Abstract
The reaction of β-diketones with 2-unsubstituted thiosemicarbazides leads to the formation of the corresponding 1-thiocarbamoyl-5-hydroxy-2-pyrazolines, which readily undergo aromatization to give pyrazoles, while the reaction of benzoylacetaldehyde leads to the formation of the corresponding hydrazone. Acetylacetone 2-methyl- and 2,4-dimethylthiosemicarbazones are inclined to undergo tautomerization and, depending on the conditions, can exist in enehydrazine, hydrazone, 1,2,4-triazoline, and 1,3,4-thiadiazoline forms or mixtures of these forms. Upon heating these substances are converted to mixtures of the 1,3,5-trimethylpyrazole and the corresponding 1,2,4-triazoline-5-thione. The structures of the compounds were studied by means of IR and 1H, 13C, and 15N NMR spectroscopy and mass spectrometry.
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Literature Cited
Yu. P. Kitaeva and B. I. Buzykin, Hydrazones [in Russian], Nauka, Moscow (1974).
S. I. Yakimovich, L. A. Kayukova, and K. B. Erzhanov, Acylation of Nitrogen Derivatives of Carbonyl Compounds [in Russian], Nauka, Alma-Ata (1985).
K. N. Zelenin, A. B. Tomchin, O. V. Solod, and M. Yu. Malov, Khim. Geterotsikl. Soedin., No. 1, 128 (1986).
K. N. Zelenin, O. V. Solod, and A. B. Tomchin, Zh. Obshch. Khim., 57, 584 (1987).
K. N. Zelenin, V. V. Alekseev, O. V. Solod, O. B. Kuznetsova, and V. N. Torocheshnikov, Dokl. Akad. Nauk SSSR, 296, 1133 (1987).
T. E. Glotova, A. S. Nakhmanovich, M. V. Sigalov, T. N. Komarova, é. I. Kositsyna, V. Yu. Vitkovskii, and N. D. Kalikhman, Izv. Akad. Nauk SSR, Ser. Khim., No. 1, 216 (1987).
T. E. Glotova, A. S. Nakhmanovich, and N. S. Mabarakshina, Nucleophilic Reactions of Carbonyl Compounds [in Russian], Saratov (1985), p. 105.
A. Hasnaoui, J.-P. Lavergne, and Ph. Viallefont, J. R. Netherl. Chem. Soc., 99, 301 (1980).
J. Elquero, C. Marzin, and J. D. Roberts, J. Org. Chem., 39, 357 (1974).
P. Cabildo, R. M. Claramunt, and J. Elquero, Org. Magn. Reson., 22, 603 (1984).
V. G. Yusupov, S. I. Yakimovich, S. D. Nasirdinov, and N. A. Parpiev, Zh. Org. Khim., 16, 415 (1980).
K. N. Zelenin, V. V. Alekseev, V. A. Khrustalev, S. I. Yakimovich, V. N. Nikolaev, and N. V. Koshmina, Zh. Org. Khim., 20, 180 (1984).
V. A. Khrustalev, O. V. Solod, and K. N. Zelenin, Zh. Org. Khim., 22, 500 (1986).
K. N. Zelenin, M. Yu. Malov, I. V. Zerova, P. B. Terent'ev, and A. G. Kalandarishvili, Khim. Geterotsikl. Soedin., No. 9, 1210 (1987).
A. Maquestiau and R. Flamming, Mass Spectrom. Rev., 1, 237 (1982).
N. Schamp and M. Vandewall, Bull. Soc. Chim. Belges, 75, 539 (1966).
N. A. Parpiev, V. G. Yusupov, S. I. Yakimovich, and Kh. T. Sharipov, Acylhydrazones and Their Complexes with Transition Metals [in Russian], Fan, Tashkent (1988).
I. Yavari and J. D. Roberts, Org. Magn. Reson., 14, 61 (1980).
M. Uda and S. Kubota, J. Heterocycl. Chem., 16, 1273 (1979).
L. Knorr, Ann., 279, 232 (1894).
R. Milcent and Nguyen Thu-Huong, J. Heterocycl. Chem., 23, 881 (1986).
V. Sherman, “Thiadiazoles,” in: Heterocyclic Compounds, R. Elderfield (ed.) [Russian translation], Vol. 7, Moscow (1965), Chap. 7, p. 416.
J. Goerdeler and J. Galinke, Chem. Ber., 90, 202 (1957).
Y. R. Rao, Indian J. Chem., 7, 836 (1969).
P. B. Terent'ev and A. P. Stankevichyus, Mass-Spectrometric Analysis of Biologically Active Nitrogen Bases [in Russian], Mokslas, Vilnius (1987).
G. Losse, W. Hessler, and A. H. Barth, Chem. Ber., 91, 150 (1958).
J. L. Barascut, J. Daunis, and R. Jacquier, Bull. Soc. Chim. Fr., No. 1, 323 (1973).
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1260–1270, September, 1990.
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Zelenin, K.N., Solod, O.V., Alekseev, V.V. et al. Synthesis of pyrazole, 1,3,4-thiadiazole, and 1,2,4-triazole derivatives by condensatoin of 1,3-dioxo compounds with thiosemicarbazide derivatives. Chem Heterocycl Compd 26, 1051–1060 (1990). https://doi.org/10.1007/BF00472492
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DOI: https://doi.org/10.1007/BF00472492