ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 2, pp. 312−313. © ©Pleiades Publishing, Ltd., 2009.
Original Russian Text © ©I.A. Shevtsova, A.G. Tyrkov, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 2, pp. 321−322.
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Reaction of 2,2-Dinitro-2-(3-phenyl-1,2,4-oxadiazol-5-l)acetonitrile
with Substituted PhenylAzides
I. A. Shevtsova andA. G. Tyrkov
Astrakhan State University, Astrakhan, 414000 Russia
e-mail: tyrkov@rambler.ru
Received November 9, 2007
DOI: 10.1134/S1070428009020250
The reaction of diazomethane with 2,2-dinitro-2-(3-
phenyl-1,2,4-oxadiazol-5-yl)acetonitrile (I) proceeded
under mild conditions and led to the formation of products
of 1,3-dipolar cycloaddition, N-methylated isomeric 1,2,3-
triazol-4-yl-(3-phenyl-1,2,4-oxadiazol-5-yl)dinitro-
methanes [1].
characteristics with the published data. In the IR spectra
of compounds VI and VII absorption bands are observed
of gem-dinitromethyl group at 1555 (ν ) and 1280 (ν )
as
s
–1
and of C=N bond at 1635 cm . The CN group in 1,2,4-
–1 1
oxadiazol VIII gave rise to a band at 2250 cm . H NMR
spectra of compounds VI–VIII are characterized by the
presence of multiplet proton signals in the region of aryl
ring at 6.95–8.15 ppm
In contrast the reaction of the substituted dinitroaceto-
nitrile I with phenyl azide (II) proceeded at heating and
resulted in N-(dinitromethylene)aniline (V) and 3-phenyl-
Synthesis of compound I was performed by procedure
[1], of aryl azides II–IV, by procedure [3].
5
-cyano-1,2,4-oxadiazole (VIII) (see the scheme). The
cyano group at this conversion of compound I lost the
quality of a dipolarophile.
Reaction of 2,2-dinitro-2-(3-phenyl-1,2,4-oxa-
diazol-5-yl)acetonitrile (I) with aryl azides II–IV. To
a solution of 10 mmol of compound I in 20 ml of chloro-
form was added at 25°C 10 mmol of aryl azide II–IV in
Likewise behaved 4-tolyl azide (III) and 4-nitrophenyl
azide (IV) in the reaction with compound I.
3
0 ml of the same solvent. The reaction mixture was
It is presumable that in the elimination of nitrogen from
aryl azides II–IV at the thermolysis the corresponding
nitrenes were generated [2] which reacting at the
electron-deficient carbon atom of the dinitroacetonitrile
fragment of compound I followed by the elimination of
nitrogen-containing fragments undergo stabilization into
sterically less loaded compounds V–VII and the decom-
position product VIII. The structure of compounds VI–
heated at reflux for 5 h, the solution was evaporated in
a vacuum, and the residue was subjected to chromato-
graphy on a column (500 × 10 mm) packed with Silicagel
1
00/400μ using Trappe set of eluents. Eluent for com-
pounds V–VII was benzene, for compoundVIII, ethyl ether.
N-(Dinitromethylene)aniline (V). Yield 28%, mp
7°C [4].
9
1
VIII were established from the IR and H NMR spectra,
and that of compound V, by comparison the physical
N-(Dinitromethylene)-4-methylaniline (VI). Yield
–1
32%, mp 112–113°C. IR spectrum, ν, cm : 1555, 1280
Scheme.
O
N
C(NO ) CN
O
N
CN
2
2
Δ
+
RC H N
6 4 3
RC H N C(NO ) +
6 4 2 2
N
CHCl3
N
Ph
I
Ph
VIII
_
_
II IV
V VII
R = H (II, V), 4-Me (III,VI), 4-NO (IV,VII).
2
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Shevtsova
