Citation: 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. doi: 10.6023/cjoc202003012 shu

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

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

Corresponding author: Quan Zhengjun, quanzhengjun@hotmail.com
Received Date: 5 March 2020
Revised Date: 17 May 2020
Available Online: 29 May 2020
Fund Project: the Natural Science Foundation of Gansu Province 17JR5RE010the National Natural Science Foundation of China 21562036Project supported by the National Natural Science Foundation of China (Nos. 21463023, 21562036) and the Natural Science Foundation of Gansu Province (No. 17JR5RE010)the National Natural Science Foundation of China 21463023

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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.
- 2-phosphaethynolate anion,
- phosphinecarboxamide,
- reaction mechanism,
- DFT
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