TRANSFORMATIONS OF PEROXIDE OLEFIN OZONOLYSIS PRODUCTS
1413
Ozonolysis of castor oil (III). The product mix-
ture, 12.5 g, was subjected to chromatography on silica
gel using hexane–tert-butyl methyl ether (4:1) as
eluent to isolate 4.61 g (71%) of ester XII, 2.66 g
(42%) of XIII, and 2.66 g (37%) of XIV.
1-H, J = 9.5, 7.4, 4.0 Hz), 1.03 s (3H, cis-CH3),
1.05 d.d.d (1H, 3-H, J = 9.5, 7.1, 5.0 Hz), 1.18 s (3H,
trans-CH3), 1.31 s [6H, CH(CH3)2, J = 6.3 Hz], 1.97 s
[3H, CH3C(NOH)], 2.24 d.d (1H, 3-CH2, J = 13.2,
5.0 Hz), 2.32 d.d (1H, 1-CH2, J = 10.4, 5.6 Hz),
2.38 d.d (1H, 3-CH2, J = 13.2, 7.1 Hz), 2.54 d.d (1H,
1-CH2, J = 10.4, 4.0 Hz), 5.02 sept [1H, CH(CH3)2],
8.30 br.s (1H, OH). 13C NMR spectrum, δC, ppm:
12.29 q (CH3C=NOH), 13.79 q (cis-CH3), 16.31 s (C2),
20.71 d (C1), 21.73 d (C3), 21.97 q [CH(CH3)2], 27.45 q
(trans-CH3), 29.31 t (3-CH2), 29.88 t (1-CH2), 66.52 d
[CH(CH3)2], 157.02 s (C=NOH), 172.0 s (C=O).
Ozonolysis of (–)-α-pinene (V). The product mix-
ture, 1.90 g, was subjected to chromatography on silica
gel using first hexane and then hexane–tert-butyl
methyl ether (20:1 to 1:1) as eluents to isolate 1.45 g
(60%) of oxime XVI and 0.46 g (26%) of nitrile XVII.
Isopropyl (R)-3-hydroxynonanoate (XII). Rf 0.52
(hexane–t-BuOMe, 2:1). IR spectrum (KBr), ν, cm–1:
1
3420 (OH), 1740 (C=O), 1140 (C–O). H NMR spec-
trum, δ, ppm: 0.89 t (3H, C9H3, J = 6.7 Hz), 1.18 d
[6H, CH(CH3)2, J = 6.3 Hz], 1.10–1.42 m (6H, 5-H,
6-H, 7-H), 1.25–1.40 m (1H, 4-H), 1.42–1.65 m (3H,
4-H, 8-H), 2.20 br.s (1H, OH), 2.41 d.d (1H, 2-H, J =
16.4, 3.3 Hz), 2.28 d.d (1H, 2-H, J = 16.4, 4.4 Hz),
3.86–4.0 m (1H, 3-H), 4.93 sept [1H, CH(CH3)2, J =
6.3 Hz]. 13C NMR spectrum, δC, ppm: 13.95 q (C9),
21.70 q [CH(CH3)2], 22.94 t (C8), 25.36 t (C5), 28.80 t
(C6), 31.70 t (C7), 36.52 t (C4), 41.66 t (C2), 67.20 d
[CH(CH3)2], 67.92 d (C3), 172.43 s (C=O).
Isopropyl {(1S,3S)-3-[(1E)-N-hydroxyethan-
imidoyl]-2,2-dimethylcyclobutyl}acetate (XVI).
Rf 0.57 (hexane–t-BuOMe, 3:2). IR spectrum (KBr), ν,
Isopropyl 8-cyanooctanoate (XIII). Rf 0.20 (hex-
ane–t-BuOMe, 2:1). IR spectrum (KBr), ν, cm–1: 2220
(C≡N), 1745 (C=O). 1H NMR spectrum, δ, ppm: 1.15–
1.40 m (8H, 3-H, 4-H, 5-H, 6-H), 1.19 d [6H,
CH(CH3)2, J = 6.4 Hz], 1.55–1.68 m (2H, 7-H), 2.28–
2.40 m (4H, 2-H, 8-H), 4.99 sept [1H, CH(CH3)2].
13C NMR spectrum, δC, ppm: 17.00 t (C8), 21.78 q
[CH(CH3)2], 24.68 t (C3), 25.20 t (C7), 28.36 t
(C6), 28.65 t (C5), 28.80 t (C4), 33.89 t (C2), 67.38 d
[CH(CH3)2], 119.69 s (CN), 173.18 s (C=O).
Propane-1,2,3-triyl tris(9-isopropoxy-9-oxo-
nonanoate) (XIV). Rf 0.14 (hexane–t-BuOMe, 2:1).
1H NMR spectrum, δ, ppm: 1.15–1.77 m (12H, 3-H,
7-H), 1.16–1.40 m (18H, 4-H, 5-H, 6-H), 1.22 d (18H,
CH3, J = 6.3 Hz), 2.15 t (6H, 8-H, J = 6.7 Hz), 2.35 t
(6H, 2-H, J = 6.6 Hz), 4.15 d.d (2H, 1′-H, 3′-H, J =
11.9, 4.1 Hz), 4.28 d.d (2H, 1′-H, 3′-H, J = 11.9,
5.7 Hz), 5.01 sept [3H, CH(CH3)2, J = 6.3 Hz], 5.27–
5.32 m (1H, 2′-H). 13C NMR spectrum, δC, ppm:
21.78 q (CH3), 24.71 t (C7), 24.88 t (C3), 28.84 t (C6),
29.16 t (C5), 29.63 t (C4), 33.91 t (C8), 34.59 t (C2),
62.06 t (C1′, C3′), 67.34 d [CH(CH3)2], 68.06 d (C2′),
172.63 s (2′-OC=O), 173.18 s (C9), 173.26 s
(1′-OC=O, 3′-OC=O).
1
cm–1: 3300 (OH), 2887 (C–H), 1637 (C=N). H NMR
spectrum, δ, ppm: 0.84 s (3H, cis-CH3), 1.21 d (3H,
trans-CH3), 1.22 d [6H, CH(CH3)2, J = 6.3 Hz], 1.80 s
[3H, CH3C(NOH)], 1.88 d.t (1H, 4-Hcis, J = –10.8,
7.4 Hz), 2.02 d.t (1H, 4-Htrans, J = 10.8, 10.6 Hz),
2.20 d.d (1H, 1-CH2, J = 14.6, 7.3 Hz), 2.21–2.45 m
(1H, 1-H), 2.28 d.d (1H, 1-CH2, J = –14.6, 6.3 Hz),
2.59 d.d (1H, 3-H, J = 10.6, 7.4 Hz), 4.98 sept [1H,
CH(CH3)2, J = 6.3 Hz], 8.30 br.s (1H, OH). 13C NMR
spectrum, δC, ppm: 14.52 q [CH3C(NOH)], 16.74 q
(cis-CH3), 21.79 q [CH(CH3)2], 24.52 t (C4), 30.15 q
(trans-CH3), 35.54 t (CH2), 38.24 d (C1), 42.83 s (C2),
47.61 d (C3), 67.51 d [CH(CH3)2], 157.35 s
[C(NOH)CH3], 172.40 s (C=O).
{(1S,3S)-3-[(1E)-N-Hydroxyethanimidoyl]-
2,2-dimethylcyclobutyl}acetonitrile (XVII). Rf 0.30
(hexane–t-BuOMe, 3:2). IR spectrum (KBr), ν, cm–1:
2220 (C≡N), 1640 (C=N). 13C NMR spectrum, δC,
ppm: 14.52 q [CH3C(NOH)], 16.77 q (CH3), 17.25 t
(C), 24.86 t (C4), 29.86 q (CH3), 38.14 d (C1), 42.59 s
(C2), 47.85 d (C3), 118.69 s (CN), 156.93 s (C=NOH).
Treatment of peroxide products of ozonolysis of
olefins I–V with semicarbazide hydrochloride.
An ozone–oxygen mixture was bubbled through a so-
lution of 10.0 mmol of olefin I–V in 30 ml of anhy-
drous isopropyl alcohol on cooling to 0°C until 1 mol
of O3 per mole of double bond was absorbed. The
mixture was purged with argon, 3.90 g (35.0 mmol) of
semicarbazide hydrochloride per double bond was
added under stirring at 0°C, and the mixture was
Ozonolysis of ∆3-carene (IV). By chromatography
on silica gel using hexane–tert-butyl methyl ether
(4:1) as eluent we isolated 1.99 g (82%) of isopropyl
{3-[(2E)-2-(hydroxyimino)propyl]-2,2-dimethylcyclo-
propyl}acetate (XV). Rf 0.53 (hexane–t-BuOMe, 3:2),
[α]D20 = +0.8° (CH2Cl2, c = 0.30). IR spectrum (KBr), ν,
cm–1: 3334 (OH), 2870 (C–H), 1730 (C=O), 1640
1
(C=N). H NMR spectrum, δ, ppm: 0.84 d.d.d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 10 2013