TRANSFORMATIONS OF PEROXIDE PRODUCTS OF OLEFIN OZONOLYSIS
931
assigned, and the coupling constants were determined,
Octanal (VII). IR spectrum (KBr): ν 1718 cm–1
(C=O). The NMR spectra were identical to those
reported in [8].
1
with the aid of double resonance and COSY H–1H
two-dimensional homonuclear correlation techniques.
The 13C NMR spectra were recorded with broad-band
decoupling from protons and in the JMOD mode. GLC
analysis was performed on Chrom-5 (1.2-m column
packed with 5% of SE-30 on Chromaton N-AW-
DMCS, 0.16–0.20 mm; oven temperature 50–300°C)
and Chrom-41 chromatographs (2.4-m column packed
with PEG-6000; oven temperature 50–200ºC); carrier
gas helium. Sorbfil silica gel (Russia) was used for
analytical thin-layer chromatography. The products
were isolated by column chromatography on silica gel
(70–230 mesh, Lancaster, England). The optical rota-
tions were measured on a Perkin Elmer 241-MC polar-
imeter. The elemental compositions of all isolated
compounds were consistent with the theoretical ones.
The ozonizer efficiency was 40 mmol/h.
Ozonolysis of olefins I–IV (general procedure).
A solution of 10.0 mmol of olefin I–IV in 30 mL of
THF was cooled to 0°C, and an ozone–oxygen mixture
was bubbled through the solution until 10.5 mmol of
ozone was absorbed.
Treatment of peroxide ozonolysis products with
hydroxylamine hydrochloride (general procedure).
The mixture obtained after ozonolysis was purged with
argon, 2.43 g (35.0 mmol) of hydroxylamine hydro-
chloride was added under stirring at 0°C, and the mix-
ture was stirred at room temperature until peroxide
products disappeared (starch–iodine test). The solvent
was distilled off, the residue was dissolved in 150 mL
of chloroform, and the solution was washed with brine
(4×15 mL), dried over Na2SO4, and evaporated.
The residue obtained in the reaction with cyclo-
octene (II), 1.64 g, was separated by silica gel chroma-
tography using hexane–tert-butyl methyl ether (20:1
to 1:1) as eluent to isolate 1.21 g (70%) of octanedioic
acid (VIII), Rf 0.21 (hexane–tert-butyl methyl ether,
2:1). IR spectrum (KBr), ν, cm–1: 1712 (C=O), 3242
1
(OH). H NMR spectrum, δ, ppm: 1.31–1.38 m (4H,
4-H, 5-H), 1.50–1.70 m (4H, 3-H, 6-H), 2.49 t (4H,
2-H, 7-H, J = 6.3 Hz). 13C NMR spectrum, δC, ppm:
24.56 t (C4, C5), 29.43 t (C3, C6), 33.82 t (C2, C7),
177.06 s (COOH) [9].
The residue obtained in the ozonolysis of (–)-α-pi-
nene (III), 2.0 g, was separated by silica gel chroma-
tography using hexane–tert-butyl methyl ether (20:1
to 1:1) as eluent to isolate 0.47 g (26%) of keto acid
IX), 0.40 g (24%) of keto nitrile X, and 0.21 g (12%)
of hydroxyimino nitrile XI.
(3-Acetyl-2,2-dimethylcyclobutyl)acetic acid (IX)
[10]. Rf 0.21 (hexane–tert-butyl methyl ether, 4:1),
[α]D20 = –39.8° (c = 0.8164, CH2Cl2). IR spectrum
1
(KBr), ν, cm–1: 1715 (C=O), 3330 (OH). H NMR
spectrum, δ, ppm: 0.83 s (3H, cis-CH3), 1.29 s (3H,
trans-CH3), 1.83–1.92 m (1H, cis-4-H), 1.94 d.d (1H,
trans-4-H, J = 10.1, 10.7 Hz), 2.03 s (3H, CH3CO),
2.12–2.36 m (3H, 1-H, 1-CH2), 2.83 d.d (1H, 3-H, J =
10.1, 7.5 Hz), 9.70 br.s (1H, COOH). 13C NMR spec-
trum, δC, ppm: 16.78 q (cis-CH3), 22.12 t (C4), 29.68 q
(CH3CO), 30.26 q (trans-CH3), 35.95 t (1-CH2),
37.10 d (C1), 42.94 s (C2), 52.88 d (C3), 178.28 s
(COOH), 208.27 s (C=O).
(3-Acetyl-2,2-dimethylcyclobutyl)acetonitrile (X)
[10]. Rf 0.33 (hexane–tert-butyl methyl ether, 3:2),
[α]D20 = –131.16° (c = 1.02, CHCl3) [10]. IR spectrum
The residue obtained in the reaction with non-1-ene
(I), 1.37 g, was separated by chromatography on silica
gel using hexane–tert-butyl methyl ether (20:1 to 1:1)
as eluent to isolate 1.15 g (80%) of octanoic acid (V),
0.20 g (15%) of octanal oxime (VI), and 0.07 g (5%)
of octanal (VII).
1
(KBr): ν 2220 cm–1 (CN). H NMR spectrum, δ, ppm:
0.95 s (cis-CH3), 1.40 s (trans-CH3), 1.94 d.t (1H,
cis-4-H, J = –11.0, 9.5 Hz), 2.03 d.t (1H, trans-4-H,
J = –11.0, 8 Hz), 2.08 s (3H, CH3CO), 2.32 d.d (1H,
1-CH2, J = 15.2, 8.00 Hz), 2.32 d.d (1H, 1-CH2, J =
15.2, 7.8 Hz), 2.37–2.43 m (1H, 1-H), 2.90 d.d (1H,
3-H, J = 9.5, 8.0 Hz). 13C NMR spectrum, δC, ppm:
16.54 q (CH3), 17.25 t (CH2), 22.89 t (C4), 29.86 q
(CH3), 30.27 q (CH3CO) 38.16 d (C1), 42.97 s (C2),
53.81 d (C3), 118.56 s (CN), 206.63 s (C=O).
Octanoic acid (V). Rf 0.25 (hexane–tert-butyl
1
methyl ether, 2:1). H NMR spectrum, δ, ppm: 0.87 t
(3H, 8-H, J = 6.6 Hz), 1.20–1.37 m (6H, 4-H, 5-H,
6-H, 1.43–1.58 m (2H, 7-H), 1.56–1.69 m (2H, 3-H),
2.24 t (2H, 2-H, J = 6.7 Hz), 11.45 br.s (1H, OH). The
IR and 13C NMR spectra were identical to those
reported previously [7].
{3-[(E)-(1-Hydroxyimino)ethyl]-2,2-dimethyl-
cyclobutyl}acetonitrile (XI). Rf 0.30 (hexane–tert-
butyl methyl ether, 3:2). The IR and NMR spectra of
XI were identical to those given in [4].
Octanal oxime (VI). Rf 0.53 (hexane–tert-butyl
methyl ether, 2 :1). The IR and NMR spectra were
identical to those reported previously [4].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 7 2014