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Oxidation of Deactivated Cage Substrates in the System H2SO4–HNO3

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Abstract

The kinetics of oxidation of 16 carboxylic acid esters of the adamantane series in the system H2SO4–HNO3 have been studied, and the effective rate constants have been determined. The reaction is described by the pseudo-first-order kinetic equation. The primary kinetic isotope effect has been estimated at 2.9±0.3. The rate-determining step of the oxidation process is cleavage of the adamantane C–H bond. The presence of an ethyl group at the bridgehead position increases the reactivity of adamantane substrates toward oxidation, whereas methyl, ethoxycarbonyl, and ethoxycarbonylmethyl groups reduce the reactivity.

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ACKNOWLEDGMENTS

The spectral and analytical data were obtained using the facilities of the joint center “Study of Physicochemical Properties of Compounds and Materials.”

Funding

This study was performed under financial support by the Russian Foundation for Basic Research (project no. 18-33-00 881).

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  1. Samara State Technical University, 443100, Samara, Russia

    E. A. Ivleva, I. S. Grinʼ, I. S. Uchaev & Yu. N. Klimochkin

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  1. E. A. Ivleva
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Ivleva, E.A., Grinʼ, I.S., Uchaev, I.S. et al. Oxidation of Deactivated Cage Substrates in the System H2SO4–HNO3. Russ J Org Chem 56, 412–421 (2020). https://doi.org/10.1134/S1070428020030082

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