Russian Journal of Organic Chemistry, Vol. 39, No. 9, 2003, pp. 1362 1363. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 9, 2003,
p. 1434.
Original Russian Text Copyright
2003 by Orlov, Kotov, Ganzha.
SHORT
COMMUNICATIONS
Reaction of 4-Nitrochlorobenzene
with 2-Methoxyphenylacetonitrile
V. Yu. Orlov, A. D. Kotov, and V. V. Ganzha
Demidov Yaroslavl State University, ul. Sovetskaya 14, Yaroslavl, 150000 Russia
e-mail: orl@bio.uniyar.ac.ru
Received May 6, 2003
The reaction of 4-substituted nitroarenes with aryl-
zene (I). The mixture was stirred for 10 h at room
temperature and poured into 500 ml of water, and the
precipitate was filtered off, dried, and recrystallized
from a 1:1 mixture of alcohol with acetone. We thus
isolated 0.7 g (21%) of compound III. To the filtrate
we added 40 ml of 20% hydrochloric acid. The pre-
cipitate was filtered off, dried, and washed with
a small amount of cold acetone to obtain 1.6 g (51%)
of compound IV.
acetonitrile in alcoholic medium in the presence of
excess alkali provides a convenient method for the
preparation of 2,1-benzisoxazoles which are versatile
synthons and intermediate products in manufacture of
monomers and bioactive substances (tranquilizers)
[1 3]. We have found that the reaction of 4-nitro-
chlorobenzene (I) with 2-methoxyphenylacetonitrile
(II) gives a mixture of methoxy and hydroxy deriva-
tives III and IV.
5-Chloro-3-(2-methoxyphenyl)-2,1-benzisoxazole
(III). mp 173 174 C; published data [4]: mp 69
1
70 C. IR spectrum, , cm : 1638 (C N), 1275
(N O). 1H NMR spectrum (DMSO-d6), , ppm:
8.22 d (1H, 4-H), 7.77 d.d (1H, 6-H), 7.29 d (1H,
7-H), 7.39 m (1H, Harom), 7.83 7.91 m (3H, Harom),
3.89 s (3H, OCH3). Mass spectrum, m/z (Irel, %): 259
[M]+ (65), 244 (74), 228 (100), 200 (30), 174 (10),
164 (28), 153 (10), 75 (20), 63 (15). Found, %:
C 64.66; H 3.80; N 5.45. C14H10ClNO2. Calculated,
%: C 64.75; H 3.88; N 5.39.
5-Chloro-3-(2-hydroxyphenyl)-2,1-benzisoxazole
1
(IV). mp >250 C. IR spectrum, , cm : 3275 (OH).
1H NMR spectrum (DMSO-d6), , ppm: 8.21 d (1H,
4-H), 7.73 d.d (1H, 6-H), 8.23 d (1H, 7-H), 7.28 m
(1H, C6H4), 7.73 7.89 m (3H, C6H4), 11.4 s (1H,
OH). Mass spectrum, m/z (Irel, %): 244 [M H]+ (42),
228 (100), 200 (50), 174 (10), 164 (50), 153 (10),
138 (20), 124 (12), 110 (12), 101 (19), 83 (19), 74
(48), 63 (34), 50 (60), 39 (22). Found, %: C 63.47;
H 3.15; N 5.14. C13H8ClNO2. Calculated, %: C 63.75;
H 3.28; N 5.70.
The major reaction product is previously unknown
5-chloro-3-(2-hydroxyphenyl)-2,1-benzisoxazole (IV)
rather than 5-chloro-3-(2-methoxyphenyl)-2,1-benz-
isoxazole (III). By special experiments we showed
that replacement of the methoxy group occurs at
an intermediate stage of the process, for compound III
was not converted into IV in a mixture of isopropyl
alcohol and sodium hydroxide.
1
The H NMR spectra were recorded on a Bruker
AC-300SF spectrometer (300.13 MHz) in DMSO-d6
using HMDS as internal reference. The IR spectra
were measured on a Specord M-80 instrument from
samples dispersed in mineral oil. The elemental
To a mixture of 50 ml of isopropyl alcohol and
8 g (0.2 mol) of finely powdered sodium hydroxide
we added 2.2 g (15 mmol) of 2-methoxyphenylaceto-
nitrile (II) and 2 g (12.7 mmol) of 4-nitrochloroben-
1070-4280/03/3909-1362$25.00 2003 MAIK Nauka/Interperiodica
Orlov
