应用量子化学计算理解溶剂对CH_(3)O^(-)/CH_(3)S^(-)亲核性的影响  

Understanding the Effect of Solvents on the Nucleophilicity of CH_(3)O^(-)/CH_(3)S^(-) Using Quantum Chemical Calculations

作　　者：朱荣秀[1] 王小莫 郭今心[1] 张冬菊[1] Rongxiu Zhu;Xiaomo Wang;Jinxin Guo;Dongju Zhang(School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,China)

机构地区：[1]山东大学化学与化工学院,济南250100

出　　处：《大学化学》2023年第2期271-276,共6页University Chemistry

基　　金：山东大学教育教学改革研究项目(2022Y072,2022Y076)。

摘　　要：溶剂对亲核试剂亲核性的影响是有机化学课程中的重要教学内容。本文以CH_(3)O^(-)/CH_(3)S^(-)与CH_(3)Cl的双分子亲核取代反应为例,设计了一个计算化学与有机化学相结合的教学案例,通过量子化学计算直观地描述了反应的分子机理,获得了反应的热力学和动力学信息,据此分析了溶剂对亲核试剂亲核性的影响,给出了表征亲核能力的亲核指数。The effect of solvents on the nucleophilicity of nucleophiles is an important teaching topic in organic chemistry.Considering the bimolecular nucleophilic substitution (S_(N)2) reaction between methoxide (CH_(3)O^(-)) and thiomethoxide (CH_(3)S^(-)) anions with chloroform (CH_(3)Cl) as a representative example,this paper designs a teaching case for integrating computational chemistry into the organic chemistry curriculum.By performing quantum chemical calculations,we determined the reaction mechanism,obtained the thermodynamic and kinetic information of the reactions,and investigated the effect of solvents on the properties of nucleophiles.Polar protic solvents,such as methanol and water,and polar aprotic solvents,such as acetone,acetonitrile,and chloroform,were analyzed.The nucleophilic index was also calculated to evaluate the nucleophilic reactivities of CH_(3)O^(-)and CH_(3)S^(-).

关 键 词：亲核性 双分子亲核取代 溶剂效应 密度泛函理论计算 

分 类 号：G64[文化科学—高等教育学] O6[文化科学—教育学]