三氟丙酮酮醇互变异构反应机理的量子化学理论研究  

Quantum chemical research on the keto-enol tautomerization mechanism of trifluoroacetone

作　　者：王晓红[1,2,3] 李宇情[1,2,3] 李玉莹 黄正国[1,2,3] WANG Xiaohong;LI Yuqing;LI Yuying;HUANG Zhengguo(College of Chemistry, Tianjin Normal University, Tianjin 300387, China;Key Laboratory of Inorganic-Organie Hybrid Functional Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin 300387, China;Tianjin Key Laboratory of Structure and Performance for Functional Moleeules, Tianjin Normal University, Tianjin 300387, China)

机构地区：[1]天津师范大学化学学院,天津300387 [2]天津师范大学无机-有机杂化功能材料化学教育部重点实验室,天津300387 [3]天津师范大学天津市功能分子结构与性能重点实验室,天津300387

出　　处：《天津师范大学学报（自然科学版）》2018年第3期42-45,65,共5页Journal of Tianjin Normal University：Natural Science Edition

基　　金：天津市高等学校创新团队培养计划资助项目(TD12-5038)

摘　　要：为了解三氟丙酮水溶液中酮式构型向烯醇式构型转变的可能性,采用二阶M覬ller-Plessset微扰理论研究了三氟丙酮的酮醇互变异构反应机理.三氟丙酮的烯醇式构型和酮式构型都可与水分子通过分子间氢键形成复合物,这些分子间氢键的形成有效降低了酮醇互变异构反应的活化能,从而使得三氟丙酮更容易由酮式构型转变为烯醇式构型.进一步使用CPCM溶剂化模型研究溶剂对酮醇互变异构反应的影响,结果发现,酮醇互变异构反应在水溶液中比在气相中更容易进行.计算三氟丙酮由酮式构型向烯醇式构型转化的活化能,结果表明,酮醇互变异构反应的活化能偏高,不会影响中性水溶液中酮式构型的主导地位.To explore the possibility of conversion of keto-configuration to enol-configuration in trifluoroacetone aqueous solution,the keto-enol tautomerization mechanism of trifluoroacetone was investigated by the second-order M覬ller-Plessset perturbation theory. Both the enol and keto configurations of trifluoroacetone can form complexes with water molecules via intermolecular hydrogen bonds. These intermolecular hydrogen bonds made the enol-keto tautomerization of trifluoroace-tone easier to happen via the decrease of activation energy. The CPCM solvation model was also used to study the effect of sol-vent molecule on the keto-enol tautomerization of trifluoroacetone,and the results showed that the keto-enol tautomerization happened more easily in aqueous solution than that in gas phase. The calculation results of the activation energy of keto-configuration to enol configuration conversion in aqueous trifluoroacetone solution showed that the activation energy was higher,and the dominant position of keto-configuration can′t be influenced in aqueous trifluoroacetone solution.

关 键 词：三氟丙酮 酮醇互变异构反应 量子化学 反应机理 二阶MФller-Plessset微扰理论 

分 类 号：O641[理学—物理化学]