无酸条件下磷氰酸钠与胺反应合成磷代脲机理的密度泛函理论研究  

Mechanism of Synthesis of Phosphinecarboxamides by Reaction of Sodium Phosphaethynolate Anion and Amines under Acid-Free Conditions:Density Functional Theory Investigation

作　　者：李志锋 王文鹏[2] 王喜存[2] 权正军[2] Li Zhifeng;Wang Wenpeng;Wang Xicun;Quan;Zhengjun(College of Chemical Engineering and Technology,Tianshui Normal University,Tianshui,Gansu 741001;College of Chemistry and Chemical Engineering,Northwest Normal University,Lanzhou 730070)

机构地区：[1]天水师范学院化学工程与技术学院,甘肃天水741001 [2]西北师范大学化学化工学院,兰州730070

出　　处：《有机化学》2020年第6期1563-1570,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21463023,21562036);甘肃省自然科学基金(No.17JR5RE010)资助项目.

摘　　要：磷氰酸钠与胺可以在室温、无酸的温和条件下反应生成磷代脲.利用密度泛函理论计算方法,在B3LYP/6-31G(d,p)水平上对磷氰酸钠与胺反应合成磷代脲的反应机理进行了研究,结果表明溶剂的辅助/催化作用可以显著降低该反应的反应势垒,使得反应快速、高转化率发生.The reaction of 2-phosphaethynolate anion and primary amines for phosphinecarboxamides synthesis using mechanochemistry has been studied using IR,13C NMR and 31P NMR spectra,and the reaction occurred under grinding,mild and acid-free conditions at room temperature.In this paper,a comprehensive mechanistic density functional theory(DFT)of B3LYP/6-31G(d,p)study reveals that H shift can be aided/catalyzed with solvents and further the activation free energies barrier can be dramatically decreased,which is responsible for the higher yield of the product in the experiment.

关 键 词：磷氰酸钠 磷代脲 反应机理 密度泛函 

分 类 号：O641.1[理学—物理化学] O621.3[理学—化学]