NITROPYRIDINES: X.
1833
was evaporated under reduced pressure. Yield
0.142 g (42%).
142.39 (C6), 162.99 (C2), 168.57 (=COH). Found, %:
C 64.68; H 4.12; N 11.65. C13H10N2O3. Calculated, %:
C 64.46; H 4.16; N 11.56.
c. Calcined potassium hydroxide, 1.52 g (2.71 mol),
was added to a solution of 0.540 g (2.62 mmol) of
nitropyridine IVc in 15.6 ml of benzene, and the mix-
ture was heated for 3 h under reflux in a stream of
argon. The mixture was filtered, the filtrate was evap-
orated, and the residue was purified by column chro-
matography. Yield 0.06 g (15%).
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 07-03-00783-a).
REFERENCES
1. Sagitullina, G.P., Garkushenko, A.K., Glizdinskaya, L.V.,
Yuldashev, F.A., Vorontsova, M.A., and Sagitullin, R.S.,
Khim. Geterotsikl. Soedin., 2010, p. 1551.
1-(5-Nitropyridin-2-yl)ethanone (VI). 2-Ethynyl-
5-nitropyridine (V), 0.1 g (0.68 mmol), was dissolved
in 3 ml of 70% aqueous acetone, 0.066 ml (1.36 mmol)
of concentrated sulfuric acid and 0.217 g (0.68 mmol)
of Hg(OAc)2 were added, and the mixture was stirred
for 2 h on heating on a water bath. The mixture was
cooled, neutralized by adding a saturated solution of
NaHCO3, and extracted with diethyl ether, the extract
was dried over anhydrous MgSO4 and evaporated, and
the residue was purified by chromatography on silica
gel (100–160 μm) using chloroform–ethyl acetate
(9:1) as eluent. Yield 0.05 g (48%), mp 87–88°C (from
petroleum ether, bp 40–70°C) [32]. 1H NMR spectrum
(CDCl3), δ, ppm: 2.79 s (3H, Me), 8.23 d (1H, 3-H,
3J = 8.5 Hz), 8.62 d.d (1H, 4-H, 3J = 8.5, 4J = 2.5 Hz),
9.49 d (1H, 6-H, 4J = 2.5 Hz).
2. Rusinov, V.L. and Chupakhin, O.N., Nitroaziny (Nitro
Azines), Novosibirsk: Nauka, 1991.
3. Caldwell, W.T., Tyson, F.T., and Lauer, L., J. Am. Chem.
Soc., 1944, vol. 66, p. 1479.
4. Parker, E.D. and Shive, W., J. Am. Chem. Soc., 1947,
vol. 69, p. 63.
5. Brown, E.V., J. Am. Chem. Soc., 1954, vol. 76, p. 3168.
6. Brown, E.V. and Burke, H.T., J. Am. Chem. Soc., 1955,
vol. 77, p. 6053.
7. Mariella, R.P., Callahan, J.J., and Jibril, A.O., J. Org.
Chem., 1955, vol. 20, p. 1721.
8. Butler, R.N., Chem. Rev., 1975, vol. 75, p. 241.
9. Kato, Y., Okada, S., Tomimoto, K., and Mase, T., Tetra-
hedron Lett., 2001, vol. 42, p. 4849.
10. Thacher, S.M., Vasudevan, J., Tsang, K.-Y., Nagpal, S.,
and Chandraratna, R.A.S., J. Med. Chem., 2001, vol. 44,
p. 281.
11. Gomtsyan, A., Didomenico, S., Lee, C.-H., Matulen-
ko, M.A., Kim, K., Kowaluk, E.A., Wismer, C.T.,
Mikusa, J., Yu, H., Kohlhaas, K., Jarvis, M.F., and
Bhagwat, S.S., J. Med. Chem., 2002, vol. 45, p. 3639.
12. Gasparani, F., Lingenhöhl, K., Stoehr, N., Flor, P.J.,
Heinrich, M., Vranesica, I., Kuhna, R., Biollaz, M.,
Allgeier, H., Heckendorn, R., Urwgler, S., Varney, M.A.,
Johnson, E.C., Hess, S.D., Rao, S.P., Sacaan, A.J.,
Santori, E.M., and Velicelebi, G., Neuropharmacology,
1999, vol. 38, p. 1493.
13. Karpov, A.S., Rominger, F., and Műller, T.J.J., J. Org.
Chem., 2003, vol. 68, p. 1503.
14. Kawano, T., Kato, T., Du, C.-X., and Ueda, I., Tetra-
hedron Lett., 2002, vol. 43, p. 6697.
15. Akhtaruzzaman, M., Tomura, M., Zaman, M.B., Nishi-
da, J., and Yamashita, Y., J. Org. Chem., 2002, vol. 67,
p. 7813.
16. Gui, T.-L., Jin, S.-H., Park, J.-W., Lim, K.-T.,
Kim, S.-Y., and Gal, Y.-S., Mater. Sci. Eng. C., 2004,
vol. 24, p. 217.
17. Tour, J.M., Rawlett, A.M., Kozaki, M., Yao, Y.,
Jagessar, R.C., Dirk, S.M., Price, D.W., Reed, M.A.,
Zhou, C.-W., Chen, J., Wang, W., and Campbell, I.,
Chem. Eur. J., 2001, vol. 7, p. 5118.
2-(5-Nitropyridin-2-yl)-1-phenylethanone (VII)
(a mixture of ketone and enol tautomers at a ratio of
1:3). Nitropyridine IVd, 0.35 g (1.14 mmol), was
dissolved in 2.5 ml of 65% sulfuric acid, 0.364 g
(1.14 mmol) of Hg(OAc)2 was added, and the mixture
was stirred for 2 h at 100°C. The mixture was cooled
and poured onto ice, and the precipitate was filtered off
and purified by chromatography on silica gel (100–
160 μm) using benzene–ethyl acetate (9:1) as eluent.
Yield 0.124 g (45%), mp 148–149°C (from ethanol).
IR spectrum, ν, cm–1: in chloroform: 3685 (OH); 1626
(C=O); 1561, 1337 (NO2); ATR: 1624 (C=O); 1562,
1
1332 (NO2). H NMR spectrum (CDCl3), δ, ppm:
ketone tautomer A: 4.65 s (2H, CH2), 7.39–7.65 m
(3H, C6H5), 7.54 d (1H, 3-H, 3J = 8.7 Hz), 8.02–8.11 m
3
4
(2H, C6H5), 8.46 d.d (1H, 4-H, J = 8.7, J = 2.6 Hz),
4
9.39 d (1H, 6-H, J = 2.6 Hz); enol tautomer B: 6.24 s
(1H, =CH), 7.15 d (1H, 3-H, 3J = 9.0 Hz), 7.39–7.65 m
(3H, C6H5), 7.82–7.95 m (2H, C6H5), 8.35 d.d (1H,
3
4
4
4-H, J = 9.0, J = 2.5 Hz), 9.20 d (1H, 6-H, J =
2.5 Hz). 13C NMR spectrum (APT, CDCl3), δC, ppm:
tautomer A: 47.98 (CH2), 124.69 (C3), 128.61 (Cm),
128.82 (Co), 131.40 (C4), 133.81 (Cp), 144.84 (C6);
tautomer B: 94.65 (CH=), 121.03 (C3), 126.06 (Cm),
128.56 (Co), 130.80 (Cp), 131.58 (C4), 134.92 (Ci),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 12 2010