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

引用本文: 李肖阳, 黄骁炜, 张艺萌, 刘欢, 金劭, 庄俊鹏. 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[J]. 大学化学, 2025, 40(7): 286-293. doi: 10.12461/PKU.DXHX202408035 shu

Citation: Xiaoyang Li, Xiaowei Huang, Yimeng Zhang, Huan Liu, Shao Jin, Junpeng Zhuang. Comprehensive Chemical Experiments on the Synthesis of 1,3-Dibromo-5,5-Dimethylhydantoin and Its Application as a Brominating Reagent[J]. University Chemistry, 2025, 40(7): 286-293. doi: 10.12461/PKU.DXHX202408035 shu

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

北京化工大学化学学院, 北京 100029

通讯作者: 庄俊鹏，Email: zhuangjp@mail.buct.edu.cn

基金项目:
北京化工大学新工科新文科实验教学改革项目

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:

English

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

College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China

Corresponding author: Junpeng Zhuang, zhuangjp@mail.buct.edu.cn

Received Date: 10 August 2024
Revised Date: 27 November 2024
Available Online: 13 February 2024

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:

1. [1]
  林源野, 彭伟, 刘耀群, 袁馨. 中国消毒学杂志, 2023, No. 4, 299.
2. [2]
  Armon, R.; Arbel, T.; Green, M. Water Sci. Technol. 1998, 38 (12), 175.Armon, R.; Arbel, T.; Green, M. Water Sci. Technol. 1998, 38 (12), 175.
3. [3]
  朱大欣, 马小燕, 段玉奇, 时梦瑶, 倪孟侨, 李哲, 王奎涛. 应用化工, 2021, 50 (4), 1073.
4. [4]
  刘传仁, 王慧, 王宁宁, 崔美红, 李红新, 鲍猛. 山东化工, 2011, 40 (11), 24.
5. [5]
  周龙梅, 张亮亮, 王金燕. 日用化学工业, 2019, 49(1), 40.
6. [6]
  李伟光, 李伟宪, 李丽敏, 李爱军, 陈波, 高燕云, 赵晓鹏, 党邵杰, 田良杰, 董利波. 山东化工, 2023, 52 (18), 16.
7. [7]
  张家康, 张月成, 赵继全. 精细化工, 2023, 40 (4), 728.
8. [8]
  马艾琳, 谌礼婷, 柳虎军, 陆黎, 侯章群, 廖洪利. 化学与生物工程, 2022, 39 (10), 6.
9. [9]
  胡艾希, 董先明, 曹声春, 范国枝, 李文生. 中国药物化学杂志, 2001, No. 2, 42.
10. [10]
  王宁宁, 鲍猛, 牟宗刚, 王慧, 刘传仁. 山东化工, 2011, 40 (12), 28.
11. [11]
  Chassaing, C.; Haudrechy, A.; Langlois, Y. Tetrahedron Lett. 1997, 38 (25), 4415.Chassaing, C.; Haudrechy, A.; Langlois, Y. Tetrahedron Lett. 1997, 38 (25), 4415.
12. [12]
  Wu, G.; Guo, H. F.; Gao, K.; Liu, Y. N.; Bastow, K. F.; Morris-Natschke, S. L.; Lee, K. H.; Xie, L. Bioorg. Med. Chem. Lett. 2008, 18 (19), 5272.Wu, G.; Guo, H. F.; Gao, K.; Liu, Y. N.; Bastow, K. F.; Morris-Natschke, S. L.; Lee, K. H.; Xie, L. Bioorg. Med. Chem. Lett. 2008, 18 (19), 5272.
13. [13]
  Ware, E. Chem. Rev. 1950, 46 (3), 403.Ware, E. Chem. Rev. 1950, 46 (3), 403.

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 60
HTML全文浏览量: 10

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

通讯作者: 庄俊鹏，Email: zhuangjp@mail.buct.edu.cn

English

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

Corresponding author: Junpeng Zhuang, zhuangjp@mail.buct.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

通讯作者: 庄俊鹏，Email: zhuangjp@mail.buct.edu.cn

English

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

Corresponding author: Junpeng Zhuang, zhuangjp@mail.buct.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs