REACTIONS OF ISOMERIC ARYLCHLOROPYRUVATES AND GLYCIDATES WITH HYDRAZINES
701
REFERENCES
N 18.18. Compound VIIIb was also obtained from
pyrazolinedione XIV in a 91% yield.
1. Kitaev, Yu.P and Buzykin, B.N., Gidrazony (Hydrazons),
Kost, A.N., Ed., Moscow: Nauka, 1974, vol. 262, p. 370.
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p. 6026.
3. Pritzkow, W., Z. Chem., 1970, vol. 10, p. 330.
4. Hassner, A. and Catsonlaccos, P., Chem. Commun., 1967,
p. 121.
2-(4'-Methoxycarbonyl-5'-phenyl)thiazolyl-3-
oxo-4-(4'-methoxycarbonyl-5'-phenyl)thiazolyl-
hydrazono-5-phenylpyrazoline (XII) was likewise
prepared from 2.8 g (0.01 mol) of 2-hydrazinothiazole
(X) and 0.64 g (0.03 mol) of chloropyruvate Ia. Yield
1
67%, mp 263265°C (MeCN). IR spectrum, n, cm :
3180 br.s, 30802500 st, 1720, 1670, 1550, 1520, 1480,
1460, 1380, 1290, 1260, 1200, 1150, 900. 1H NMR spec-
trum (250 MHz), d, ppm: 3.75 s (3H, CH3CO2), 3.79 s
(3H, CH3CO2), 7.518.17 br.s (15H, 3C6H4), 9.06 br.s
(1H, NH). Found, %: C 60.04; H 3.41; N 13.78; S 10.21.
C31H22N6O5S2. Calculated, %: C 59.81; H 3.53; N 13.50;
S 10.30.
5. Simon, H., Moldenhauer, W., and Kraus, A., Chem. Ber.,
1969, vol. 102, p. 2777.
6. Stickler, W.C. and Hoffman, W.C., Angew. Chem., 1970,
vol. 82, p. 254.
7. Roeding, A. and Wenzel, W., Lieb. Ann., 1969, vol. 728,
p. 1.
8. Wharton, P.S., Dunug, S., and Krebs, L.S., J. Org. Chem.,
1964, vol. 29, p. 958.
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vol. 52, p. 4033.
10. Shvaika, O.P. andArtemov, V.N., Usp. Khim., 1972, vol. 10,
p. 1788.
11. Slagel, R.S., J. Org. Chem., 1968, vol. 33, p. 1374.
12. Europe Patent 52333, 1996; Chem. Abstr., 1997, 144854g.
13. Shkineva, T.G., Dalinger, I.L., and Shevelev, S.A., Khim.
Geterotsikl. Soed., 1995, p. 579.
14. Wolfrom, M.L. and Wood, H.B., J. Am. Chem. Soc., 1951,
vol. 73, p. 2933.
2-(4'-Methoxycarbonyl-5'-phenyl)thiazolyl-3-
oxo-4-(4'-methoxycarbonyl-5'-phenyl)-N-thiazolyl-
N-acetylhydrazono-5-phenylpyrazoline (XIII).
A mixture of 2.8 g (0.01 mol) of 2-hydrazinothiazole (X)
and 64 g (0.03 mol) of chloropyruvate Ia was heated at
reflux in 15 ml of acetic acid for 10 h. On cooling the
solution the separated precipitate was filtered off, dried,
and recrystallized. Yield 61%, mp 259260°C (MeCN).
1
IR spectrum, n, cm : 1720, 1715, 1675, 1545, 1520, 1480,
1
1465, 1380, 1295, 1260, 1200, 1145, 910. H NMR
spectrum (250 MHz), d, ppm: 3.71 s (3H, CH3CO2),
3.76 s (3H, CH3CO2), 2.13 br.s (3H, CH3CO), 7.45
8.12 m (15H, 3C6H5). Found, %: C 59.43; H 3.87;
N 12.68; S 9.59. C33H24N6O6S2. Calculated, %: C 59.65;
H 3.61; N 12.65; S 9.65.
15. Patai, S., The Chemistry of the Hygrazo, Azo, and Azoxy
Groups, part I, 1975, p. 154.
16. Strakov, A.Ya., Petrova, M.V., Strakova, I.A., and Lakho-
vich, O.F., Khim. Geterotsikl. Soed., 1995, p. 336.
17. Mamedov, V.A., Valeeva, V.N., Antokhina, L.A., and
Nuretdinov, I.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1991,
p. 1422.
18. Mamedov, V.A., Berdnikov, E.A., Valeeva, V.N., Ismaev, I.E.,
Rizvanov, I.Kh., Antokhina, L.A., Nuretdinov, I.A., and
Chernov, P.P., Izv. Akad. Nauk, Ser. Khim., 1993, p. 1962.
19. Mustakimova, L.V., Mamedov, V.A., and Levin, Ya.A.,
Khimiya i primenenie fosfor-, sera-, i kremniiorgani-
cheskikh soedinenii (Chemistry and Application of
Phosphor, Sulfur, and Silicon Containing Compounds),
St. Petersburg, 1998, p. 107.
20. Singh, S.P., Kodai, D.R., Dhindsa, G.S., and Sawhney, S.N.,
Indian J. Chem., 1982, vol. 21B, p. 30.
21. Singh, S.P., Sehgal, S., Tarar, L.G., and Dhawan, S.N., Indian
J. Chem., 1990, vol. 29B, p. 310.
22. Mahajan, M.P., Sondhi, S.M., and Ralhan, N.K., Austral. J.
Chem., 1977, vol. 30, p. 2053.
23. Minkin, V.I., Olekhnovich, L.P., and Zhdanov, Yu.A.,
2-Phenyl-5-(3-nitrophenyl)-3,4-pyrazolinedione
(XIV). A mixture of 0.02 mol of chloroglycidate II and
0.02 mol of phenylhydrazine was stirred in 5 ml of
methanol at room temperature for 3 h, then the solution
was heated to boiling, and the reaction was continued at
reflux for 5 h more. On cooling the separated precipitate
was filtered off, dried, and recrystallized from a 5%
methanol solution of DMSO.
Reaction of pyrazolinedione XIV with phenyl-
hydrazine. A mixture of 1.5 g (0.005 mol) of
pyrazolinedione XIV and 0.64 g (0.006 mol) of
phenylhydrazine was heated at reflux in 10 ml of methanol
for 3 h. On cooling the solution the separated precipitate
was filtered off and recrystallized.
The study was carried out under the financial support
of the Russian Foundation of Basic Research (grants nos.
03-03-32865 and 02-03-32280) and NIOKR Foundation
of Tatarstan Republic (contract 07-7.4-39/ 2002 (T).
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005