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2020 , Vol. 40 >Issue 6: 1563 - 1570

DOI: https://doi.org/10.6023/cjoc202003012

研究论文

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

  • 李志锋 ,
  • 王文鹏 ,
  • 王喜存 ,
  • 权正军
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  • 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

  网络出版日期: 2020-06-01

基金资助

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

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

  • Li Zhifeng ,
  • Wang Wenpeng ,
  • Wang Xicun ,
  • Quan Zhengjun
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  • 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 date: 2020-03-05

  Revised date: 2020-05-17

  Online 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).

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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.

关键词： 磷氰酸钠; 磷代脲; 反应机理; 密度泛函

本文引用格式

李志锋 , 王文鹏 , 王喜存 , 权正军 . 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[J]. 有机化学, 2020 , 40(6) : 1563 -1570 . DOI: 10.6023/cjoc202003012

Abstract

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

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