BONDARENKO et al.
224
a calculated quantity of NOCl was added in solution in
dichloromethane, and 5 ml of liquid SO2. The test tube
was tightly stoppered, warmed to the required
temperature, shaken till the formation of a homogeneous
solution, and maintained at the desired temperature.After
a lapse of the required time the reaction mixture was
diluted with 20 ml of cooled dichloromethane, the mixture
was warmed to 0°C, and the organic layer was neutralized
with a water solution of Na2CO3, and then washed with
water. The water layer was extracted with dichloro-
methane, the combined organic solutions were dried with
sodium sulfate. The solution was evaporated, the residue
was subjected to chromatography on silica gel. Yields of
compounds obtained are compiled in Table 2.
3J 7.1 Hz), 3.29 m (1H, C4H), 5.02 d (1H, HCO,
3J 8.0 Hz), 7.12 br.s, 7.30–7.40 m (5H).
As a result of a reaction of 0.200 g (1 mmol) of 1-bromo-
2-phenylcyclopropane (IV) and 0.130 g (2 mmol) of NOCl
in 5 ml of SO2 for 18 h at –20°C after the standard workup
of the reaction mixture and the chromatographic isolation
on a column (SiO2, 40/100 μm, ethyl acetate–petroleum
ether, 1:3) we isolated 0.10 g (54%) of cyclopropane IV,
0.047 g (21%) of 3-bromo-5-phenylisoxazoline (XII-
A), 0.010 g (4%) of 4-bromo-5-phenylisoxazoline
1
(XII-B), Rf 0.60. H NMR spectrum, δ, ppm: 5.02 d.d
3
3
(1H, C4H, J 2.8, J 1.6 Hz), 5.86 d (1H, HCO,
3J 2.8 Hz), 7.30 d (1H, HC=N, 3J 1.6 Hz), 7.36–7.41 m
(5H).
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant no.
08-03-00707-a) and of the Presidium of the Russian
Academy of Sciences (program “Theoretical and experi-
mental investigation of the nature of the chemical bond
and the mechanism of chemical reactions and
processes”).
As a result of a reaction of 0.132 g (1 mmol) of 1-methyl-
1-phenylcyclopropane (I) and 0.130 g (2 mmol) of NOCl
in 5 ml of SO2 for 2 h at –40°C after the standard workup
of the reaction mixture and the chromatographic isolation
on a column (SiO2, 40/100 μm, ethyl acetate–petroleum
ether, 1:3) we isolated 0.007 g (4%) of trans-3-methyl-
3-phenylacrylonitrile (XVIII), Rf 0.80. IR spectrum,
ν, cm–1: 2225 (CN). 1H NMR spectrum, δ, ppm: 2.46 d
REFERENCES
4
4
(3H, CH3, J 1.1 Hz), 5.61 q (1H, J 1.1 Hz), 7.38–
7.45 m (5HapOm.) [16]; 0.015 g (8%) of 3-phenyl-3-
chlorobutyronitrile (XVII), Rf 0.75. IR spectrum, ν,
1. Bondarenko, O.B., Gavrilova, A.Yu., Kazantseva, M.A.,
Tikhanushkina, V.N., Nifant’ev, E.E., Saginova, L.G., and
Zyk, N.V., Zh. Org. Khim., 2007, vol. 43, p. 566.
2. Bondarenko, O.B., Gavrilova, A.Yu., Kazantseva, M.A.,
Tikhanushkina, V.N., Nifant’ev, E.E., Saginova, L.G.,
Zyk, N.V., Zh. Org. Khim., 2006, vol. 42, p. 265.
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Zyk, N.V., and Zefirov, N.S., Izv. Akad. Nauk, Ser. Khim.,
2003, p. 741.
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1
cm–1: 2250 (CN). H NMR spectrum, δ, ppm: 2.09 s
2
(3H, CH3), 3.08 d (1H, CH2, J 16.7 Hz), 3.16 d (1H,
CH2, 2J 16.7 Hz), 7.29 d (1H, 3J 7.2 Hz), 7.34 m (2H),
3
7.51 d (2H, J 7.8 Hz); 0.129 g (80%) of 5-methyl-5-
phenylisoxazoline (IX), Rf 0.50. 1H NMR spectrum,
δ, ppm: 1.62 s (3H, CH3), 2.98 d.d (1H, CH2, 2J 17.5,
3J 1.8 Hz), 3.04 d.d (1H, CH2, 2J 17.5, 3J 1.8 Hz), 6.98 t
3
3
(1H, HC=N, J 1.8 Hz), 7.18 d (1H, J 7.7 Hz) 7.25 t
(2H, 3J 7.7 Hz) 7.32 d (2H, 3J 7.7 Hz) [17].
5. Bondarenko, O.B., Gavrilova,A.Yu., Saginova, L.G., and
Zyk, N.V., Zh. Org. Khim., 2003, 39, 1084.
As a result of a reaction of 0.132 g (1 mmol) of 1-methyl-
2-phenylcyclopropane (III) and 0.328 g (5 mmol) of
NOCl in 5 ml of SO2 for 3 h at–40°C after the standard
workup of the reaction mixture and the chromatographic
isolation on a column (SiO2, 40/100 μm, ethyl acetate–
petroleum ether, 1:3) we isolated 0.030 g (24%) of
cyclopropane III (100% trans-isomera), 0.080 g (50%)
of 3-methyl-5-phenyl-isoxazoline (XI-A), Rf 0.50.
1H NMR spectrum, δ, ppm: 2.01 t (3H, CH3, 4J 1.0 Hz),
6. Mizuno, K., Ichinose, N., Tamai, T., and Otsuji, Y., J. Org.
Chem., 1992, 57, 4669; Mochalov, S.S., Kuz’min, Ya.I.,
Fedotov, A.N., Trofimova, E.V., Gazzaeva, R.A., Shaba-
rov,Yu.S., and Zefirov, N.S., Zh. Org. Khim., 1998, 34, 1379.
7. Saginova, L.G., Mokhammad, Al’khamdan, and Petro-
syan, V.S., Vestn. MGU, Ser. Khim., 1999, 40, 46
8. Saginova, L.G., Kukhareva, I.L., Lebedev,A.T., and Shaba-
rov, Yu.S., Zh. Org. Khim., 1991, 27, 1852.
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Saginova, L.G., Tafeenko, V.A. and Shabarov, Yu.S., Zh.
Org. Khim., 1987, vol. 23, p. 1736.
2
3
4
2.89 d.d.q (1H, CH2, J 17.0, J 8.2, J 1.0 Hz), 3.34
d.d.q (1H, CH2, 2J 17.0, 3J 10.8, 4J 1.0 Hz), 5.54 d.d (1H,
3
3
HCO, J 10.8, J 8.2 Hz), 7.30–7.35 m (5H); 0.016 g
(10%) of 4-methyl-5-phenylisoxazoline (XI-B),
Rf 0.37. 1H NMR spectrum, δ, ppm: 1.35 d (3H, CH3,
10. Mochalov, S.S., Kosynkin, O.V., Yudin, I.D., Zavod-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 2 2009