化工学报 ›› 2024, Vol. 75 ›› Issue (1): 302-311.DOI: 10.11949/0438-1157.20230643
收稿日期:
2023-06-28
修回日期:
2023-12-14
出版日期:
2024-01-25
发布日期:
2024-03-11
通讯作者:
陈立芳
作者简介:
咸国义(1998—),男,硕士研究生,1796424721@qq.com
基金资助:
Guoyi XIAN(), Lifang CHEN(), Zhiwen QI
Received:
2023-06-28
Revised:
2023-12-14
Online:
2024-01-25
Published:
2024-03-11
Contact:
Lifang CHEN
摘要:
为了研究质子酸催化的环己酮肟液相贝克曼重排反应机理,使用密度泛函理论中的B3LYP-D3/6-31G(d)方法研究了反应中的过渡态内禀反应坐标,并使用SMD隐式溶剂模型模拟了液相环境。利用前线分子轨道和表面静电势确定了反应的主导因素,通过频率计算获得了过渡态和中间体的Gibbs自由能,确定了速率控制步骤。重排反应不可逆,而水解可逆,环己酮肟先进行双分子重排,然后进行反向水解。低温下,少量水对反应影响较小,提出了环己酮肟最有可能发生双分子重排-水解反应路径。在乙腈溶剂中,静电效应是环己酮肟与质子发生亲电反应的主导因素,局部亲电/亲核性是质子化环己酮肟与水或环己酮肟发生亲核反应的主导因素。本研究有助于深入理解环己酮肟液相贝克曼重排过程,并为避免发生副反应的固体催化剂设计提供理论基础。
中图分类号:
咸国义, 陈立芳, 漆志文. 基于DFT的环己酮肟液相贝克曼重排机理研究[J]. 化工学报, 2024, 75(1): 302-311.
Guoyi XIAN, Lifang CHEN, Zhiwen QI. DFT-based study of liquid-phase Beckmann rearrangement mechanism of cyclohexanone oxime[J]. CIESC Journal, 2024, 75(1): 302-311.
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