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Kinetics and mechanism of benzyl para-chlorophenyl ketone oxidation

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Abstract

The oxidation of benzyl para-chlorophenyl ketone in chlorobenzene at 100°C occurs through the formation of short chains. Non-peroxide reaction products (1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone, para-chlorobenzyl, benzaldehyde, and para-chlorobenzoic acid) are formed not only by the transformation of hydroperoxide (1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone) but also (or solely) through the recombination of α-ketoperoxyl radicals with or without chain termination. α-Hydroperoxide decomposes predominantly through a heterolytic route to form para-chlorobenzoic acid and benzaldehyde. Benzaldehyde and 1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone undergo radical chain oxidation in the reaction medium to form benzoic acid (benzaldehyde), para-chlorobenzyl, and benzoic and para-chlorobenzoic acids (1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone). The homolytic decomposition of α-hydroperoxy ketone and α-hydroxy-α-hydroperoxy ketone causes the self-acceleration of the process and affords 1-(4-chlorophenyl)-2-hydroxy-2-phenyl-1-ethanone or, to a lesser extent, benzaldehyde and para-chlorobenzoic acid (α-hydroperoxy ketone). para-Chlorobenzoic acid substantially accelerates the heterolytic decomposition of α-hydroxy-α-hydroperoxy ketone and the oxidation of benzyl para-chlorophenyl ketone with peroxy acids to ester according to the Baeyer-Villiger mechanism. The rate constants of the main steps of the process and kinetic parameters are calculated by solving the inverse kinetic problem.

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Authors and Affiliations

  1. Department of Chemical Technology, Kuzbass State Technical University, Kemerovo, Russia

    O. A. Revkov, S. G. Voronina & A. L. Perkel’

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  1. O. A. Revkov
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  2. S. G. Voronina
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  3. A. L. Perkel’
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Original Russian Text © O.A. Revkov, S.G. Voronina, A.L. Perkel’, 2007, published in Kinetika i Kataliz, 2007, Vol. 48, No. 1, pp. 22–31.

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Revkov, O.A., Voronina, S.G. & Perkel’, A.L. Kinetics and mechanism of benzyl para-chlorophenyl ketone oxidation. Kinet Catal 48, 17–25 (2007). https://doi.org/10.1134/S002315840701003X

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  • DOI: https://doi.org/10.1134/S002315840701003X

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