大学化学 >> 2025, Vol. 40 >> Issue (7): 286-293.doi: 10.12461/PKU.DXHX202408035

化学实验 上一篇    下一篇

1,3-二溴-5,5-二甲基海因的合成及其作为溴化试剂应用的综合化学实验

李肖阳, 黄骁炜, 张艺萌, 刘欢, 金劭, 庄俊鹏   

  1. 北京化工大学化学学院, 北京 100029
  • 收稿日期:2024-08-10 录用日期:2024-11-27 发布日期:2025-07-01
  • 通讯作者: 庄俊鹏 E-mail:zhuangjp@mail.buct.edu.cn
  • 基金资助:
    北京化工大学新工科新文科实验教学改革项目

Comprehensive Chemical Experiments on the Synthesis of 1,3-Dibromo-5,5-Dimethylhydantoin and Its Application as a Brominating Reagent

Xiaoyang Li, Xiaowei Huang, Yimeng Zhang, Huan Liu, Shao Jin, Junpeng Zhuang   

  1. College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2024-08-10 Accepted:2024-11-27 Published:2025-07-01
  • Contact: Junpeng Zhuang E-mail:zhuangjp@mail.buct.edu.cn

摘要: 采用微通道法,在聚四氟乙烯软管中利用HBr和NaBrO3在水溶液中的逆歧化反应原位生成液溴,直接滴加到反应体系中与5,5-二甲基海因反应,并通过滴加NaOH溶液控制体系的pH值,制备了1,3-二溴-5,5-二甲基海因(简称二溴海因)。该反应后处理简单,通过抽滤和水洗获得目标化合物。然后,用所合成的二溴海因作为溴化试剂,在化合物(6-甲氧基萘-2-基)丙-1-酮的5-位引入溴原子,得到制备S-萘普生的关键中间体。溴代反应30分钟完成,简洁高效,选择性好,收率高。该实验所采用连续流原位生成单质溴的方法为本科大学化学实验中液溴参与的水相体系实验提供了新途径。随后的溴化反应展现了二溴海因作为一种溴化试剂相比于NBS和液溴具有明显的优势。该实验综合了有机化学和无机化学实验的原理与操作,在理论上加强了有机酸碱的概念,在操作上强化了有机合成基本技能的训练,是一项适合本科高年级学生开展的综合化学实验。

关键词: 海因类消毒剂, 逆歧化反应, 微通道反应器, 溴化反应

Abstract: In this paper, a microchannel method was used to generate liquid bromine in situ in a polytetrafluoroethylene hose by the reverse disproportionation reaction of HBr and NaBrO3 in aqueous solution, which was directly added to the reaction system to react with 5,5-dimethylhydantoin, and the pH value of the system was controlled by adding NaOH solution to prepare 1,3-dibromo-5,5-dimethylhydantoin (DBDMH). The post-treatment of the reaction is simple, and the target compound is obtained by filtration and water washing. Then, the synthesized dibromohydantoin is used as a bromination reagent to introduce a bromine atom at the 5-position of the compound (6-methoxynaphthalen-2-yl) propan-1-one to obtain a key intermediate for the preparation of S-naproxen. The bromination reaction is completed in 30 minutes, which is simple and efficient, with good selectivity and high yield. The method of continuous flow in-situ generation of bromine used in this experiment provides a new approach for aqueous phase system experiments involving liquid bromine in undergraduate university chemistry experiments. The subsequent bromination reaction shows that dibromohydantoin has obvious advantages as a bromination reagent compared to NBS and liquid bromine. This experiment combines the principles and operations of organic chemistry and inorganic chemistry experiments, strengthens the concept of organic acids and bases in theory, and strengthens the training of basic skills in organic synthesis in operation. It is a comprehensive chemistry experiment suitable for senior undergraduate students.

Key words: Hydantoin-based disinfectants, Reverse disproportionation reaction, Microchannel reactor, Bromination reaction