5
16
KHALILOVA et al.
2
0
oily substance, [α] = –103.78° (c = 3.75, CHCl3),
of 0.507 g (1.7 mmol) of acetate V and 0.30 g of
potassium hydroxide in a mixture of 1 ml of water and
2 ml of ethanol was stirred for 1 h (TLC). The mixture
was neutralized with 10% hydrochloric acid to pH 7
and extracted with ethyl acetate (3×5 ml), the com-
bined extracts were washed with a saturated solution of
D
R 0.65 (petroleum ether–EtOAc, 1:1). IR spectrum, ν,
cm : 2719, 1739, 1707, 933. H NMR spectrum, δ,
ppm: 1.05 d (3H, CH , J = 7.3 Hz), 1.71 d.d (1H, 6-H,
J = 7.0, 9.5 Hz), 1.83 d.d.d (1H, 7-H, J = 6.6, 8.3,
.5 Hz), 2.03 s (3H, CH CO), 2.32 d.d (1H, 5-H , J =
.71, 18.4 Hz), 2.51 d.d.d (1H, 5-H , J = 2.8, 5.9,
8.4 Hz), 3.22 d.d.d (1H, 2-H, J = 2.3, 2.8, 7.3 Hz),
.20 d.d (1H, 8-H , J = 11.8, 8.3 Hz), 4.32 d.d (1H,
-H , J = 6.6, 11.8 Hz), 5.50 d.d.d (1H, 3-H, J = 2.8,
.8, 10.3 Hz), 5.57 d.d.d (1H, 4-H, J = 2.3, 5.9,
0.3 Hz), 8.78 s (1H, CHO). C NMR spectrum, δ ,
ppm: 18.97 (CH ), 19.91 (C ), 20.30 (C ), 20.87
CH CO), 25.01 (C ), 25.99 (C ), 38.38 (C ), 59.75
C ), 122.97 (C ), 129.95 (C ), 170.84 (CH CO),
f
–
1
1
3
9
1
1
4
8
2
1
3 A
sodium chloride, dried over MgSO , and evaporated,
B
4
and the residue was purified by chromatography. Yield
2
0
0.407 g (93%), oily substance, [α] = –46.68° (c =
A
D
5.85, CHCl ), R = 0.18 (petroleum ether–EtOAc, 3:1).
B
3
f
–
1
1
IR spectrum, ν, cm : 3400, 910. H NMR spectrum, δ,
1
3
ppm: 1.11 d (3H, CH , J = 7.3 Hz), 1.35 d.d.d (1H,
C
3
6
5
7-H, J = 2.7, 6.1, 8.8 Hz), 1.80 d.d (1H, 6-H, J = 7.3,
3
7
2
1
(
(
8.8 Hz), 2.12 d (1H, 5-H , J = 17.0 Hz), 2.43 d.d.d.d
3
A
8
4
3
(1H, 5-H , J = 2.4, 3.2, 7.3, 17.0 Hz), 2.80 d.d (1H,
3
B
2
01.29 (CHO). Found, %: C 69.21; H 7.74. C H O .
2-H, J = 2.3, 7.3 Hz), 2.82 m (6H, 4′-H, 5′-H, 6′-H),
12
16
3
Calculated, %: C 69.20; H 7.74.
3.52 d.d (1H, 8-H , J = 2.7, 10.8 Hz), 3.55 s (1H,
A
(
1S,2R,6R,7S)-1-(1,3-Dithian-2-yl)-2-methylbi-
cyclo[4.1.0]hept-3-en-7-yl acetate (V). Acetate IV,
.08 g (0.38 mmol), was dissolved in 5 ml of methyl-
2′-H), 3.79 d.d (1H, 8-H
(1H, 3-H, J = 2.3, 2.4, 10.3 Hz), 5.55 d.d.d (1H, 4-H,
B
, J = 6.1, 10.8 Hz), 5.38 d.d.d
1
3
0
J = 3.2, 3.5, 10.3 Hz). C NMR spectrum, δ , ppm:
C
6
7
5
5′
ene chloride, 0.11 ml (1.14 mmol) of propane-1,3-di-
thiol and 0.004 g (5%) of p-toluenesulfonic acid were
added, and the mixture was stirred for 30 min (TLC).
The mixture was treated with water, the organic phase
was separated, the aqueous phase was extracted with
methylene chloride (3×5 ml), the extracts were com-
20.24 (C ), 20.47 (C ), 20.55 (C ), 25.71 (C ), 27.90
1
2
4′
6′
(CH
), 30.22 (C ), 30.51 (C ), 31.11 (C ), 31.78 (C ),
3
8
2′
4
3
58.28 (C ), 61.07 (C ), 123.42 (C ), 130.43 (C ).
Found, %: C 60.89; H 7.86; S 25.01. C13
culated, %: C 60.90; H 7.87; S 25.79.
H22OS . Cal-
2
(
1S,2R,6R,7S)-1-(1,3-Dithian-2-yl)-2-methylbi-
bined with the organic phase and dried over MgSO4,
cyclo[4.1.0]hept-3-ene-7-carbaldehyde (VII). Pyri-
dinium chlorochromate, 0.43 g (2.0 mmol), was added
in small portions under vigorous stirring to a solution
of 0.25 g (1.0 mmol) of alcohol VI in 10 ml of methyl-
ene chloride. The mixture was stirred for 1 h (TLC),
5 ml of diethyl ether was added, the precipitate was
filtered off, the filtrate was evaporated, and the residue
was purified by chromatography on silica gel. Yield
the solvent was distilled off on a rotary evaporator, and
the residue was purified by chromatography on silica
gel. Yield 0.105 g (91%), oily substance, [α] = –11.4°
c = 0.4, CHCl ), R 0.48 (petroleum ether–EtOAc,
:1). IR spectrum, ν, cm : 2960, 1732, 968, 910.
H NMR spectrum, δ, ppm: 1.13 d (3H, CH , J =
.3 Hz), 1.42 d.d (1H, 7-H, J = 6.3, 8.9 Hz), 1.81 d.d
2
0
D
(
3 f
–
1
3
1
3
7
(
1H, 6-H, J = 5.9, 8.9 Hz), 2.02 s (3H, CH CO),
0.157 g (63%), oily substance, R 0.4 (petroleum ether–
3
f
–1
2
2
2
6
1
5
.15 d.d.d.d (1H, 5-H , J = 2.3, 3.0, 5.9, 19.3 Hz),
EtOAc, 3:1). IR spectrum, ν, cm : 2233, 1695, 925.
B
1
.44 d.d (1H, 5-H , J = 2.3, 19.3 Hz), 2.90 d.d (1H,
H NMR spectrum, δ, ppm: 1.20 d (3H, CH , J =
3
A
-H, J = 2.3, 7.3 Hz), 2.72–2.90 m (6H, 4′-H, 5′-H,
7.15 Hz), 1.81 d.d (1H, 7-H, J = 7.0, 7.1 Hz),
2.07 d.d.d (1H, 6-H, J = 2.0, 6.2, 7.0 Hz), 2.39 d (1H,
′-H), 3.60 s (1H, 2′-H), 3.90 d.d (1H, 8-H , J = 8.9,
B
1.5 Hz), 4.25 d.d (1H, 8-H , J = 6.3, J = 11.5 Hz),
5-H
2.64 d.d.d.d (1H, 5-H
3.07 d.d.d (1H, 2-H, J = 1.6, J = 2.6, 3.07 Hz), 3.67 s
1H, 2′-H), 5.54 d.d.d.d (1H, 3-H, J = 2.0, 2.5, 2.6,
B
, J = 19.4 Hz), 2.80 m (6H, 4′-H, 5′-H, 6′-H),
A
.53 d.d.d (1H, 4-H, J = 3.0, 5.9, 10.2 Hz), 5.37 d.d.d.d
A
, J = 3.0, 3.0, 6.2, 19.4 Hz),
1
3
(
1H, 3-H, J = 2.3, 2.3, 2.3, 10.2 Hz). C NMR spec-
5
6
(
trum, δ , ppm: 20.02 (CH CO), 20.62 (C ), 20.68 (C ),
2
(
1
C
3
7
5'
2
1
1
0.3 Hz), 5.64 d.d.d.d (1H, 4-H, J = 1.6, 3.0, 3.0,
0.68 (C ), 25.78 (C ), 26.44 (C ), 27.92 (CH ), 30.60
3
1
3
1
4′
6′
2′
8
0.3 Hz), 9.38 d (1H, CHO, J = 7.1 Hz). C NMR
C ), 31.25 (C ), 31.91 (C ), 60.71 (C ), 61.07 (C ),
6
5
7
4
3
spectrum, δ , ppm: 20.72 (C ), 21.74 (C ), 20.47 (C ),
2
23.45 (C ), 130.60 (C ), 170.90 (C=O). Found, %:
C
5
′
2
4′
5.54 (C ), 27.72 (CH ), 28.15 (C ), 31.08 (C ), 31.62
C 60.36; H 7.43; S 21.49. C H O S . Calculated, %:
3
1
5
22
2 2
6
′
1
8
4
3
(
C ), 38.63 (C ), 58.87 (C ), 122.67 (C ), 130.65 (C ),
C 60.37; H 7.42; S 21.50.
(1S,2R,6R,7S)-1-(1,3-Dithian-2-yl)-2-methylbi-
cyclo[4.1.0]hept-3-en-7-yl]methanol (VI). A solution
+
1
99.24 (CHO). Mass spectrum: m/z 355 [M + H] .
[
Found, %: C 61.37; H 7.13; S 25.21. C H OS . Cal-
1
3
18
2
culated, %: C 61.40; H 7.20; S 25.11. M 354.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012