Thermally induced transformation tert-butyl peroxyethyl esters of carboxylic acids

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Аннотация

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.

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Авторлар туралы

T. Aleinikova

Volgograd State Technical University

Хат алмасуға жауапты Автор.
Email: aleynikova_tp@vstu.ru
Ресей, 400005 Volgograd

M. Vaniev

Volgograd State Technical University

Email: aleynikova_tp@vstu.ru
Ресей, 400005 Volgograd

A. Seleznev

Volgograd State Technical University

Email: aleynikova_tp@vstu.ru
Ресей, 400005 Volgograd

V. Navrotsky

Volgograd State Technical University

Email: aleynikova_tp@vstu.ru
Ресей, 400005 Volgograd

I. Novakov

Volgograd State Technical University

Email: aleynikova_tp@vstu.ru

Academician of the RAS

Ресей, 400005 Volgograd

Әдебиет тізімі

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Әрекет
1. JATS XML
2. Fig. 1. Geometrical structure of the optimized structure of the peroxide molecule 1.

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3. Fig. 2. The structure of one of the possible conformers of the peroxide molecule 1.

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4. Scheme 1

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