SOLVENT EFFECTS IN THE THERMAL-DECOMPOSITION REACTIONS OF CYCLIC KETONE DIPEROXIDES

被引：59

作者：

CAFFERATA, LFR

EYLER, GN

SVARTMAN, EL

CANIZO, AI

ALVAREZ, E

机构：

[1] Institute de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, (1900) La Plata, Casilla de Correo 16

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 01期

关键词：

D O I：

10.1021/jo00001a074

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The kinetics of the thermal decomposition reactions of acetone, pinacolone, and cyclohexanone cyclic diperoxides were investigated in various solvents at different temperatures. Linear relationships were observed between the enthalpy and entropy of activation of the unimolecular reactions of those diperoxides. The acetone cyclic diperoxide (ACDP) reaction is relatively more sensitive to solvent changes, behavior attributed to a reduced steric hindrance of the methyl groups of its molecule. Qualitatively different ground or transition states for the corresponding unimolecular reactions of the ACDP may be postulated according to the strong solvent dependence.

引用

页码：411 / 414

页数：4

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