文献类型：期刊文献

英文题名：Thermolysis kinetics of diethyl 2,3-dicyano-2,3-di(p-substituted phenyl)succinates

作者：Qi, Chenze[1,2];Shao, Linjun[1,2];Lu, Yueqing[1,2];Wang, Chen[1,2];Zhang, Xian-Man[1,2]

机构：[1]Univ Shaoxing, Inst Appl Chem, Shaoxing 312000, Zhejiang, Peoples R China;[2]Univ Shaoxing, Dept Chem, Shaoxing 312000, Zhejiang, Peoples R China

年份：2012

卷号：25

期号：6

起止页码：523

外文期刊名：JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

收录：SCI-EXPANDED(收录号：WOS:000304092600013)、、EI(收录号：20122115058217)、Scopus(收录号：2-s2.0-84861333997)、WOS

基金：We greatly appreciate the financial support from the Shaoxing medical and chemical engineering projects and Shaoxing University.

语种：英文

外文关键词：activation enthalpy and entropy; dl; meso thermal isomerization; hexasubstituted ethane; thermolysis kinetics; polymerization initiators

外文摘要：An experimental approach was developed to determine the intrinsic thermolysis rate constants of the central carboncarbon bond during the dl/meso isomerization of diethyl 2,3-dicyano-2,3-di(p-substituted phenyl)succinates (G=H, Me, OMe, Cl, and NO2) at temperatures ranging from 80 to 120 degrees C. The obtained rate constants are significantly affected by the polarity of the para substituents, in sharp contrast to their negligible effects on the dl/meso isomerization equilibrium constants. Moreover, the substituent effects on the activation enthalpies can be linearly correlated with the Hammett substituent resonance constants and the homolytic dissociation enthalpies (bond dissociation energies) of the benzylic CH bonds of ethyl 2-cyano-2-(p-substituted phenyl)acetates. Copyright (c) 2011 John Wiley & Sons, Ltd.