Conclusions
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1.
The reaction of oxopiperidinium salts with alkylketones involves the enolization of the ketones. The rate constants for the enolization of the ketones and the rate constants for the reaction of the oxopiperidinium cation with the enols have been determined.
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2.
With respect to the ketones, the oxopiperidinium salts with halide anions are not only electrophilic, but are also halogenating agents. The ratio between the reaction products depends on the ratio between the rate constants for the reaction of the enols with the oxopiperidinium cation and the halogens and on the value of the oxidation-reduction equilibrium constant of the oxopiperidinium cation with the halide anion.
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3.
A spectrophotometric method has been proposed for the determination of the concentration of enol forms inβ-dicarbonyl compounds on the basis of the fast reaction between the oxopiperidinium cation and the enol forms.
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Literature cited
V. A. Golubev, R. I. Zhdanov, I. T. Protsishin, and É. G. Rozantsev, Izv. Akad. Nauk SSSR, Ser. Khim., 2158 (1970).
V. A. Golubev, R. I. Zhdanov, I. T. Protsishin, and É. G. Rozantsev, Dokl. Akad. Nauk SSSR,195, 1139 (1970).
V. A. Golubev, G. N. Voronina, and É. G. Rozantsev, Izv. Akad. SSSR, Ser. Khim., 2605 (1970).
V. A. Golubev, R. V. Miklyush, and É. G. Rozantsev, Izv. Akad. Nauk SSSR, Ser. Khim., 656 (1972).
V. A. Golubev and R. V. Miklyush, Zh. Organ. Khim.,8, 1356 (1972).
V. A. Golubev, R. I. Zhdanov, and É. G. Rozantsev, Izv. Akad, Nauk SSSR, Ser. Khim., 184 (1970).
L. O. Atovmyan, V. A. Golubev, N. I. Golovina, and G. Klitskaya, Zh. Struktur. Khim.,16, 92 (1975).
R. P. Bell and P. Jones, J. Chem. Soc., 88 (1953).
L. Hammett, Physical Organic Chemistry; Reaction Rates, Equilibria, and Mechanisms, McGraw-Hill, New York (1970).
R. P. Bell and P. Yates, J. Chem. Soc., 1927 (1962).
A. J. Green, T. J. Kemp, J. S. Littler, and W. A. Waters, J. Chem. Soc., 2722 (1964).
J. E. Dubois and J. Toullens, Tetrahedron,29, 2859 (1973).
R. P. Bell and P. W. Smith, J. Chem. Soc., Sec. B, 241 (1966).
G. M. Panchenkov and V. P. Lebedev, Chemical Kinetics and Catalysis [in Russian], Khimiya (1974), p. 569.
É. M. Arnett, in: Contemporary Problems in Physical Organic Chemistry [Russian translation), Mir (1967), p. 195.
O. Ya. Neiland and G. Ya. Vanag, Usp. Khim.,28, 436 (1959).
V. A. Golubev, V. D. Sen', I. V. Kulyk, and A. L. Aleksandrov, Izv. Akad. Nauk SSSR, Ser. Khim., 2235 (1975).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 763–771, April, 1976.
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Golubev, V.A., Rudyk, T.S., Sen', V.D. et al. Mechanism of the reaction of di-tert-alkyloxoammonium salts with alkyl ketones. Russ Chem Bull 25, 744–750 (1976). https://doi.org/10.1007/BF00922372
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DOI: https://doi.org/10.1007/BF00922372