4,5-Dihydroisoxazoles from arylcyclopropanes by reactions with nitrosyl chloride activated with sulfur trioxide

Full text of DOI:10.1023/A:1023964302707

778
Russian Chemical Bulletin, International Edition, Vol. 52, No. 3, p. 778, March, 2003
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,5ꢀDihydroisoxazoles from arylcyclopropanes
by reactions with nitrosyl chloride activated with sulfur trioxide
ꢀ
O. B. Bondarenko, A. Yu. Gavrilova, L. G. Saginova, N. V. Zyk, and N. S. Zefirov
Department of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119899 Moscow, Russian Federation.
Fax: +7 (095) 939 0290. Eꢀmail: bondarenko@org.chem.msu.ru
Modern organic synthesis needs convenient starting
ylene chloride (3×10 mL); the organic extracts were combined
and dried with sodium sulfate. Then the solvent was removed to
give a pure crystalline product (the yields are given under the
1
reagents such as, e.g., an dihydroisoxazole ring. On the
one hand, this ring is fairly resistant to various modificaꢀ
tions in side chains, while on the other hand, desirable
functions can be imparted by transforming the central
structure at the final step of the synthesis. For this reason,
a search for new reactions and reagents suitable for conꢀ
struction of this heterocycle itself still remains topical.
In the present work, we propose to synthesize 5ꢀarylꢀ
scheme). The NMR spectra and melting points of compounds
,6,7
2
a—h,j were identical with the literature data.3
5
ꢀ(4ꢀAcetylphenyl)ꢀ4,5ꢀdihydroisoxazole (2i) was obtained
from 4ꢀ(acetylphenyl)cyclopropane 1i (0.04 g, 0.25 mmol) and
NOCl•2SO (0.06 g, 0.25 mmol) in 15 mL of CH Cl . Chromaꢀ
3
2
2
tography on SiO in light petroleum—ethyl acetate (3 : 1) gave
2
the title compound (0.3 g, 62%) as colorless crystals, m.p. 55 °C,
Rf 0.24. Found (%): C, 69.73; H, 5.46. C11H11NO2. Calcuꢀ
4
1
,5ꢀdihydroisoxazoles by reactions of arylcyclopropanes
–
1
lated (%): C, 69.84; H, 5.29. IR (ν/cm ): 1685 (C=O), 1580,
with NOCl•2SO . Unlike previous nitrosating sysꢀ
3
1
tems,2 this complex makes it possible to obtain isoxazoꢀ
—4
1280, 820. H NMR (CDCl ), δ: 2.58 (s, 3 H, MeCO); 2.87
3
2
3
3
(
(
(
3
ddd, 1 H, CH , J = 17.5 Hz, J = 7.6 Hz, J = 1.8 Hz); 3.44
2
ddd, 1 H, CH , J = 17.5 Hz, J = 11.2 Hz, J = 1.8 Hz); 5.57
dd, 1 H, CHO, J = 11.2 Hz, J = 7.6 Hz); 7.21 (t, 1 H, CH=,
J = 1.8 Hz); 7.40 (d, 2 H, C H , J = 8.3 Hz); 7.94 (d, 2 H,
lines under mild conditions (CH Cl , 0 °C) in high yields
2
2
2
3
3
2
from arylcyclopropanes containing both donor and acꢀ
ceptor substituents in the aromatic ring.
3
3
3
6
4
3
13
C H , J = 8.3 Hz). C NMR (CDCl ), δ: 26.63, 43.81,
6
4
3
7
1
9.15 (CHO); 125.77, 128.80, 136.85, 145.31, 146.14 (C=N);
97.52 (C=O).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ33347)
and the Ministry of Education of the Russian Federation
(
the Program "Russian Universities", Project No. 990 879).
References
1
. G. Desimony and G. Faita, 16th Seminar on Organic Syntheꢀ
sis, Summer School "A. Corbella", Polo Ed. Chem., Milan, 1991.
R1
H
H
F
MeO
H
H
Br
R2
H
Ph
R3
H
H
H
H
H
Me
H
Yield (%)
95
a
b
c
d
e
f
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cyclic Chemistry, 16—19 February, 2002, Luxor—Egypt, 131, 40.
99
99
95
99
93
99
4ꢀFC H
6
4
4ꢀMeOC H
6
4
3
. Yu. S. Shabarov, L. G. Saginova, and R. A. Gazzaeva, Khim.
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Me
H
H
(
Engl. Transl.)].
g
h
i
I
H
H
H
H
H
H
99
62
85
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4ꢀMeCO
oꢀNO /pꢀNO (4 : 1)
j
2
2
6
. R. A. Gazzaeva, Yu. S. Shabarov, and L. G. Saginova, Khim.
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Synthesis of 4,5ꢀdihydroisoxazoles 2 from arylcyclopropanes
and NOCl•2SO3 (general procedure). An arylcyclopropane
1
(
(
Engl. Transl.)].
0.001 mol) in 2 mL of methylene chloride was added at 0 °C to
7
. L. G. Saginova, I. L. Kukhareva, A. T. Lebedev, and Yu. S.
Shabarov, Zh. Org. Khim., 1991, 27, 1852 [J. Org. Chem. USSR,
5
a suspension of NOCl•2SO3 (0.001 mol) in 10 mL of the same
solvent. The precipitate dissolved immediately to give a colored
solution. After 1 h (TLC), the reaction mixture was neutralized
with aqueous sodium carbonate and washed with water. The
products were extracted from the aqueous fractions with methꢀ
1
991, 27 (Engl. Transl.)].
Received October 7, 2002;
in revised form December 11, 2002
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 741—742, March, 2003.
066ꢀ5285/03/5203ꢀ778 $25.00 © 2003 Plenum Publishing Corporation
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