IVANOVA et al.
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on silica gel using petroleum ether–ethyl acetate (9:1)
as eluent to isolate 0.08 g (20%) of compound VI and
0.16 g (51%) of VII.
(1S,5S)-1-Allyl-2,5-dichloro-4,4-ethylenedioxy-3-
phenylsulfonyl-2-cyclopentenol (IX). Yellow oily
substance, Rf 0.49 (petroleum ether–ethyl acetate,
1:1). IR spectrum, ν, cm–1: 1040, 1220, 1340, 1590,
Diethyl 2-(4-chloro-3,3-ethylenedioxy-2-phenyl-
sulfonyl-5-oxo-1-cyclopentenyl)propanedioate (VI).
Yellow oily substance, Rf 0.16 (petroleum ether–ethyl
acetate, 8:2, 4 runs). IR spectrum, ν, cm–1: 1045, 1165,
1
1610, 3020, 3080, 3460. H NMR spectrum, δ, ppm:
2.44–2.46 m (2H, 1'-H), 4.21 s (1H, OH), 4.27 t (1H,
6-H), 4.15–4.54 m (4H, CH2O), 4.24 s (1H, 5-H),
5.11–5.21 m (2H, 3'-H), 5.46 m (1H, 2'-H), 7.56 t (2H,
m-H, J = 7.3 Hz), 7.67 t (1H, p-H, J = 7.1 Hz), 7.99 t
(2H, o-H, J = 7.9 Hz). 13C NMR spectrum, δ, ppm:
38.61 (C1'), 66.24 (C5), 67.29 (CH2O), 79.54 (C1),
113.13 (C4), 121.37 (C3'), 127.55 (Co), 128.73 (Cp),
130.12 (Cm), 133.87 (C2'), 139.05 (C3), 140.04 (Ci),
151.39 (C2). Found, %: C 49.23; H 4.05; Cl 18.08;
S 8.11. C16H16Cl2O5S. Calculated, %: C 49.12; H 4.12;
Cl 18.12; S 8.20.
1
1340, 1590, 1728, 1752. H NMR spectrum, δ, ppm:
1.21 t (3H, CH3, J = 6.98 Hz), 2.75 s (2H, CH2), 4.13 q
(2H, CH2O, J = 6.9 Hz), 4.15 q (2H, CH2O, J =
7.2 Hz), 3.99 m [4H, (CH2O)2, J = 8.03 Hz], 4.24 m
[4H, (CH2O)2, J = 8.03 Hz], 5.38 s (1H, CH), 7.56 d.d
(2H, m-H, J = 7.84, 7.38 Hz), 7.67 d.d (2H, o-H,
J = 7.40, 7.23 Hz), 7.97 d (1H, p-H, J = 7.86 Hz).
13C NMR spectrum, δC, ppm: 13.91 (CH3), 48.39 (C4),
62.40 (CH2CH3), 66.44 (CH2O), 111.24 (C3), 128.05
(Co), 129.27 (Cp), 134.43 (Cm), 140.51 (Ci), 145.42
(C1), 158.91 (C2), 164.99 (COO), 198.01 (C5). Found,
%: C 50.62; H 4.30; Cl 7.70; S 6.43. C20H21ClO9S.
Calculated, %: C 50.80; H 4.48; Cl 7.50; S 6.78.
(1R,5S)-1,3-Diallyl-2,5-dichloro-4,4-ethylenedi-
oxy-2-cyclopentenol (X). Yellow oily substance,
Rf 0.35 (petroleum ether–ethyl acetate, 9:1, 2 runs).
IR spectrum, ν, cm–1: 748, 784, 1204, 1636, 3448.
1H NMR spectrum, δ, ppm: 2.56–2.69 m (2H, 1'-H),
2.58 br.s (1H, OH), 2.92–2.94 m (2H, 1''-H), 3.98–
4.09 m (4H, CH2O), 4.19–4.24 (2H, 3''-H), 4.36 s (1H,
5-H), 5.03–5.06 m (2H, 3'-H), 5.19 m (1H, 2''-H),
5.75 m (1H, 2'-H). 13C NMR spectrum, δC, ppm: 38.85
(C12), 66.58 (C6), 67.56 (CH2O), 79.82 (C7), 113.44
(C2), 121.64 (C14), 134.20 (C13), 151.39 (C7). Found,
%: C 53.32; H 5.68; Cl 24.18. C13H16Cl2O3. Calcu-
lated, %: C 53.62; H 5.54; Cl 24.35.
Diethyl 2-(2,4-dichloro-5,5-ethylenedioxy-3-oxo-
1-cyclopentenyl)propanedioate (VII). Yellow crystal-
line substance, mp 85–88°C, Rf 0.25 (petroleum ether–
ethyl acetate, 8:2, 4 runs). IR spectrum, ν, cm–1: 1045,
1
1165, 1320, 1470, 1730, 1752, 2936. H NMR spec-
trum, δ, ppm: 1.21–1.26 m (6H, 2CH3), 4.08–4.25 m
(8H, CH2O, CH2CH3), 4.43 s (1H, 4-H), 4.47 s (1H,
CHCO2). 13C NMR spectrum, δC, ppm: 14.05 (CH3),
49.51 (CHCO2), 61.41 (C4), 62.47 (CH3CH2O), 66.75
(CH2O), 108.51 (C5), 136.91 (C2), 153.49 (C1), 164.36
(COO), 188.75 (C3). Found, %: C 46.10; H 4.25;
Cl 19.50. C14H16Cl2O7. Calculated, %: C 45.80;
H 4.39; Cl 19.31.
(1S,5S)-1,3-Diallyl-2,5-dichloro-4,4-ethylenedi-
oxy-2-cyclopentenol (XI). Yellow oily substance,
Rf 0.30 (petroleum ether–ethyl acetate, 9:1, 2 runs).
IR spectrum, ν, cm–1: 748, 784, 1204, 1636, 3448.
1H NMR spectrum, δ, ppm: 2.43–2.62 m (2H, 1'-H),
2.48 br.s (1H, OH), 2.93–2.94 m (2H, 1''-H), 3.98–
4.14 m (4H, CH2O), 4.20–4.23 (2H, 3''-H), 4.29 s
(1H, 5-H), 5.03–5.06 m (2H, 3'-H), 5.19 m (1H, 2''-H),
5.75 (1H, 2'-H). 13C NMR spectrum, δC, ppm: 29.17
(C1''), 38.96 (C1'), 66.28 (C6), 66.61 (CH2O), 79.37
(C7), 113.10 (C5), 116.31 (C3'), 120.48 (C3'), 131.65
(C2''), 133.09 (C2'), 136.18 (C9), 139.04 (C8). Found, %:
C 53.32; H 5.68; Cl 24.18. C13H16Cl2O3. Calculated,
%: C 53.62; H 5.54; Cl 24.35.
Reaction of sulfone II with allylmagnesium
chloride. Copper(I) cyanide, 0.01 g (0.95 mmol), was
added under argon to 7 ml of a 0.6 M solution of
allylmagnesium chloride (4.30 mmol) in THF, and the
mixture was stirred for 20 min. The mixture was then
cooled to –60°C, and a solution of 0.30 g (0.95 mmol)
of sulfone II in 10 ml of THF was slowly added in
a dropwise manner. The mixture was stirred or 1 h at
0°C (until complete conversion of sulfone II), treated
with 5 ml of a saturated solution of ammonium
chloride, and extracted with ethyl acetate. The com-
bined extracts were washed with a saturated solution of
sodium chloride, dried over MgSO4, and evaporated,
and the residue was subjected to column chromatog-
raphy on silica gel using petroleum ether–ethyl acetate
(95:5) as eluent to isolate 0.14 g (42%) of compound
IX, 0.03 g (12%) of X, 0.07 g (28%) of XI, and 0.04 g
(16%) of XII.
4,4-Diallyl-2,5-dichloro-3-(2-hydroxyethoxy)-2-
cyclopentenone (XII). Yellow oily substance, Rf 0.26
(petroleum ether–ethyl acetate, 1:1). IR spectrum, ν,
cm–1: 935, 1020, 1070, 1580, 1600, 1728, 3090, 3400.
1H NMR spectrum, δ, ppm: 2.15–2.61 m (4H, 1'-H,
1''-H), 3.77 m (1H, OH), 3.95 t (2H, CH2OH, J =
4.42 Hz ), 4.47 s (1H, 5-H), 4.74–4.87 m (2H, CH2O),
5.06–5.25 m (4H, 3'-H, 3''-H), 5.13 m (2H, 6-H), 5.03
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 4 2005