A initio study of the SN2 and E2 mechanisms in the reaction between the cyanide ion and ethyl chloride in dimethyl sulfoxide solution
A initio study of the SN2 and E2 mechanisms in the reaction between the cyanide ion and ethyl chloride in dimethyl sulfoxide solution
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DOI：
10.1021/ol0504547
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发表时间：
2005-04-28
期刊：
影响因子：
5.2
通讯作者：
Pliego, JR Jr
中科院分区：
文献类型：
--
作者：
Almerindo, GI;Pliego, JR Jr
可靠的理论计算预测，在DMSO溶剂中氰根离子和氯乙烷之间反应形成腈的自由能垒为24.1 kcal/mol，接近实验值22.6 kcal/mol。我们还预测，异腈的形成是不太有利的4.7千卡/摩尔，而消除机制是不太有利的超过10千卡/摩尔。这些结果表明，异腈的形成和双分子消除不是伯烷基氯反应的重要副反应。
Reliable theoretical calculations predict a free energy barrier for nitrile formation from the reaction between the cyanide ion and ethyl chloride in DMSO solvent of 24.1 kcal/mol, close to the experimental value of 22.6 kcal/mol. We have also predicted that the isonitrile formation is less favorable by 4.7 kcal/mol, while the elimination mechanism is less favorable by more than 10 kcal/mol. These results indicate that isonitrile formation and bimolecular elimination are not significant side reactions for primary alkyl chloride reactions.