四川师范大学学报(自然科学版)2012,Vol.35Issue(4):539-543,5.DOI:10.3969/j.issn.1001-8395.2012.04.022
α-乙酰基二硫缩烯酮在TiCl4催化下的酰化反应机理研究
Research on Reaction Mechanism of α-Acetyl Ketendithioacetals in the Presence of TiCl4-Catalyst
摘要
Abstract
Based on B3LYP/6 -311G(p) principle, the reaction mechanism of a - acetyl ketendithioacetals in the presence of TiCl4 catalyst was investigated. PCM model was applied to calculate charge density in the bond critical points for optimized configuration of reactanta, intermediates, transition states and products. Meanwhile, reaction process was also simulated in dichloronethane solution. In addition, nature bond orbital (NBO) and atoms in molecules (AIM) theories were used to discuss bond natures and orbital interactions. Hie computational results indicate that the activation barrier with TiCl4 -catalyst is lower than that without TiCl4-catalyst which indicate that TiCl4 can promote the reaction and enhance the yield of product. Furthermore, solvent effect also decreases the barriers in a significant way.关键词
α-乙酰基二硫缩烯酮/反应机理/活化能/溶剂效应Key words
α-acetyl ketendithioacetals with acyl chloride/ reaction mechanism/ activation barrier/ solvent effects分类
化学化工引用本文复制引用
苏心桐,李来才..α-乙酰基二硫缩烯酮在TiCl4催化下的酰化反应机理研究[J].四川师范大学学报(自然科学版),2012,35(4):539-543,5.基金项目
四川省教育厅自然科学青年基金(11ZB085)资助项目 (11ZB085)