大学化学 >> 2024, Vol. 39 >> Issue (12): 258-264.doi: 10.12461/PKU.DXHX202404015

所属专题： 有机化学课程与实验教学(2024)

化学实验 上一篇    下一篇

还原胺化反应：以间苯二甲醛制备间苯二甲胺为例

吕雷阳1, 路广印1, 罗亚妮1, 高歌1, 闫晓宇1, 徐肇中2, 姚丽菲2, 李洪娟2, 李志平1   

  1. 1 中国人民大学化学与生命资源学院, 北京 100872;
    2 开滦煤化工研发中心, 河北 唐山 063018
  • 收稿日期:2024-04-02 录用日期:2024-05-15 发布日期:2024-06-04
  • 通讯作者: 李志平 E-mail:zhipingli@ruc.edu.cn
  • 基金资助:
    中国人民大学教育教学改革研究项目、课程训练项目和金课建设项目;开滦(集团)有限责任公司科技创新计划项目

Reductive Amination Reaction: Preparation of m-Xylylenediamine from Isophthalaldehyde as an Example

Leiyang Lv1, Guangyin Lu1, Yani Luo1, Ge Gao1, Xiaoyu Yan1, Zhaozhong Xu2, Lifei Yao2, Hongjuan Li2, Zhiping Li1   

  1. 1 School of Chemistry and Life Resources, Renmin University of China, Beijing 100872, China;
    2 Coal Chemical R&D Center of Kailuan Group, Tangshan 063018, Hebei Province, China
  • Received:2024-04-02 Accepted:2024-05-15 Published:2024-06-04
  • Contact: Zhiping Li E-mail:zhipingli@ruc.edu.cn

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摘要： 还原胺化反应是一种将醛酮转换成胺的实用方法。我们以还原胺化反应为例，介绍一个面向高年级本科生的有机化学综合实验——硅烷参与的间苯二甲醛还原胺化制备间苯二甲胺。该反应以氨基甲酸叔丁酯(BocNH2)为氮源，三乙基硅烷(Et3SiH)为还原剂，在三氟乙酸的催化下，间苯二甲醛经过还原胺化得到叔丁氧基羰基(Boc)保护的间苯二甲胺；随后，通过脱除Boc保护基团，得到间苯二甲胺盐酸盐；最后经氢氧化钠处理，得到产物间苯二甲胺。实验过程涉及了多种操作技术，如萃取、减压蒸馏、干燥、重结晶、熔点测定，同时还包括了薄层色谱、红外光谱和核磁共振等分析测试方法。该路线适用于实验室合成，产品收率高且易于纯化。本实验对于学生有机合成实验能力的培养和提高，加深对波谱理论知识的理解和应用等具有很好的教学效果。

关键词: 还原胺化, 间苯二甲胺, 间苯二甲醛, 胺

Abstract: Reductive amination is a practical method for converting carbonyl compounds to amines. Using this reaction as an example, we introduce a comprehensive organic chemistry experiment designed for senior undergraduates: the reductive amination of isophthalaldehyde with silane to synthesize m-xylylenediamine. In this reaction, tert-butyl carbamate (BocNH2) serves as the nitrogen source, and triethylsilane (Et3SiH) acts as the reducing agent, with trifluoroacetic acid as the catalyst. Isophthalaldehyde undergoes reductive amination to produce Boc-protected m-xylylenediamine, which is subsequently deprotected to yield m-xylylenediamine hydrochloride. The final product, m-xylylenediamine, is obtained by treating the hydrochloride salt with sodium hydroxide. The experimental procedure includes techniques such as extraction, vacuum distillation, drying, recrystallization, and melting point determination, along with analytical methods like thin-layer chromatography (TLC), infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. This synthetic route is well-suited for laboratory synthesis, providing high yields and easy purification of the product. The experiment enhances students’ skills in organic synthesis and deepens their understanding and application of spectroscopic techniques.

Key words: Reductive amination, m-Xylylenediamine, Isophthalaldehyde, Amine