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

doi:10.6023/cjoc202003012

有机化学 ›› 2020, Vol. 40 ›› Issue (6): 1563-1570.DOI: 10.6023/cjoc202003012 上一篇下一篇

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^a, 王文鹏^b, 王喜存^b, 权正军^b

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 E-mail:quanzhengjun@hotmail.com
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.

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

Li Zhifeng^a, Wang Wenpeng^b, Wang Xicun^b, Quan Zhengjun^b

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).

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摘要/Abstract

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

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

引用此文

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.

Li Zhifeng, Wang Wenpeng, Wang Xicun, Quan Zhengjun. Mechanism of Synthesis of Phosphinecarboxamides by Reaction of Sodium Phosphaethynolate Anion and Amines under Acid-Free Conditions: Density Functional Theory Investigation[J]. Chinese Journal of Organic Chemistry, 2020, 40(6): 1563-1570.

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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

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