ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 8, pp. 1248-1249. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó V.V. Ganzha, A.D. Kotov, V.G. Sokolov, V.Yu. Orlov, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42,
No. 8, pp. 1263-1264.
SHORT
COMMUNICATIONS
Direct Amination of 5-Halo-3-phenyl-2,1-benzisoxazoles
V.V. Ganzha,A.D. Kotov, V.G. Sokolov, and V.Yu. Orlov
Demidov Yaroslavskii State University, Yaroslavl, 150000 Russia
e-mail: kot@bio.uniyar.ac.ru
Received February 1, 2006
DOI: 10.1134/S107042800608029X
oxide (catalyst) [3]. We established that under these
conditions 5-halo-3-phenyl-2,1-benzisoxazoles IIIa and
IIIb obtained from 4-halonitrobenzenes Ia and Ib and
a phenylacetonitrile (II) were converted into 3-(4-amino-
phenyl)-5-halo-2,1-benzisoxazoles IVa and IVb.
2,1-Benzisoxazoles are multipurpose synthons [1],
therefore their functionalization, in particular, an
introduction of an amino group, extends the bank of initial
compounds for the combinatorial chemistry.Aconvenient
procedure for preparation of 5-R-3-aryl-2,1-benzisox-
azoles consists in the reaction of 4-substituted arenas with
arylacetonitriles in alcohol in the presence of excess alkali
[2]. The attempts to build up the target structures from
initial compounds containing an amino group meet some
difficulties.Adirect amination of alkylbenzenes and aryl
halides conjugate with sulfonation occurs in a system
hydroxylamine sulfateconcn. H2SO4vanadium(V)
The method we developed for the synthesis of 5-R-3-
aryl-2,1-benzisoxazoles amino derivatives is advantageous
compared to the other procedures for it is a simple
preparative process giving a high yield of the target
product.
3-(4-Aminophenyl)-5-chloro-2,1-benzisoxazole
(IVa). To a solution of 5 mg (0.026 mmol) of vanadium(V)
oxide in 20 ml of hot concn. H2SO4 was aded 0.4 g
(4.35 mmol) of hydroxylamine sulfate, the mixture was
heated to 120°C, then 1 g (4.35 mmol) of compound IIIa
was added thereto. The reaction mixture was heated for
6 h at 120°C, then cooled and poured into 300 ml of water.
The separated precipitate was filtered off, dried, and
recrystallized from 50 ml of a mixture 2-propanol
benzene, 3:1. Yield 0.9 g (85%), brown lustrous plates,
&1
12
+ &
ꢀ
;
, ꢁꢂ,E
,,
1
mp >310°C. IR spectrum, cm : 3504, 3376 (NH2).
1
1H NMR spectrum, d, ppm: 8.15 d (1H, H4), 7.92 d (2H,
H2', H6'), 7.74 d (1H, H7), 7.38 d.d (1H, H6), 6.94 d (2H,
H3', H5'), 6.3 br.s (2H, NH2). Mass spectrum, m/z (Irel,
%): 244 [M]+ (100), 209 [M Cl]+ (97), 181 (58),
154 (20), 92 (27), 77 (19), 65 (72). Found, %: C 63.57;
H 3.35; N 11.14. C13H9ClN2O. Calculated, %: C 63.82;
H 3.71; N 11.45. M 244.67.
2
Lꢀ3U2+ 1D2+
,,, ꢁꢂ,,,E
1
2
3-(4-Aminophenyl)-5-bromo-2,1-benzisoxazole
+ 62 9 2
(IVb) was prepared similarly to compound IVa. Yield
1+ 2+ꢁꢂꢃꢄ+ 62
1
81%, mp >310°C. H NMR spectrum, d, ppm: 8.29 d
(1H, H4), 7.86 d (2H, H2', H6'), 7.61 d (1H, H7), 7.46 d.d
(1H, H6), 6.83 d (2H, H3', H5'), 5.3 br.s (2H, NH2). Mass
spectrum, m/z (Irel , %): 288 [M]+ (54), 209 [M Br]+
(95), 181 (63), 166 (65), 154 (31), 92 (49), 77 (100),
;
1+
,9 ꢁꢂ,9E
X = Cl (a), Br (b).
1248
Ganzha
