Russian Journal of Organic Chemistry, Vol. 39, No. 11, 2003, pp. 1674 1675. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 11, 2003,
pp. 1743 1744.
Original Russian Text Copyright
2003 Orlov, Kotov, Ganzha, Mironov.
SHORT
COMMUNICATIONS
Synthesis of 9-Bromo-3-methoxydibenzo[c,f][1,2]oxazepine-
1-carbonitrile
1
V. Yu. Orlov, A. D. Kotov, V. V. Ganzha, and G. S. Mironov
Demidov Yaroslavl State University, Yaroslavl, 150000 Russia
Received February 7, 2003
Reactions of 4-substituted nitroarenes with acyl-
acetonitriles in alcohol in the presence of excess alkali
1, 2] is a convenient procedure for preparation of
.1-benzisoxazoles (anthranils), synthons for the fine
organic synthesis, semiproducts in monomers produc-
tion [3], and bioactive substances [4].
(I) and 1.6 ml (11.9 mmol) of nitrile II. The reaction
mixture was stirred for 15 h at 20 C, and then poured
into 500 ml of 3% HCl mixed with ice. The separated
precipitate was filtered off and dried in air to get
[
2
2
.8 g of dry mixture of the reaction products.
-Bromo-3-(4-methoxyphenyl)-2,1-benzisoxazole
III). The dry residue obtained above was boiled in
-propanol and filtered hot. The light-orange crystals
5
We found that the reaction of 4-nitrobromobenzene
I) with 4-methoxyphenylacetonitrile (II) in
(
2
(
2
-propanol in the presence of excess sodium hydr-
precipitated from the filtrate on cooling were filtered
off, washed with ethanol, and dried in air for 6 h. We
oxide (molar ratio of the reagents 1: 1.2 : 15 respec-
tively) afforded a mixture of products.
obtained 1.9 g (63%) of compound III, mp 128
1
1
(
,
29 C (134 135 C [1]). IR spectrum, , cm : 1638
1
C=N), 1275 (N O). H NMR spectrum (DMSO-d ),
ppm: 8.31 d (1H, H ), 7.36 d.d (1H, H ), 7.52 d
6
4
6
7
(
1H, H ), 7.96 d (2H, C H ), 7.17 d (2H, C H ),
6 4 6 4
3
3
.88 s (3H, OCH ). Mass spectrum, m/z (I , %):
3 rel
03 [M] (60), 288 (20), 260 (60), 224 (40), 153
+
(
100), 107 (20), 92 (90), 77 (90), 63 (80). Found, %:
C 55.10; H 3.15; N 4.22. C H BrNO . Calculated,
1
4
10
2
%
: C 55.29; H 3.31; N 4.61.
-Bromo-3-methoxydibenzo[c,f][1,2]oxazepine-
1-carbonitrile (IV). The residue retained on the
9
1
filter after filtration of the hot solution in 2-propanol
was crushed into powder and carefully washed on
a filter with boiling 2-propanol with benzene added,
then it was dried in air for 6 h. We obtained 0.3 g
(9.2%) of bright-red compound, mp 233 234 C. IR
Alongside the main reaction product, 5-bromo-3-
4-methoxyphenyl)-2,1-benzisoxazole (III) (synthesiz-
ed in [1] for the first time), was isolated as an
individual compound previously unknown 9-bromo-3-
methoxydibenzo[c,f][1,2]oxazepine-11-carbonitrile
IV). No mention of compound IV was also in the
other publication dealing with the reactions of this
type [2].
(
1
1
spectrum, , cm : 2219 (C N). H NMR spectrum
3
(
(DMSO-d ), , ppm: 8.62 d (1H, H ), 8.37 d (1H,
6
4
6
1
7
H ), 8.25 d.d (1H, H ), 7.95 d (2H, H ,H ), 7.55 d.d
2
(
(
(
1H, H ), 4.10 s (3H, OCH ). Mass spectrum, m/z
Irel, %): 328 [M] (100), 312 (40), 298 (20), 283
30), 269 (30), 190 (45), 178 (50), 163 (30), 151
3
+
Reaction of 4-nitrobromobenzene (I) with
-methoxyphenylacetonitrile (II). To a mixture of
0 ml of 2-propanol and 6 g (150 mmol) of fine
powder of sodium hydroxide was added at room
temperature 2 g (9.9 mmol) of 4-nitrobromobenzene
4
5
(40), 113 (30), 74 (30), 63 (20), 50 (20), 40 (40).
Found, %: C 54.47; H 2.35; N 8.24. C H BrN O .
1
5
9
2
2
Calculated, %: C 54.74; H 2.75; N 8.51.
1
070-4280/03/3911-1674$25.00 2003 MAIK Nauka/Interperiodica
Orlov
