TRANSFORMATIONS OF 3-NITROPYRIDIN-4(1H)-ONE
125
samples prepared as described above in a and b. Its IR
and H NMR spectra coincided with those of the hy-
drazinolysis products of nitropyridines Ia and Ib.
2. Yutilov, Yu.M. and Smolyar, N.N., Khim. Geterotsikl.
Soedin., 1984, p. 132; Yutilov, Yu.M. and Smo-
lyar, N.N., Zh. Org. Khim., 1986, vol. 22, p. 1793;
Yutilov, Yu.M., Smolyar, N.N., and Gres’ko, S.V., Russ.
J. Org. Chem., 1995, vol. 31, p. 273; Yutilov, Yu.M. and
Svertilova, I.A., Russ. J. Org. Chem., 1999, vol. 35,
p. 583; Gres’ko, S.V., Smolyar, N.N., and Yuti-
lov, Yu.M., Ukr. Khim. Zh., 2003, vol. 69, p. 110;
Yutilov, Yu.M., Smolyar, N.N., Eres’ko, A.B., and
Gres’ko, S.V., Russ. J. Org. Chem., 2004, vol. 40,
p. 1015; Smolyar, N.N., Lomov, D.A., and Yuti-
lov, Yu.M., Russ. J. Org. Chem., 2007, vol. 43, p. 897.
1
1
H-Pyrazole-3-carboxylic acid (IV). Potassium
permanganate, 9.0 g (5.7 mmol), was added in portions
to a solution of 1.2 g (9.6 mmol) of hydrazone II in
6
8 ml of water, heated to 85–90°C, and the mixture
was kept for 2 h at that temperature. The precipitate of
MnO was filtered off and washed with several portions
2
of hot water. The filtrate was combined with the wash-
ings, evaporated to 1/3 of the initial volume, cooled,
and acidified with concentrated hydrochloric acid, and
the precipitate was filtered off and dried. Yield 0.75 g
3. Smolyar, N.N. and Yutilov, Yu.M., Russ. J. Org. Chem.,
2008, vol. 44, p. 274.
(
[
(
70%), mp 214–216°C (from ethanol); published data
10]: mp 216–217°C. H NMR spectrum, δ, ppm: 7.33 d
1H, 4-H, J = 2.2 Hz), 8.25 d (1H, 5-H, J = 2.2 Hz).
4. Yutilov, Yu.M. and Smolyar, N.N., Khim. Geterotsikl.
Soedin., 1985, p. 1686.
5. Smolyar, N.N. and Yutilov, Yu.M., Russ. J. Org. Chem.,
1
2
008, vol. 44, p. 1205.
Acetophenone azine (XI). a. A mixture of 1.81 g
12 mmol) of α-nitroethylbenzene (VIII) and 6.0 ml of
6
7
8
9
. Yutilov, Yu.M. and Smolyar, N.N., Khim. Geterotsikl.
Soedin., 1986, p. 1136.
. Smolyar, N.N. and Yutilov, Yu.M., Russ. J. Org. Chem.,
(
hydrazine hydrate was heated for 4–5 h at 130–140°C.
Excess hydrazine hydrate was distilled in a vacuum
under nitrogen. The residue was ground with propan-2-
ol, and the precipitate was filtered off and dried. Yield
2
008, vol. 44, p. 1640.
. Yutilov, Yu.M. and Smolyar, N.N., Zh. Org. Khim.,
994, vol. 30, p. 1569.
1
1
.32 g (93%), mp 122°C (from propan-2-ol); published
1
. Fries, R.W., Bohlken, D.P., and Plapp, B.V., J. Med.
Chem., 1979, vol. 22, p. 356.
data [16]: mp 124°C. H NMR spectrum, δ, ppm:
.34 s (6H, CH ), 7.49–7.54 m (5H, C H ), 7.96–8.04 m
2
(
3
6
5
1
0. Jones, R.G., J. Am. Chem. Soc., 1949, vol. 71, p. 3994.
11. Letsinger, R.L. and Collat, R., J. Am. Chem. Soc., 1952,
5H, C H ). Found, %: C 81.12; H 6.76; N 11.70.
6 5
C H N . Calculated, %: C 81.32; H 6.82; N 11.85.
1
6
16
2
vol. 74, p. 621.
b. A mixture of 1.62 g (12 mmol) of acetophenone
1
1
2. Sohn, G., Noris, R.H., and Pugh, W., J. Chem. Soc.,
955, p. 1753.
oxime (X) and 6.0 ml of hydrazine hydrate was heated
for 4 h at 130–140°C. The product was isolated as
described above in a. Yield 1.42 g (~100%), mp 123°C
(
(
1
3. Koenigs, E. and Freter, K., Chem. Ber., 1924, vol. 57,
p. 1187; Gruber, W., Can. J. Chem., 1953, vol. 31,
p. 1181; Ahmad, Y. and Hey, D.H., J. Chem. Soc., 1954,
p. 4516.
1
from propan-2-ol). H NMR spectrum, δ, ppm: 2.32 s
6H, CH ), 7.49–7.54 m (5H, C H ), 7.96–8.04 m (5H,
3
6
5
C H ). Samples of XI prepared as described in a and b
showed no depression of the melting point on mixing.
6
5
1
1
4. Spravochnik khimika (Chemist’s Handbook), Leningrad:
Khimiya, 1979, vol. 2, p. 28.
5. Marvel, C.S. and Jenkins, R.L., Organic Syntheses,
Blatt, A.H., Ed., New York: Wiley, 1941, collect. vol. 1,
p. 347.
16. Cohen, S.G., Groszos, S.J., and Sparrov, D.B., J. Am.
Chem. Soc., 1950, vol. 72, p. 3947.
REFERENCES
1
. Yutilov, Yu.M. and Svertilova, I.A., Khim. Geterotsikl.
Soedin., 1982, p. 705; Yutilov, Yu.M., Adv. Heterocycl.
Chem., 2005, vol. 89, p. 169.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 1 2010