VOSTRIKOV et al.
1372
19.66 (CH3), 21.16 (CH3), 26.30 (C5 , C6), 43.78 (C3),
44.18 (C4), 49.12 (C7), 51.76 (OCH3), 67.03 (C1),
170.15 (COO), 210.99 (C2).
was distilled off, and the residue was subjected to
chromatography on silica gel using petroleum ether–
ethyl acetate (10:1) as eluent. Yield 86 mg (71%),
mp 59–60.5°C (from hexane), Rf 0.61 (hexane–EtOAc,
5:1), [α]D20 = +100° (c = 1, CHCl3). IR spectrum, ν,
Acid IV was synthesized by alkaline hydrolysis of
ester III under standard conditions. mp 225–228°C
(from water); published data: mp 227–229°C [8].
1
cm–1: 1644, 1748. H NMR spectrum, δ, ppm: 1.05 s
(3H, CH3), 1.07 s (3H, CH3), 1.40 d.d.d (1H, endo-
5-H, J = 3.9, 9.1, 12.6 Hz), 1.60 d.d.d (1H, endo-6-H,
The IR spectra were recorded on a UR-20 spectro-
photometer from samples dispersed in mineral oil. The
1H and 13C NMR spectra were obtained on a Bruker
3
J = 4.5, 9.1, 13.5 Hz), 1.93 d (1H, endo-3-H, J = 0.9,
2J = 18.4 Hz), 2.10–2.30 m (2H, exo-5-H, exo-6-H),
1
AM-300 spectrometer (300 and 75.47 MHz for H
3
2.40 m (1H, 4-H), 2.50 d.t (1H, exo-3-H, J = 4.13,
and 13C, respectively) from solutions in CDCl3 using
TMS as internal reference. Silica gel L 100/160 µm
(Lachema) was used for column chromatography.
Thin-layer chromatography was performed on Silufol
plates. The optical rotations were measured on
a Perkin–Elmer 241 MC polarimeter. The mass spec-
trum (electron impact, 70 eV) was recorded on
an MKh-1320 instrument.
2
18.4 Hz), 5.34 d (1H, J = 1.5 Hz), 5.56 d (1H, =CH2,
2J = 1.5 Hz). 13C NMR spectrum, δC, ppm: 20.05 q
(CH3), 21.63 q (CH3), 26.54 t (C5), 28.40 t (C6), 43.75 t
(C3), 43.84 d (C4), 49.55 s (C7), 67.58 s (C1), 117.54 t
and 137.43 s (C=CH2), 212.69 s (C2). Mass spectrum
(EI), m/z (Irel, %): 198 (28) [M]+, 183 (28) [M – CH3]+,
170 (12) [M – C2H4]+, 163 (60) [M – Cl]+, 155 (38),
41 (100). Found, %: C 66.29; H 7.55; Cl 17.49.
C11H15ClO. Calculated, %: C 66.49; H 7.61; Cl 17.84.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 01-03-32638).
Methyl 7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-
1-carboxylate (III) and 7,7-dimethyl-2-oxobicyclo-
[2.2.1]heptane-1-carboxylic acid (IV). A solution of
100 mg (0.51 mmol) of compound II in 5 ml of
methanol was cooled to–78°C, and an ozone–oxygen
mixture was passed through the solution until it
became light blue. Excess ozone was removed by
flushing with argon, and the mixture was allowed to
gradually warm up to 20°C and was stirred for 2 days
at that temperature. The solvent was distilled off, and
the residue was subjected to chromatography on SiO2
using petroleum ether–ethyl acetate (10:1) as eluent.
Yield 77 mg (78%), mp 49–51°C (from hexane),
Rf 0.72 (hexane–EtOAc, 5:1), [α]D20 = +25.8° (c = 1,
CHCl3). 1H NMR spectrum, δ, ppm: 1.05 s (3H, CH3),
1.13 s (3H, CH3), 1.40 d.d.d (1H, endo-6-H, J = 4.0,
9.5, 13.0 Hz), 1.75 d.d.d (1H, endo-7-H, J = 4.8,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 9 2004