of phase-transfer catalysis using benzene as organic
phase and tetrabutylammonium bromide as catalyst
1070-4280/05/4103-0370 © 2005 Pleiades Publishing, Inc.

SYNTHESIS OF SULFIDES BY REACTIONS OF 1,1-DICHLORO-2-CHLOROMETHYL...
371
Scheme 1.
Cl
Cl
ArSH, EtOH
SAr
Cl
IIa–IIc
Cl
Cl
Cl
Na2S, H2O, BTEAC
S
Cl
Cl
IId
NH2
NH2
Cl
X–
HB'
SR
HA'
I
HA
RS
a
HB
Cl
HC
Cl
RX (V)
EtONa/EtOH
b
IIe–IIj
Cl
Cl
Cl
Cl
H2NC(=S)NH2
NaOH
I2
S
S
SH
Cl
Cl
III
IV
II, Ar = Ph (a), 4-CH3C6H4 (b), 1H-1,2,4-triazol-5-yl (c); R = Me (e), Et (f), Pr (g), Bu (h), C5H11 (i), PhCH2 (j);
V, X = I (e, f, g), Br (h, i), Cl (j).
(method a). According to method b, 2,2-dichlorocyclo-
propylmethanethiol was treated with the corresponding
alkyl halide V in anhydrous ethanol in the presence of
sodium ethoxide. Method b ensured greater yields of
sulfides IIe–IIj, regardless of the order of reactant
stretching vibrations of the SO2 group. Signals from
the exocyclic methylene protons H' and H'B appeared
A
in the 1H NMR spectra of VIa–VIj in a weaker field as
compared to the initial sulfides, while the positions of
the HC, HA, and HB signals remained essentially un-
changed in going from sulfides II to sulfones VI. The
1H NMR spectrum of symmetric sulfone VId con-
tained a double set of signals, indicating formation of
a mixture of two diastereoisomers. We succeeded in
separating these isomers by fractional recrystallization
of sulfone VId from diethyl ether–hexane.
1
mixing. In the H NMR spectra of sulfides IIa–IIj,
signals from the exocyclic methylene protons HA' and
HB' are displaced upfield (δ 2.52–3.37 ppm) relative to
the corresponding signals of initial chloride I (δ 3.58–
3.64 ppm).
Most sulfides IIa–IIj are liquids. By treatment with
hydrogen peroxide in acetic acid they were oxidized
to the corresponding sulfones VIa–VIj (Scheme 2).
Sulfones VIa–VIj characteristically showed in the
IR spectra absorption bands at 1140–1160 and 1300–
1320 cm–1 due to symmetric and antisymmetric
Thus we have found that 1,1-dichloro-2-chloro-
methylcyclopropane reacts with S-nucleophiles via
replacement of the side-chain chlorine atom, the
dichlorocyclopropane fragment remaining intact. The
corresponding sulfides are formed in good yields, and
they can readily be converted into the respective
sulfones.
Scheme 2.
Cl
Cl
O
S
EXPERIMENTAL
H2O2, AcOH
IIa–IIj
R
The IR spectra were recorded on a Specord M-82
spectrometer from samples prepared as thin films
O
VIa–VIj
1
(liquids) or KBr pellets. The H NMR spectra were
VI, R = Ph (a), 4-MeC6H4 (b), 1H-1,2,4-triazol-5-yl (c),
2,2-dichlorocyclopropylmethyl (d), Me (e), Et (f), Pr (g),
Bu (h), C5H11 (i), PhCH2 (j).
obtained on a Varian Mercury VX-200 spectrometer
(200 MHz) from solutions in DMSO-d6 or CDCl3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005

MIKHED’KINA et al.
372
using tetramethylsilane as internal reference. The prog-
ress of reactions and the purity of products were
monitored by thin-layer chromatography on Silufol
UV-254 plates using hexane–chloroform (5:1) as
eluent; the chromatograms were developed by treat-
ment with iodine vapor in a moist chamber.
125°C (3 mm); published data [1]: bp 96–99°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.21 t (1H, HA,
J = 7.4 Hz), 1.62–1.70 d.d (1H, HB, J = 7.2, 10.3 Hz),
1.79–1.95 m (1H, HC), 2.89–3.29 m (2H, HA', HB' , J =
6.8, 7.3, 13.7 Hz), 7.20–7.46 m (5H, Harom). Found, %:
C 51.25; H 4.16; Cl 30.08. C10H10Cl2S. Calculated, %:
C 51.52; H 4.32; Cl 30.41.
1,1-Dichloro-2-chloromethylcyclopropane (I) was
synthesized by the procedure described in [8].
2,2-Dichlorocyclopropylmethyl 4-methylphenyl
sulfide (IIb). Following method b, from 9.94 g of
p-methylbenzenethiol and 14.03 g of chloride I we
obtained 16.81 g (85%) of sulfide IIb as a colorless
General procedure for the preparation of iso-
thiuronium salts. A mixture of 0.1 mol of appropriate
alkyl halide, 0.1 mol of thiourea, and 35 ml of 96%
ethanol was heated for 4 h under reflux with stirring.
The mixture was cooled, and the precipitate was
filtered off, washed with alcohol, and dried in air.
1
liquid. bp 175–176°C (13 mm). H NMR spectrum
(DMSO-d6), δ, ppm: 1.39 t (1H, HA, J = 6.8 Hz), 1.72–
1.81 d.d (1H, HB, J = 6.8, 10.5 Hz), 1.80–1.96 m
(1H, HC), 2.29 s (3H, CH3), 3.10 d (2H, H' , HB' , J =
A
Sulfides IIa–IIj (general procedure). a. A mixture
of 80 mmol of isothiuronium salt, 12.76 g (80 mmol)
of chloride I, 0.25 g of tetrabutylammonium bromide,
150 ml of benzene, and 150 g of 30% aqueous sodium
hydroxide was stirred for 4 h at 20°C under nitrogen.
The organic phase was separated, the aqueous phase
was extracted with benzene (2×20 ml), the extracts
were combined with the organic phase, washed with
100 ml of water, dried over MgSO4, and evaporated,
and the residue was distilled under reduced pressure.
6.8 Hz), 7.15–7.36 m (4H, Harom). Found, %: C 53.12;
H 4.75; Cl 28.38. C11H12Cl2S. Calculated, %: C 53.45;
H 4.89; Cl 28.69.
2,2-Dichlorocyclopropylmethyl 1H-1,2,4-triazol-
5-yl sulfide (IIc). A mixture of 10.1 g (0.1 mol) of
1H-1,2,4-triazole-5-thiol, 17.54 g (0.11 mol) of chlo-
ride I, 15.2 g (0.11 mol) of K2CO3, and 100 ml of
DMF was stirred for 6 h at room temperature and
poured into 100 ml of water. The aqueous phase was
separated by decanting, and the residue was recrys-
tallized from methanol. Yield 12.77 g (57%), mp 74–
76°C. 1H NMR spectrum (CDCl3), δ, ppm: 1.32 t (1H,
HA, J = 7.5 Hz), 1.66–1.75 d.d (1H, HB, J = 7.3,
b. A solution of sodium ethoxide, prepared from
1.84 g of metallic sodium and 27 ml of anhydrous
ethanol, was cooled to 0°C, 80 mmol of appropriate
thiol was added with stirring under nitrogen, and
(5 min later), 88 mmol of the corresponding alkyl
halide V was added. After 30 min, the cooling bath
was removed, and the mixture was allowed to warm up
to 20°C and was stirred at that temperature, the
progress of the reaction being monitored by TLC.
When the reaction was complete, the solvent was
partially distilled off, and water was added to the
residue in an amount sufficient to dissolve the
inorganic precipitate. The organic phase was separated,
the aqueous phase was extracted with diethyl ether
(2×10 ml), the extracts were combined with the
organic phase, washed with a 1 M solution of NaOH
and with water, dried over MgSO4, and evaporated,
and the residue was distilled under reduced pressure.
In the synthesis of compound IIc, 1.84 g of sodium
and 50 ml of ethanol were used, and the residue
obtained by removal of the solvent was recrystallized
from methanol.
10.4 Hz), 2.04–2.20 m (1H, HC), 3.37 d (2H, H' , HB' ,
A
J = 7.4 Hz), 8.33 s (1H, CH), 9.78 s (1H, NH). Found,
%: C 31.83; H 3.01; Cl 31.35. C6H7Cl2N3S. Calcu-
lated, %: C 32.16; H 3.15; Cl 31.64.
Following method b, from 8.09 g of 1H-1,2,4-
triazole-5-thiol and 14.03 g of chloride I we obtained
11.65 g (65%) of sulfide IIc as a viscous liquid. The
product was purified by recrystallization from
methanol, mp 74–76°C; no depression of the melting
point was observed on mixing with a sample prepared
as described above.
Bis(2,2-dichlorocyclopropylmethyl) sulfide (IId).
A mixture of 15.95 g (0.1 mol) of chloride I, 14.41 g
(0.06 mol) of Na2S·9H2O, 3 g of benzyltriethylam-
monium chloride, and 30 ml of water was stirred for
7 h at 90°C. The mixture was poured into 150 ml of
water, the organic phase was separated, and the
aqueous phase was extracted with diethyl ether (2×
20 ml). The extracts were combined with the organic
phase, washed with water, dried over MgSO4, and
evaporated, and the residue was distilled under reduced
pressure. Yield 11.20 g (80%), yellowish liquid,
2,2-Dichlorocyclopropylmethyl phenyl sulfide
(IIa). Following method b, from 8.81 g of benzene-
thiol and 14.03 g of chloride I we obtained 16.79 g
(90%) of sulfide IIa as a colorless liquid. bp 123–
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SYNTHESIS OF SULFIDES BY REACTIONS OF 1,1-DICHLORO-2-CHLOROMETHYL...
373
bp 166°C (13 mm); published data [7]: bp 117–118°C
Following method b, from 12.56 g of thiol III and
1
(1–1.5 mm). H NMR spectrum (CDCl3), δ, ppm:
12.06 g of butyl bromide we obtained 12.62 g (74%)
of sulfide IIh as a colorless liquid. The product was
identical to a sample prepared according to method a.
1.25 t (1H, HA, J = 7.0 Hz), 1.68–1.77 d.d (1H, HB, J =
7.0, 10.4 Hz), 1.80–2.00 m (1H, HC), 2.65–3.00 m (2H,
H' , HB' , J = 6.6, 7.2, 13.5 Hz). Found, %: C 34.05;
H 3.46; Cl 50.23. C8H10Cl4S. Calculated, %: C 34.31;
H 3.60; Cl 50.64.
A
2,2-Dichlorocyclopropylmethyl pentyl sulfide
(IIi). Following method a, from 18.17 g of S-pentyl-
isothiuronium bromide and 12.76 g of chloride I we
obtained 8.54 g (47%) of sulfide IIi as a colorless
2,2-Dichlorocyclopropylmethyl methyl sulfide
(IIe). Following method b, from 12.56 g of thiol III
and 12.49 g of methyl iodide we obtained 8.62 g (63%)
of sulfide IIe as a colorless liquid, bp 90°C (20 mm).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.37 t (1H,
HA, J = 7.3 Hz), 1.75–1.83 d.d (1H, HB, J = 7.0,
10.6 Hz), 1.88–2.04 m (1H, HC), 2.16 s (3H, CH3),
2.58–2.78 m (2H, HA' , H'B, J = 6.5, 7.5, 13.8 Hz).
Found, %: C 34.85; H 4.66; Cl 41.28. C5H8Cl2S. Cal-
culated, %: C 35.10; H 4.71; Cl 41.45.
1
liquid, bp 110–112°C (12 mm). H NMR spectrum
(CDCl3), δ, ppm: 0.90 t (3H, CH3), 1.20 t (1H, HA, J =
7.1 Hz), 1.26–1.72 m [6H, (CH2)3], 1.64–1.70 d.d (1H,
HB, J = 7.1, 10.4 Hz), 1.77–1.92 m (1H, HC), 2.52–
2.89 m (2H, H' , H' , J = 6.8, 13.6 Hz), 2.56–2.71 q
A
B
(2H, CH2). Found, %: C 47.25; H 6.96; Cl 30.88.
C9H16Cl2S. Calculated, %: C 47.58; H 7.10; Cl 31.21.
Following method b, from 12.56 g of thiol III and
13.29 g of n-pentyl bromide we obtained 13.45 g
(74%) of sulfide IIi as a colorless liquid. The product
was identical to a sample prepared according to
method a.
2,2-Dichlorocyclopropylmethyl ethyl sulfide
(IIf). Following method b, from 12.56 g of thiol III
and 13.73 g of ethyl iodide we obtained 10.37 g (70%)
of sulfide IIf as a colorless liquid, bp 85–87°C
(13 mm). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.22 t
(3H, CH3), 1.36 t (1H, HA, J = 7.2 Hz), 1.74–1.83 d.d
(1H, HB, J = 7.0, 10.4 Hz), 1.86–2.02 m (1H, HC),
Benzyl 2,2-dichlorocyclopropylmethyl sulfide
(IIj). Following method a, from 16.22 g of S-benzyl-
isothiuronium chloride and 12.76 g of chloride I we
obtained 12.85 g (65%) of sulfide IIj as a colorless
1
2.57–2.68 m (2H, CH2), 2.64–2.80 m (2H, H' , HB' , J =
A
liquid, bp 110–112°C (12 mm). H NMR spectrum
7.4, 14.0 Hz). Found, %: C 38.65; H 5.28; Cl 37.98.
C6H10Cl2S. Calculated, %: C 38.93; H 5.44; Cl 38.30.
(DMSO-d6), δ, ppm: 1.32 t (1H, HA, J = 7.3 Hz), 1.69–
1.78 d.d (1H, HB, J = 7.1, 10.5 Hz), 1.83–1.99 m (1H,
HC), 2.56–2.73 m (2H, H' , H' , J = 7.4, 13.9 Hz),
A
B
2,2-Dichlorocyclopropylmethyl propyl sulfide
(IIg). Following method b, from 12.56 g of thiol III
and 14.96 g of propyl iodide we obtained 11.63 g
(73%) of sulfide IIg as a colorless liquid, bp 105°C
3.86 s (2H, CH2), 7.20–7.46 m (5H, Harom). Found, %:
C 53.14; H 4.77; Cl 28.38. C11H12Cl2S. Calculated, %:
C 53.45; H 4.89; Cl 28.69.
1
(12 mm). H NMR spectrum (DMSO-d6), δ, ppm:
Following method b, from 12.56 g of thiol III and
11.14 g of benzyl chloride we obtained 17.40 g (88%)
of sulfide IIj as a colorless liquid. The product was
identical to a sample prepared according to method a.
0.96 t (3H, CH3), 1.36 t (1H, HA, J = 7.2 Hz), 1.49–
1.67 m (2H, CH2), 1.74–1.83 d.d (1H, HB, J = 7.0,
10.5 Hz), 1.86–2.02 m (1H, HC), 2.55–2.63 m (2H,
CH2), 2.67–2.78 m (2H, H' , H' , J = 7.5, 14.0 Hz).
A
B
2,2-Dichlorocyclopropylmethanethiol (III).
a. Chloride I, 12.76 g (80 mmol), was added in one
portion to a solution of 6.09 g (80 mmol) of thiourea in
26 ml of 96% ethanol, and the mixture was refluxed
for 6 h under vigorous stirring. The mixture was
diluted under nitrogen with 50 ml of 10% aqueous
sodium hydroxide, stirred for 2 h, cooled to room
temperature, and 10 ml of 20% sulfuric acid was
added. The organic phase was separated, and the
aqueous phase was extracted with benzene (2×20 ml).
The extracts were combined with the organic phase,
washed with water, and dried over MgSO4. The solvent
was removed, and the residue was distilled under
reduced pressure in a stream of nitrogen. We isolated
Found, %: C 41.85; H 5.88; Cl 35.28. C7H12Cl2S. Cal-
culated, %: C 42.22; H 6.07; Cl 35.61.
Butyl 2,2-dichlorocyclopropylmethyl sulfide
(IIh). Following method a, from 17.05 g of S-butyl-
isothiuronium bromide and 12.76 g of chloride I we
obtained 8.53 g (50%) of sulfide IIh as a colorless
1
liquid, bp 110–112°C (12 mm). H NMR spectrum
(CDCl3), δ, ppm: 0.92 t (3H, CH3), 1.20 t (1H, HA, J =
7.2 Hz), 1.36–1.62 m [4H, (CH2)2], 1.63–1.72 d.d (1H,
HB, J = 7.1, 10.4 Hz), 1.76–1.92 m (1H, HC), 2.52–
2.89 m (2H, H' , H' , J = 6.8, 13.7 Hz), 2.57–2.71 q
A
B
(2H, CH2). Found, %: C 44.84; H 6.47; Cl 32.94.
C8H14Cl2S. Calculated, %: C 45.08; H 6.62; Cl 33.26.
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MIKHED’KINA et al.
374
extracts were combined with the oily material, dried
over MgSO4, and evaporated, and the residue was
distilled under reduced pressure.
3.77 g (30%) of sulfide III as a colorless liquid, bp 74–
75°C (19 mm), and 1.35 g (12%) of sulfide IId as
a yellowish liquid, bp 177–180°C (19 mm). According
to the TLC data (Rf 0.38), product IId was identical to
a sample prepared as described above. IR spectrum of
2,2-Dichlorocyclopropylmethyl phenyl sulfone
(VIa). Yield 1.13 g (85%), colorless crystals, mp 87–
88°C (from AcOH). IR spectrum, ν, cm–1: 752, 1088,
1
III, ν, cm–1: 760, 1232, 1432, 2576, 2936. H NMR
1
spectrum (DMSO-d6), δ, ppm: 1.39 t (1H, HA, J =
7.3 Hz), 1.71–1.80 d.d (1H, HB, J = 7.3, 10.4 Hz),
1.87–2.03 m (1H, HC), 2.54–2.74 m (2H, H' , H' , J =
1152, 1268, 1308, 2952. H NMR spectrum
(DMSO-d6), δ, ppm: 1.21 t (1H, HA, J = 7.6 Hz), 1.67–
1.76 d.d (1H, HB, J = 7.6, 10.5 Hz), 1.91–2.07 m (1H,
HC), 3.09–3.59 m (2H, H' , H' , J = 6.6, 7.5, 14.6 Hz),
A
B
7.0, 14.0 Hz), 2.61 m (1H, SH). Found, %: C 30.42;
H 3.69; Cl 44.83. C4H6Cl2S. Calculated, %: C 30.59;
H 3.85; Cl 45.15.
A
B
7.56–7.98 m (5H, Harom). Found, %: C 45.05; H 3.65;
Cl 26.59. C10H10Cl2O2S. Calculated, %: C 45.30;
H 3.80; Cl 26.74.
b. A solution of 11.16 g (70 mmol) of chloride I in
19 ml of ethanol was added to a solution of 17.37 g
(70 mmol) of Na2S2O3·5H2O in 18 ml of water. The
mixture was heated for 6 h at the boiling point under
vigorous stirring, 31 ml of 50% sulfuric acid was
added under nitrogen, and the mixture was heated for
an additional 2 h. It was then cooled, and the product
was isolated as described above in a. Yield of thiol III
9.34 g (85%). The product was identical to a sample
prepared as described in a in the TLC (Rf 0.51) and IR
data (νSH 2576 cm–1).
2,2-Dichlorocyclopropylmethyl 4-methylphenyl
sulfone (VIb). Yield 1.30 g (93%), colorless crystals,
mp 73–74°C (from AcOH). IR spectrum, ν, cm–1: 752,
1
1104, 1160, 1308, 1320, 1408, 2916. H NMR spec-
trum (DMSO-d6), δ, ppm: 1.32 t (1H, HA, J = 5.5 Hz),
1.77–1.84 d.d (1H, HB, J = 6.0, 10.6 Hz), 1.83–1.96 m
(1H, HC), 2.43 s (3H, CH3), 3.35–3.71 m (2H, H' , H' ,
A
B
J = 6.4, 14.8 Hz), 7.47–7.84 m (4H, Harom). Found, %:
C 47.05; H 4.00; Cl 25.05. C11H12Cl2O2S. Calculated,
%: C 47.32; H 4.33; Cl 25.40.
Bis(2,2-dichlorocyclopropylmethyl) disulfide
(IV). Thiol III, 7.54 g (48 mmol), was added to a so-
lution of 1.92 g of sodium hydroxide and 0.12 g of
potassium iodide in 12 ml of water. The mixture was
stirred for 40 min, and 6.09 g (24 mmol) of iodine was
added until the mixture turned slightly colored. The
mixture was decolorized by adding a 20% solution of
Na2SO3, the organic phase was separated, and the
aqueous phase was extracted with diethyl ether (2×
20 ml). The extracts were combined with the organic
phase, dried over MgSO4, and evaporated, and the
residue was distilled under reduced pressure. Yield
5.02 g (67%), yellowish viscous liquid, bp 145°C
(2 mm). 1H NMR spectrum (DMSO-d6), δ, ppm: 1.50 t
(1H, HA, J = 7.3 Hz), 1.81–1.91 d.d (1H, HB, J = 7.3,
10.4 Hz), 2.02–2.19 m (1H, HC), 3.02 d (2H, H' , H' ,
2,2-Dichlorocyclopropylmethyl 1H-1,2,4-triazol-
5-yl sulfone (VIc). Yield 0.82 g (64%), colorless
crystals, mp 174–175°C (from AcOH). IR spectrum, ν,
cm–1: 760, 1000, 1152, 1192, 1340, 1468, 1776, 2572,
1
2916. H NMR spectrum (DMSO-d6), δ, ppm: 1.43 t
(1H, HA, J = 7.4 Hz), 1.81–1.90 d.d (1H, HB, J = 7.4,
10.7 Hz), 1.96–2.12 m (1H, HC), 3.55–3.87 m (2H,
H' , HB' , J = 6.7, 13.7 Hz), 8.92 s (1H, CH), 15.13 s
A
(1H, NH). Found, %: C 27.85; H 2.61; Cl 27.45.
C6H7Cl2N3O2S. Calculated, %: C 28.14; H 2.75;
Cl 27.69.
Bis(2,2-dichlorocyclopropylmethyl) sulfone (Vd).
Yield 1.42 g (91%), colorless crystals. Fractional re-
crystallization from diethyl ether–hexane (1:1) gave
0.57 g of isomer A, mp 82–84°C, and 0.51 g of isomer
B, mp 118–120°C, both as colorless crystals. Isomer
A: IR spectrum, ν, cm–1: 760, 1116, 1142, 1316, 1405,
A
B
J = 7.0 Hz). Found, %: C 30.52; H 3.07; Cl 45.11.
C8H10Cl4S2. Calculated, %: C 30.79; H 3.23; Cl 45.44.
1
2927. H NMR spectrum (CDCl3), δ, ppm: 1.53 t
Sulfones VIa–VIj (general procedure). Sulfide
IIa–IIj, 5 mmol, was dissolved in 5 ml of acetic acid,
15 mmol of 30% hydrogen peroxide was added, and
the mixture was heated for 4–5 h at 85°C. It was then
poured into 50 ml of water, and the precipitate was
filtered off, dried over NaOH, and recrystallized from
appropriate solvent. In the synthesis of sulfone Vf, the
oily material was separated, and the aqueous phase
was extracted with two portions of diethyl ether. The
(1H, HA, J = 7.6 Hz), 1.89–1.98 d.d (1H, HB, J = 7.6,
10.4 Hz), 2.07–2.24 m (1H, HC), 3.06–3.61 m (2H,
H' , HB' , J = 6.3, 7.6, 14.3 Hz). Found, %: C 30.48;
A
H 3.07; Cl 45.14. C8H10Cl4O2S. Calculated, %: C 30.79;
H 3.23; Cl 45.45. The IR spectrum of isomer B was
identical to that of isomer A. Found, %: C 30.49;
H 3.08; Cl 45.15. C8H10Cl4O2S. Calculated, %: C 30.79;
H 3.23; Cl 45.45.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005

SYNTHESIS OF SULFIDES BY REACTIONS OF 1,1-DICHLORO-2-CHLOROMETHYL...
375
2,2-Dichlorocyclopropylmethyl methyl sulfone
(Ve). Yield 0.98 g (97%), colorless crystals, mp 52–
53°C (from MeOH). IR spectrum, ν, cm–1: 760, 1108,
2,2-Dichlorocyclopropylmethyl pentyl sulfone
(Vi). Yield 1.06 g (82%), colorless crystals, mp 44–
45°C (from AcOH). IR spectrum, ν, cm–1: 743, 1091,
1
1
1136, 1152, 1264, 1308, 2928. H NMR spectrum
1136, 1258, 1290, 1315, 2926. H NMR spectrum
(DMSO-d6), δ, ppm: 1.61 t (1H, HA, J = 7.3 Hz), 1.90–
1.99 d.d (1H, HB, J = 7.3, 10.5 Hz), 2.02–2.18 m (1H,
HC), 3.13–3.66 m (2H, H' , H' , J = 5.6, 7.4, 14.5 Hz),
3.06 s (3H, CH3). Found, %: C 29.21; H 3.82; Cl 34.60.
C5H8Cl2O2S. Calculated, %: C 29.57; H 3.97; Cl 34.91.
(CDCl3), δ, ppm: 0.92 t (3H, CH3), 1.32–1.58 m [4H,
(CH2)2 ], 1.47 t (1H, HA, J = 7.6 Hz), 1.81–1.97 m (2H,
CH2), 1.85–1.94 d.d (1H, HB, J = 7.5, 10.5 Hz), 2.04–
2.20 m (1H, HC), 2.95–3.49 m (2H, H' , H' , J = 6.5,
7.2, 14.5 Hz), 3.01–3.08 m (2H, CH2). Found, %:
C 41.42; H 6.03; Cl 27.03. C9H16Cl2O2S. Calculated,
%: C 41.71; H 6.22; Cl 27.36.
A
B
A
B
2,2-Dichlorocyclopropylmethyl ethyl sulfone
(Vf). The oily product was purified by vacuum dis-
tillation. Yield 0.78 g (72%), colorless viscous liquid,
bp 144°C (2 mm). IR spectrum, ν, cm–1: 756, 1108,
Benzyl 2,2-dichlorocyclopropylmethyl sulfone
(Vj). Yield 1.24 g (89%), colorless crystals, mp 85–
86°C (from AcOH). IR spectrum, ν, cm–1: 776, 1080,
1
1148, 1288, 1316, 2932. H NMR spectrum
1
(DMSO-d6), δ, ppm: 1.25 t (3H, CH3), 1.59 t (1H, HA,
J = 7.1 Hz), 1.90–1.99 d.d (1H, HB, J = 7.0, 10.7 Hz),
2.00–2.16 m (1H, HC), 3.11–3.63 m (2H, HA' , H'B, J =
6.0, 7.4, 14.4 Hz), 3.13–3.24 m (2H, CH2). Found, %:
C 32.85; H 4.48; Cl 32.35. C6H10Cl2O2S. Calculated,
%: C 33.19; H 4.64; Cl 32.66.
1136, 1316, 1360, 2968. H NMR spectrum
(DMSO-d6), δ, ppm: 1.58 t (1H, HA, J = 7.3 Hz), 1.87–
1.96 d.d (1H, HB, J = 7.3, 10.5 Hz), 2.00–2.15 m (1H,
HC), 3.12–3.62 m (2H, H' , H' , J = 5.9, 7.7, 14.9 Hz),
A
B
4.58 s (2H, CH2), 7.31–7.51 m (5H, Harom). Found, %:
C 47.03; H 4.20; Cl 25.14. C11H12Cl2O2S. Calculated,
%: C 47.32; H 4.33; Cl 25.40.
2,2-Dichlorocyclopropylmethyl propyl sulfone
(Vg). Yield 1.03 g (89%), colorless crystals, mp 34–
35°C (from diethyl ether–hexane, 1:1). IR spectrum, ν,
REFERENCES
1
cm–1: 756, 1108, 1144, 1292, 1316, 2964. H NMR
1. Jonczyk, A., Dabrowski, M., and Wozniak, W.,
Tetrahedron Lett., 1983, vol. 24, p. 1065.
2. Jonczyk, A. and Kmiotek-Skarzynska, I., Synthesis, 1992,
spectrum (DMSO-d6), δ, ppm: 1.01 t (3H, CH3), 1.59 t
(1H, HA, J = 7.3 Hz), 1.65–1.84 m (2H, CH2), 1.90–
1.99 d.d (1H, HB, J = 7.0, 10.4 Hz), 2.01–2.16 m (1H,
HC), 3.10–3.63 m (2H, H' , H' , J = 6.0, 7.6, 13.7 Hz),
p. 985.
A
B
3. Steinbeck, K., Justus Liebigs Ann. Chem., 1979, p. 920.
4. Jonczyk, A., Kmiotek-Skarzynska, I., and Zdrojewski, T.,
J. Chem. Soc., Perkin Trans. 1, 1994, p. 1605.
5. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
3.13–3.24 m (2H, CH2). Found, %: C 36.05; H 4.94;
Cl 30.32. C7H12Cl2O2S. Calculated, %: C 36.38;
H 5.23; Cl 30.68.
Butyl 2,2-dichlorocyclopropylmethyl sulfone
(Vh). Yield 1.13 g (92%), colorless crystals, mp 59–
60°C (from AcOH). IR spectrum, ν, cm–1: 752, 1116,
Moscow: Novaya Volna, 2002, vol. 1, p. 448.
6. Franke, H. and Arndt, F., FRG Patent no. 2804739, 1979;
Chem. Abstr., 1979, vol. 91, no. 157478; Kruger, B.W.,
Presnitz, P., Jaeger, G., and Behrenz, W., FRG Patent
no. 3305835, 1984; Chem. Abstr., 1985, vol. 102,
no. 24174.
1
1148, 1268, 1316, 2964. H NMR spectrum
(DMSO-d6), δ, ppm: 0.91 t (3H, CH3), 1.34–1.52 m
(2H, CH2), 1.59 t (1H, HA, J = 7.3 Hz), 1.66–1.78 m
(2H, CH2), 1.90–1.99 d.d (1H, HB, J = 7.1, 10.5 Hz),
2.01–2.17 m (1H, HC), 3.11–3.22 m (2H, CH2), 3.11–
3.62 m (2H, H' , H' , J = 6.0, 7.5, 14.5 Hz). Found, %:
7. Kazimirchik, I.V., Lukin, K.A., Bebikh, G.F., and Zefi-
rov, N.S., Zh. Org. Khim., 1983, vol. 19, p. 2523.
A
B
8. Mandel’shtam, T.V., Kharicheva, E.M., Labeish, N.N.,
and Kostikov, R.R., Zh. Org. Khim., 1980, vol. 16,
p. 2513.
C 38.98; H 5.61; Cl 28.76. C8H14Cl2O2S. Calculated,
%: C 39.19; H 5.76; Cl 28.92.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005