Abstract
The reaction of chloroacetyl chloride with 1,2-dichloroethene in the presence of AlCl3 unexpectedly led to the formation of (E)-1,1,4-trichlorobut-3-en-2-one whose structure was proved by 1H and 13C NMR, IR, and mass spectra and independent synthesis. A probable reaction scheme was proposed, which involves transformation of initially formed 1,2,4-trichloro-3-oxobutan-2-yl cation by the action of AlCl3. The high reactivity of the vinylic halogen atom in (E)-1,1,4-trichlorobut-3-en-2-one was demonstrated by its reactions with nitrogen-centered nucleophiles (triethylamine, aniline, 3,5-dimethyl-1H-pyrazole) and sodium sulfide. These reactions involved only the C-Cl bond in the vinyl fragment and afforded (4,4-dichloro-3-oxobut-2-en-1-yl)triethylammonium chloride, 1,1-dichloro-4-phenylaminobut-3-en-2-one, 1-(4,4-dichloro-3-oxobut-2-en-1-yl)-3,5-dimethyl-1H-pyrazole, and 4,4′-thiobis(1,1-dichlorobut-3-en-2-one), respectively. The reaction of 1,1,4-trichlorobut-3-en-2-one with benzylhydrazine gave a mixture of 1,3- and 1,5-disubstituted pyrazoles.
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References
Kochetkov, N.K., Usp. Khim., 1955, vol. 24, p. 32; Pohland, A.E. and Benson, W.R., Chem. Rev., 1966, vol. 66, p. 161; Levkovskaya, G.G., Bozhenkov, G.V., and Mirskova, A.N., Izbrannye metody sinteza i modifikatsii geterotsiklov (Selected Methods of Synthesis and Modification of Heterocycles), Kartsev, V.G., Ed., Moscow: IBS, 2003, vol. 2, p. 284; Moiseev, I.K., Makarova, N.V., and Zemtsova, M.N., Izv. Vyssh. Uchebn. Zaved., Ser. Khim. Khim. Tekhnol., 2007, vol. 59, p. 3.
Bozhenkov, G.V., Levkovskaya, G.G., Larina, L.I., Ushakov, P.E., Dolgushin, G.V., and Mirskova, A.N., Russ. J. Org. Chem., 2004, vol. 40, p. 1583.
Prins, H.J. and Haring, H.G., Recl. Trav. Chim. Pays-Bas, 1954, vol. 73, p. 479; Chem. Abstr., 1955, vol. 49, p. 12265b.
Atavin, A.S., Mirskova, A.N., and Levkovskaya, G.G., Zh. Org. Khim., 1973, vol. 9, p. 318.
Bozhenkov, G.V., Levkovskaya, G.G., Larina, L.A., Evstaf’eva, I.T., and Mirskova, A.N., Russ. J. Org. Chem., 2001, vol. 37, p. 644.
Voronina, T.A., Chernyavskii, A.I., and Dobrov, I.V., Zh. Org. Khim., 1981, vol. 17, p. 918.
Mekhryushev, Yu.Ya. and Poluektov, V.A., Zh. Fiz. Khim., 1973, vol. 47, p. 1695.
Levkovskaya, G.G., Mirskova, A.N., Atavin, A.S., and Kalikhman, I.D., Zh. Org. Khim., 1974, vol. 10, p. 2293.
Soulen, R.L., Kundiger, D.G., Searles, S., Jr., and Sanchez, R.A., J. Org. Chem., 1967, vol. 32, p. 2661.
Polyakova, A.A. and Khmel’nitskii, R.A., Mass-spektrometriya v organicheskoi khimii (Mass Spectrometry in Organic Chemistry), Leningrad: Khimiya, 1972, p. 367; Zaikin, V.G., Varlamov, A.V., Mikaya, A.I., and Prostakov, N.S., Osnovy mass-spektrometrii organicheskikh soedinenii (Principles of Mass Spectrometry of Organic Compounds), Moscow: MAIK Nauka/Interperiodica, 2001, p. 285.
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Original Russian Text © G.V. Bozhenkov, V.A. Savosik, E.V. Rudyakova, Kha Kuok Khan’, A.I. Albanov, L.V. Klyba, A.N. Mirskova, G.G. Levkovskaya, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 12, pp. 1772–1777.
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Bozhenkov, G.V., Savosik, V.A., Rudyakova, E.V. et al. Unusual reaction of chloroacetyl chloride with 1,2-dichloroethene. Synthesis and properties of 2-chlorovinyl dichloromethyl ketone. Russ J Org Chem 44, 1745–1751 (2008). https://doi.org/10.1134/S1070428008120038
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DOI: https://doi.org/10.1134/S1070428008120038