大学化学 >> 2025, Vol. 40 >> Issue (3): 16-22.doi: 10.12461/PKU.DXHX202403010

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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计算化学方法再探“碘催化氯苯的氯代反应”

闫虹廷, 冯爱利, 朱荣秀, 刘磊, 张冬菊   

  1. 山东大学化学与化工学院, 济南 250100
  • 收稿日期:2024-03-03 录用日期:2024-05-06 发布日期:2024-09-02
  • 通讯作者: 刘磊, 张冬菊 E-mail:leiliu@sdu.edu.cn;zhangdj@sdu.edu.cn
  • 基金资助:
    国家自然科学基金(22273051)；山东省高等教育本科教学改革研究项目(Z2022169)；山东大学教育教学改革研究项目(2024Z07,2023Y061)

Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods

Hongting Yan, Aili Feng, Rongxiu Zhu, Lei Liu, Dongju Zhang   

  1. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
  • Received:2024-03-03 Accepted:2024-05-06 Published:2024-09-02
  • Contact: Lei Liu, Dongju Zhang E-mail:leiliu@sdu.edu.cn;zhangdj@sdu.edu.cn

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摘要： 本文研究课题“碘催化氯苯的氯代反应”来源于2021年全国统考高考化学试卷(浙江卷)的考题，其试题背后隐含了一系列化学基本概念和基本理论。前期文献对该题目进行了研究，所得结果与高考题目中的描述不一致。本文用密度泛函理论(DFT)方法重新对该反应进行了系统研究，确立了反应的催化活性组分及其形成机理，计算了氯苯氯代反应的分子机制、反应的热力学和动力学性质，比较了邻位、间位及对位取代的反应性能，分析了电子效应和空间效应对反应性能的影响。本文计算结果与高考题目中的描述一致，表明了该题目的严谨性和科学性。本文研究结果有助于学生加深对芳香化合物亲电取代反应的认识和理解。

关键词: 氯苯, 氯代, 碘, 反应机理, 计算化学

Abstract: This paper explores the “Iodine-Catalyzed Chlorination Reaction of Chlorobenzene”, a topic derived from a question in the 2021 National College Entrance Examination chemistry paper for Zhejiang, which embodies a myriad of fundamental chemical concepts and theories. Previous work has delved into this topic, yet their findings diverged from the descriptions provided in the exam paper. Utilizing Density Functional Theory (DFT) calculations, this study conducts a comprehensive reexamination of the reaction, identifying the catalytically active component and its formation mechanism. It elucidates the molecular mechanisms, thermodynamics, and kinetics of the chlorination reaction of chlorobenzene, evaluates the reactivity of ortho, meta, and para substitutions, and investigates the impact of electronic and steric effects on the reactivity. The computational results align with the description in the exam paper, affirming the question’s precision and scientific accuracy. The insights gained from this research significantly contribute to students’ deeper understanding of electrophilic aromatic substitution reactions in aromatic compounds.

Key words: Chlorobenzene, Chlorination, Iodine, Reaction Mechanism, Computation Chemistry