大学化学 >> 2025, Vol. 40 >> Issue (3): 153-159.doi: 10.12461/PKU.DXHX202405172

所属专题： 理论与计算化学在化学及其交叉学科教学中的应用

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基于量子化学计算阐明基础化学课程中的Beckmann重排反应机制

黄嘉博1, 黎权鑫1, 曹中艳2, 党丽1, 倪绍飞1   

  1. 1 汕头大学化学化工学院, 广东省有序结构材料的制备与应用重点实验室, 广东 汕头 515063;
    2 河南大学化学与分子科学学院, 河南 开封 475004
  • 收稿日期:2024-05-27 录用日期:2024-09-02 发布日期:2025-03-19
  • 通讯作者: 党丽, 倪绍飞 E-mail:sfni@stu.edu.cn;ldang@stu.edu.cn
  • 基金资助:
    松山湖实验室开放课题(2023SLABFN16)；广东省自然科学基金-面上项目(2024A1515010323)；成都大学四川抗菌素工业研究所国际科技合作基地资助(ISTC202204)；汕头大学科研启动经费项目(NTF20022)

Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations

Jiabo Huang1, Quanxin Li1, Zhongyan Cao2, Li Dang1, Shaofei Ni1   

  1. 1 Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, College of Chemistry & Chemical Engineering, Shantou University, Shantou 515063, Guangdong Province, China;
    2 College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, Henan Province, China
  • Received:2024-05-27 Accepted:2024-09-02 Published:2025-03-19
  • Contact: Li Dang, Shaofei Ni E-mail:sfni@stu.edu.cn;ldang@stu.edu.cn

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摘要： Beckmann重排反应是有机化学教学课程中的经典重排反应，但目前主流教材中对该重排反应的反应机理阐述不够具体，学生在学习过程中缺乏对反应更深刻的理解和认知。本案例以三类酮肟结构在两种不同的质子源环境下为例，通过量子化学计算对Beckmann重排反应的反应机理进行对比研究，阐明其重排反应机制，并利用前线分子轨道分析σ-型和π-型腈鎓离子中间体的电子结构。本文旨在帮助学生加深对Beckmann重排反应的认知，并学习使用理论计算化学方法研究化学反应及其内在机制。

关键词: Beckmann重排, DFT计算, 反应机理

Abstract: Beckmann rearrangement is a classical reaction in the courses of organic chemistry. However, mainstream textbooks often lack detailed explanations of its reaction mechanism, leaving students with a superficial understanding. This study investigates the Beckmann rearrangement mechanism of three types of ketoxime structures under two different proton sources using quantum chemical calculations. The detailed comparison and analysis provide insights into rearrangement process, including the migration rules of cis- and trans-ketoxime structures. Additionally, the electronic structures of the σ-type and π-type nitrilium ion intermediates are analyzed through frontier molecular orbital theory. This work aims to deepen students’ understanding of Beckmann rearrangement and introduce them to the application of theoretical computational chemistry in studying chemical reactions and their underlying mechanisms.

Key words: Beckmann rearrangement, DFT calculations, Reaction mechanism