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Mechanisms for the formation of ester compounds in the liquid-phase oxidation of cyclohexane

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Abstract

The channels of formation of ester compounds in the liquid-phase oxidation of cyclohexane are reviewed. At least 99.8% cyclohexyl esters of mono- and dicarboxylic acids are formed as a result of cyclohexanol acylation with mixed anhydrides including residues of all compounds with carboxyl groups present in the oxidized cyclohexane. The formation of mixed anhydrides is related to the fast reacylation of adipic anhydride with carboxylic acids. Alcoholysis of mixed anhydrides containing the formic acid residue with cyclohexanol leads mainly to cyclohexyl formate. The formation of ε-caprolactone during cyclohexane oxidation is the result of the Baeyer–Villiger oxidation of cyclohexanone with peroxy acids through α-hydroxy-α-hydroperoxy ester. A decrease in the yield of ε-caprolactone is reached under the conditions of decomposition or reduction of peroxy acids in the presence the compounds of variable valency metals or sulfur-containing reagents, respectively. The cobalt(II) and manganese(II) compounds stimulate the homolytic decomposition of α-hydroxy-α-hydroperoxy ester during which no lactone is formed. The cyclization of 5-hydroxypentanoic acid, which was formed by the oxidative transformations of cyclohexanone, leads to δ-valerolactone. The compounds of variable valency metals slightly affect the yield of δ-valerolactone. The mechanism of ester formation associated with the acylation of oxiranes formed by the radical chain oxidation of carbonyl compounds at the β-CH bonds was proposed.

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  1. Institute of Chemical and Oil-Gas Technologies, Kuzbass State Technical University named after T. F. Gorbachev, 28 ul. Vesennyaya, 650000, Kemerovo, Russian Federation

    A. L. Perkel & S. G. Voronina

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  1. A. L. Perkel
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1803–1820, October, 2019.

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Perkel, A.L., Voronina, S.G. Mechanisms for the formation of ester compounds in the liquid-phase oxidation of cyclohexane. Russ Chem Bull 68, 1803–1820 (2019). https://doi.org/10.1007/s11172-019-2630-0

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