Thermally induced transformation tert-butyl peroxyethyl esters of carboxylic acids

T. P. Aleinikova; Алейникова Т. П.; M. A. Vaniev; Ваниев М. А.; A. A. Seleznev; Селезнев А. А.; V. A. Navrotsky; Навроцкий В. А.; I. A. Novakov; Новаков И. А.

doi:10.31857/S2686953524030017

Thermally induced transformation tert-butyl peroxyethyl esters of carboxylic acids

Authors: Aleinikova T.P.¹, Vaniev M.A.¹, Seleznev A.A.¹, Navrotsky V.A.¹, Novakov I.A.¹
Affiliations:
1. Volgograd State Technical University
Issue: Vol 516, No 1 (2024)
Pages: 3-7
Section: CHEMISTRY
URL: https://ter-arkhiv.ru/2686-9535/article/view/651903
DOI: https://doi.org/10.31857/S2686953524030017
EDN: https://elibrary.ru/ZJPGLC
ID: 651903

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Abstract

The features of thermolysis of tert-butyl peroxyethyl esters of carboxylic acids (CH₃)₃COOCH(CH₃)OC(O)R are investigated. Based on the identification of reaction products and the analysis of kinetic parameters, the fact of simultaneous transformation of four bonds (O–O, C–O, C–C and C–H) in a molecule with the formation of two molecules was proved for the first time [RC(O)OH and CO] and two free radicals [(CH₃)₃CO• and •CH₃], which, under experimental conditions, do not enter into a cross-break reaction, but detach the hydrogen atom from the solvent. Evidence of the coordinated (simultaneous) transformation of four bonds is the low (compared with the energy of bond dissociation) values of the activation energy and the pre-exponential multiplier, as well as negative values of the activation entropy.

Keywords

tert-butyl peroxyethyl esters of carboxylic acids, coordinated decomposition, thermally induced exposure

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Academician of the RAS

Russian Federation, 400005 Volgograd

References

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