OXIDATIVE DIMERIZATION OF SULFENYL CHLORIDES
3
Cl(2)
I
> 2σ(I). Molecular structure of compound IIa is
shown in the figure.
Reactions of HMPA with sulfenyl chlorides in methꢀ
ylene chloride. A solution of 11.8 mmol of sulfenyl
chloride in 5 mL of methylene chloride was added to a
solution of 2.1 g (11.8 mmol) of HMPA in 15 mL of
methylene chloride at ambient temperature with stirꢀ
ring in a flow of dry nitrogen, and stirring was continꢀ
ued for 4 h. The resultant precipitate of dimethylamꢀ
monium chloride (III) was separated by filtration and
recrystallized from acetonitrile. The solvent was
removed from the filtrate under reduced pressure.
According to IR spectra, the residue consisted of thioꢀ
sulfonate IIa or IIb and phosphorus chloride. Thiosulꢀ
fonates IIa and IIb were purified by recrystallization
from an acetonitrile–carbon tetrachloride mixture.
C(9)
C(10)
C(8)
Cl(1)
C(11)
C(5)
C(1)
C(7)
C(12)
C(4)
C(6)
C(3)
S(2)
C(2)
S(1)
O(2)
The yield of compound IIa was 2.6 g (70%), mp
O(1)
134–136
IR (Nujol,
ing vibrations of C–H bonds of benzene ring), 1000
°
С.
, cm–1): 750, 810 (outꢀofꢀplane bendꢀ
Molecular structure of pꢀchlorobenzenethiosulfonate IIa.
ν
δ
+
δ–
S O
…
(S–O bond vibrations), 1080 (
1140–1330 (vibrations of O2S–S fragment).
bond vibrations),
ylene chloride with stirring at ambient temperature.
Then, a solution of 7.9 mmol of sulfenyl chloride in
5 mL of the same solvent was added dropwise. The
mixture was stirred for 4 h. The resultant precipitate of
dimethylammonium tetrachlorozincate (IV) was sepꢀ
arated by filtration and recrystallized from acetoniꢀ
trile. The solvent was removed from the filtrate under
reduced pressure. According to IR spectra, the residue
consisted of thiosulfonate IIa or IIb and phosphoꢀ
rus(III) chloride. Thiosulfonates IIa and IIb were
purified by recrystallization from an acetonitrile–carꢀ
bon tetrachloride mixture.
For C12H8Cl2O2S2 anal. calcd. (%): C, 45.14; H,
2.51; O, 10.03; S, 20.06; Cl, 22.26.
Found (%): C, 44.82; H, 2.83; O, 10.33; S, 20.16;
Cl, 21.86.
The yield of compound IIb was 2.1 g (70%), mp
41–43
°
C.
IR (Nujol,
ν
, cm–1): 690, 750, 820, 1000 (benzene
ring vibrations), 1140, 1620 (vibrations of O2S–Ph
fragment); 1130–1310 (vibrations of O2S–S fragꢀ
ment).
The yields of compounds IIa and IIb were 0.68 g
(27%) and 0.49 g (25%), respectively.
For C12H10O2S2 anal. calcd. (%): C, 57.60; H, 4.00;
O, 12.80; S, 25.60.
The yield of dimethylammonium tetrachlorozinꢀ
cate (IV) was 1.65 g (70%), mp 124–126
°
C (dec.).
Found (%): C, 56.10; H, 4.50; O, 13.20; S, 26.20.
1H NMR (CD3CN,
2.66 (s, 3H, CH3).
δ
, ppm): 2.72 (s, 3H, CH3),
The yield of dimethylammonium chloride (III
)
was 0.24 g (25%), mp 170–171 C.
°
1H NMR (CDCl3,
(s, 3H, CH3).
δ
, ppm): 2.74 (s, 3H, CH3), 2.67
IR (Nujol,
, cm–1): 1000–1020 (CH3 bending
vibrations), 1100 (C–N stretching vibrations), 3450
(NH2 stretching vibrations).
ν
IR (Nujol,
, cm–1): 1000–1020 (CH3 bending
ν
vibrations), 1100 (C–N stretching vibrations), 3450
(NH2 stretching vibrations).
ACKNOWLEDGMENTS
Phosphorus chloride, IR (thin film,
(P–Cl).
ν
, cm–1): 550
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 09–03–00683a).
Reactions of HMPA with sulfenyl chloride–ZnCl2
system in methylene chloride. The experiment was carꢀ
ried out under conditions that excluded air moisture
access. A solution of 1.4 g (7.9 mmol) of HMPA in
5 mL of methylene chloride was added to a mixture of
1.1 g (7.9 mmol) of zinc dichloride in 10 mL of methꢀ
REFERENCES
1. Smit, W.A., Zefirov, N.S., Bodrikov, I.V., and
Krimer, M.Z., Acc. Chem. Res., 1979, vol. 12, pp. 282–
288.
DOKLADY CHEMISTRY Vol. 436
Part 1
2011