OZONOLYTIC TRANSFORMATIONS OF (S)-(–)-LIMONENE
23
4 3 . 3 0 d ( C H ) , 5 1 . 3 5 q ( O C H 3 ) , 1 0 8 . 5 3 s
[C(OH)(OCH3)], 112.46 t (CH2=C), 119.75 s
(CH2CN), 145.17 s (CH2=C).
[(1S)-2,4-Dimethoxy-2,4-dimethylcyclohexyl]-
acetonitrile (VIII). Yield 0.61 g (15%), Rf 0.45 (pe-
troleum ether–tert-butyl methyl ether, 2:1). H NMR
1
spectrum, δ, ppm: 1.11 s (3H, CH3), 1.15 s (3H, CH3),
1.34–1.78 m (2H, 5-Hax, 6-Hax), 1.82–2.10 m (2H,
5-Heq, 6-Heq), 1.89–2.03 m (1H, CH), 1.94 d (1H, 3-H,
J = 11.2 Hz), 2.01 d (1H, 3-H, J = 11.2 Hz), 2.05 d.d
(1H, CH2CN, J = 8.1, 4.5 Hz), 2.27 d.d (1H, CH2CN,
J = 8.1, 5.4 Hz), 3.18 s (3H, OCH3), 3.20 s (3H,
OCH3). 13C NMR spectrum, δC, ppm: 18.19 (18.50) t
(CH2CN), 18.50 q (CH3), 25.43 (21.67) q (CH3), 26.12
(25.05) t (C6), 35.27 (34.84) t (C5), 42.75 d (CH),
43.19 (41.66) t (C3), 49.08 q (OCH3), 49.52 q (OCH3),
74.41 (74.19) s [C(CH3)OCH3], 75.51 (75.34) s
[C(CH3)OCH3], 119.75 s (CN).
d. Dimethyl sulfide, 6.0 ml (80 mmol), was added
under stirring at 0°C to a solution of ozonide II, and
the mixture was stirred for 16 h at room temperature.
The mixture was evaporated, the residue was dissolved
in 100 ml of methylene chloride, and the solution was
washed with water (4×25 ml), dried over MgSO4, and
evaporated to isolate 2.56 g (85%) of ketoaldehyde
XIV. Rf 0.30 (petroleum ether–tert-butyl methyl ether,
2:1). IR spectrum (KBr), ν, cm–1: 2725 [C(O)H], 1710
1
(C=O), 1645 (C=CH2). The H and 13C NMR spectra
of the product were identical to those reported in [1].
Compound XIV, 1.6 g (9.5 mmol), was dissolved
in 30 ml of methanol, 2.3 g (33.3 mmol) of hydroxyl-
amine hydrochloride was added, and the mixture was
stirred for 48 h at room temperature. The mixture was
evaporated, the residue was dissolved in 100 ml of
methylene chloride, and the solution was washed with
water (4×25 ml), dried over MgSO4, and evaporated.
According to the GLC data, the residue (1.3 g) con-
tained ester IV and oxime XVII at a ratio of 85:15.
The products were separated by chromatography on
silica gel using petroleum ether and petroleum ether–
tert-butyl methyl ether (10:1 and 5:1) as eluents.
Methyl (3S)-6-oxo-3-(prop-1-en-2-yl)heptanoate
(IX). Yield 0.25 g (7%), Rf 0.37 (petroleum ether–tert-
1
butyl methyl ether, 2:1). H NMR spectrum, δ, ppm:
1.43–1.60 m (2H, CH2), 1.66 s (3H, CH3), 1.89–2.43 m
(2H, CH2), 2.08–2.39 m (2H, CH2), 2.12 s [3H,
CH3C(O)], 2.43–2.55 m (1H, CH), 3.64 s [3H,
C(O)OCH3], 4.48 d (2H, C=CH2, J = 1.7 Hz).
13C NMR spectrum, δC, ppm: 18.20 q (CH3), 29.89 q
(CH3), 26.14 t (CH2), 34.57 t (CH2), 41.07 t (CH2),
43.03 d (CH), 51.34 s (COOCH3), 112.82 t (CH2=C),
145.23 s (CH2=C), 172.64 s (COOCH3), 208.34 s
(C=O).
Compound IV. Yield 0.95 g (41%), Rf 0.53 (petro-
leum ether–tert-butyl methyl ether, 2:1). The product
was identical to a sample isolated as described in a.
Methyl (3S,6Z)-6-hydroxyimino-3-(prop-1-en-2-
yl)heptanoate (X). Yield 0.07 g (2%), Rf 0.13 (petro-
1
leum ether–tert-butyl methyl ether, 2:1). H NMR
(3S)-6-Hydroxyimino-1-methoxy-3-(prop-1-en-2-
yl)heptan-1-ol (XVII). Yield 0.12 g (6%), Rf 10.22 (pe-
troleum ether–tert-butyl methyl ether, 2:1). H NMR
spectrum, δ, ppm: 1.35–1.70 m (2H, CH2), 1.65 s (3H,
CH3), 1. 82 s (3H, CH3), 2. 15–2. 25 m [1H,
CH2CH(OH)(OCH3)], 2.21–2.35 m (1H, CH), 2.23 t
(2H, CH2, J = 7. 0 Hz), 2. 25–2. 40 m [1H,
CH2CH(OH)(OCH3)], 3.62 s (3H, OCH3), 4.65 t [1H,
CH2CH(OH)(OCH3), J = 6.5 Hz], 4.65–4.93 m
(2H, C=CH2), 5.17 s (1H, OH), 8.2 br.s (1H, NOH).
13C NMR spectrum, δC, ppm: 17.05 q (CH3), 21.60 q
(anti-CH3), 28.49 t (CH2), 38.66 t (CH2), 40.86 t
(CH2), 42.81 d (CH), 51.17 q (OCH3), 101.52 d
[CH(OH)(OCH3)], 112.72 t (CH2=C), 145.19 s
(CH2=C), 157.83 s (C=N).
spectrum, δ, ppm: 1.40–1.81 m (2H, CH2), 1.72 s (3H,
CH3), 1.79 s (3H, CH3), 1.85–2.18 m (2H, CH2), 1.90–
2.50 m (2H, CH2COOCH3), 1.90–2.50 m (1H, CH),
3.65 s (3H, COOCH3), 4.41–4.53 m (2H, C=CH2, J =
13
1.7 Hz), 7.40 br.s (1H, NOH). C NMR spectrum, δC,
ppm: 18.08 q (CH3), 24.65 t (CH2), 24.86 q (anti-CH3),
33.03 t (CH2), 34.08 t (CH2), 42.59 d (CH), 50.83 s
(COOCH3), 112.07 t (CH2=C), 144.95 s (CH2=C),
155.63 s (C=NOH), 173.59 s (COOCH3).
(3S)-6-Hydroxy-6-methoxy-3-(prop-1-en-2-yl)-
heptanenitrile (XI). Yield 0.068 g (2%), Rf 0.10 (pe-
1
troleum ether–tert-butyl methyl ether, 2:1). H NMR
spectrum, δ, ppm: 1.03 s (3H, CH3), 1.42–1.82 m (2H,
CH2), 1.85–2.10 m (2H, CH2), 2.14 s (3H, CH3),
2.43 d.d (1H, CH2CN, J = 12.3, 6.1 Hz), 2.61 d.d (1H,
CH2CN, J = 12.3, 5.7 Hz), 2.60–2.71 m (1H, CH),
3.53 s (3H, OCH3), 3.80 s (1H, OH), 4.30–5.00 m
(2H, C=CH2). 13C NMR spectrum, δC, ppm: 17.68 t
(CH2CN), 18.20 (18.52) q (CH3), 29.88 (29.54) q
(CH3), 26.14 (25.32) t (CH2), 41.07 (36.07) t (CH2),
e. Sodium tetrahydridoborate, 1.89 g (50.0 mmol),
was added under stirring at 10°C to a solution of
ozonide II, and the mixture was stirred for 3 h at room
temperature. A solution of 0.54 ml of acetic acid in
5.4 ml of water was added, the mixture was stirred for
3 h and filtered, and the filtrate was evaporated. The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 1 2012