Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (6): 1563-1570.DOI: 10.6023/cjoc202003012 Previous Articles     Next Articles


李志锋a, 王文鹏b, 王喜存b, 权正军b   

  1. a 天水师范学院化学工程与技术学院 甘肃天水 741001;
    b 西北师范大学化学化工学院 兰州 730070
  • 收稿日期:2020-03-05 修回日期:2020-05-17 发布日期:2020-06-01
  • 通讯作者: 权正军
  • 基金资助:

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

Li Zhifenga, Wang Wenpengb, Wang Xicunb, Quan Zhengjunb   

  1. a College of Chemical Engineering and Technology, Tianshui Normal University, Tianshui, Gansu 741001;
    b College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070
  • Received:2020-03-05 Revised:2020-05-17 Published:2020-06-01
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21463023, 21562036) and the Natural Science Foundation of Gansu Province (No. 17JR5RE010).

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.

Key words: 2-phosphaethynolate anion, phosphinecarboxamide, reaction mechanism, DFT