卤素交换法绿色合成1,3-二溴丙酮——推荐一个基础有机合成教学实验

引用本文: 苏胤伍, 郑绚文, 杜江辉, 李伯达, 王涛, 黄治炎. 卤素交换法绿色合成1,3-二溴丙酮——推荐一个基础有机合成教学实验[J]. 大学化学, 2024, 39(5): 307-314. doi: 10.3866/PKU.DXHX202311092 shu

Citation: Yinwu Su, Xuanwen Zheng, Jianghui Du, Boda Li, Tao Wang, Zhiyan Huang. Green Synthesis of 1,3-Dibromoacetone Using Halogen Exchange Method: Recommending a Basic Organic Synthesis Teaching Experiment[J]. University Chemistry, 2024, 39(5): 307-314. doi: 10.3866/PKU.DXHX202311092 shu

卤素交换法绿色合成1,3-二溴丙酮——推荐一个基础有机合成教学实验

陕西师范大学化学化工学院, 西安 710119
基金项目:
国家自然科学基金面上项目(21872090)

摘要: 基于有机合成方法学研究的一般过程，围绕“科学问题为目标导向”的实验教学指导原则，本文将1,3-二溴丙酮的绿色合成工艺开发为有机化学基础教学实验，首次将卤素交换反应应用于实验教学中。以1,3-二氯丙酮和溴化锂为原料，采用二氯甲烷和丙酮组成的混合溶剂(体积比10 : 1)打破卤素交换反应平衡，有效促进正向反应进行。在此基础上，本文使用3.5当量溴化锂，40 °C回流反应1.5 h，以97%的分离产率实现了1,3-二溴丙酮的绿色合成，纯度高于97%，精制后纯度为98.8%。本实验所用试剂环境友好，安全性高，教学时长约为4 h，不仅涉及多种有机化学实验的基本操作，还包含反应监测、结构表征、纯度分析等重要环节，非常适合用于有机化学基础实验教学。同时，以本实验方案为蓝本，结合有关卤素交换反应发展历史和1,3-二溴丙酮应用发展的微课学习和拓展练习，实现理论知识与合成实践之间的互动，提升化学专业本科生解决有机合成问题的综合能力，夯实化学类人才的培养质量。

关键词:

English

Green Synthesis of 1,3-Dibromoacetone Using Halogen Exchange Method: Recommending a Basic Organic Synthesis Teaching Experiment

School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China
Received Date: 29 November 2023
Revised Date: 13 March 2024

Abstract: Based on the general process of synthetic chemistry methodology and the “scientific problem-oriented” principle in laboratory teaching, this paper has developed a basic experiment of organic chemistry derived from the green synthesis of 1,3-dibromoacetone, and firstly applied halogen exchange reaction to laboratory teaching. Starting with 1,3-dichloroacetone and lithium bromide, the halogen exchange equilibrium was broken efficiently using mixture solvent of dichloromethane and acetone (10 : 1). Therefore, in the presence of 3.5 equivalents of lithium bromide, the green synthesis of 1,3-dibromoacetone was achieved with 97% isolated yield after refluxing 1.5 hours at 40 °C. The purity of desired product was higher than 97%, and up to 98.8% after recrystallization. The all reagents used in this experiment are safe and environmentally benign. The teaching time is about 4 hours, which not only involves basic operations of various organic chemistry experiments, but also includes important aspects such as reaction monitoring, structure characterization, and purity analysis. It is very suitable for basic organic chemistry laboratory teaching. At the same time, based on this experimental scheme, combined with the micro-course learning and exercises on the development history of halogen exchange reaction in application and development of 1,3-dibromoacetone, the interaction between theoretical knowledge and synthetic practice was realized. This improved the comprehensive ability of undergraduate of chemistry majors to solve synthetic chemistry problems and solidified the quality of talent cultivation in the field of chemistry.

Key words:

1. [1]
  习近平. 在中国科学院第二十次院士大会、中国工程院第十五次院士大会、中国科协第十次全国代表大会上的讲话.[2024-04-12]. https://www.moj.gov.cn/pub/sfbgw/gwxw/ttxw/202105/t20210528_424683.html
2. [2]
  李维红, 张奇涵, 吴忠云, 朱志伟, 高珍, 裴坚. 大学化学, 2018, 33(10), 7.
3. [3]
  陈水生, 乔瑞, 张淑萍, 时兆菊, 盛良全. 大学化学, 2014, 29(6), 51.
4. [4]
  向丹, 高培红, 张雯. 大学化学, 2016, 31(2), 11.
5. [5]
  张树永, 朱亚先，张剑荣. 大学化学, 2018, 33(10), 1.
6. [6]
  2013–2017年教育部高等学校化学类专业教学指导委员会. 大学化学, 2017, 32(8), 1.
7. [7]
  张树永, 朱亚先. 中国大学教学, 2018, No. 7, 55.
8. [8]
  田福平, 张艳娟, 贺民, 贾翠英, 陈静, 孟长功. 大学化学, 2018, 33(2), 29.
9. [9]
  欧阳小清. 大学化学, 2018, 33(2), 75.
10. [10]
  闫生忠, 张尊听, 白云山, 赵华荣, 周青. 大学化学, 2018, 33(2), 65.
11. [11]
  Tanabe, K.; Sugiura, M.; Ito, T.; Nishimoto, S.-i. Biorg. Med. Chem. 2012, 20, 5164.Tanabe, K.; Sugiura, M.; Ito, T.; Nishimoto, S.-i. Biorg. Med. Chem. 2012, 20, 5164.
12. [12]
  Gao, W.; Zhang, Y.; Ye, R.; Qi, X.; Chen, L.; Liu, X.; Tang, L.; Chen, L.; Chen, H.; Fan, Z. J. Agric. Food Chem. 2022, 70, 1047.Gao, W.; Zhang, Y.; Ye, R.; Qi, X.; Chen, L.; Liu, X.; Tang, L.; Chen, L.; Chen, H.; Fan, Z. J. Agric. Food Chem. 2022, 70, 1047.
13. [13]
  Yu, Y.; Li, G.; Wu, D.; Zheng, F.; Zhang, X.; Liu, J.; Hu, N.; Wang, H.; Wu, Y. J. Agric. Food. Chem. 2020, 68, 876.Yu, Y.; Li, G.; Wu, D.; Zheng, F.; Zhang, X.; Liu, J.; Hu, N.; Wang, H.; Wu, Y. J. Agric. Food. Chem. 2020, 68, 876.
14. [14]
  Storer, R. I.; Takemoto, T.; Jackson, P. S.; Brown, D. S.; Baxendale, I. R.; Ley, S. V. Chem. Eur. J. 2004, 10, 2529.Storer, R. I.; Takemoto, T.; Jackson, P. S.; Brown, D. S.; Baxendale, I. R.; Ley, S. V. Chem. Eur. J. 2004, 10, 2529.
15. [15]
  Kale, S. S.; Villequey, C.; Kong, X.-D.; Zorzi, A.; Deyle, K.; Heinis, C. Nat. Chem. 2018, 10, 715.Kale, S. S.; Villequey, C.; Kong, X.-D.; Zorzi, A.; Deyle, K.; Heinis, C. Nat. Chem. 2018, 10, 715.
16. [16]
  Finkelstein, H. Ber. 1910, 43, 1528.Finkelstein, H. Ber. 1910, 43, 1528.
17. [17]
  Kim, K. S.; Szarek, W. A. Can. J. Chem. 1981, 59, 878.Kim, K. S.; Szarek, W. A. Can. J. Chem. 1981, 59, 878.
18. [18]
  Menger, F. M.; Persichetti, R. A. J. Org. Chem. 1987, 52, 3451.Menger, F. M.; Persichetti, R. A. J. Org. Chem. 1987, 52, 3451.
19. [19]
  Eskandari, R.; Hess, J. P.; Tochtrop, G. P. Chem. Commun. 2021, 57, 7136.Eskandari, R.; Hess, J. P.; Tochtrop, G. P. Chem. Commun. 2021, 57, 7136.

扫一扫看文章

计量

PDF下载量: 1
文章访问数: 257
HTML全文浏览量: 21

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

卤素交换法绿色合成1,3-二溴丙酮——推荐一个基础有机合成教学实验

English

Green Synthesis of 1,3-Dibromoacetone Using Halogen Exchange Method: Recommending a Basic Organic Synthesis Teaching Experiment

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

卤素交换法绿色合成1,3-二溴丙酮——推荐一个基础有机合成教学实验

English

Green Synthesis of 1,3-Dibromoacetone Using Halogen Exchange Method: Recommending a Basic Organic Synthesis Teaching Experiment

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