香豆素-3-羧酸的绿色合成及其光谱性质研究

doi:10.3866/PKU.DXHX202209093

Abstract

Abstract:

In this study, the preparation of coumarin-3-carboxylic acid was improved. For the preparation of the intermediate, green and nontoxic L-proline was used as the catalyst under solvent-free conditions. Subsequently, the target product (coumarin-3-carboxylic acid) was obtained in high yield by a "one-pot" reaction without separation. The molecular structure was characterized by infrared and nuclear magnetic resonance spectroscopies. Additionally, the properties of ultraviolet (UV) absorption and fluorescence were characterized. The improved experimental method is environmentally friendly and inexpensive, with high yield, good reproducibility, and strong comprehensiveness. This program cultivates the exploration, innovative research ideas, and teamwork ability of students. Moreover, it helps to improve the comprehensive experimental skills of students for analyzing and processing data and using theoretical knowledge to solve problems, which is suitable for promoting higher-grade undergraduate teaching.

Key words: Coumarin-3-carboxylic acid, Green synthesis, Solvent-free, Spectroscopic properties, Innovative design and improvement

Jing Wang, Fuxiang Song, Junze Zuo, Yuecheng Gong, Bingqian Zhang, Shuwen Wang, Hongtao Gao. Green Synthesis and Spectroscopic Properties of Coumarin-3-carboxylic Acid[J].University Chemistry, 2023, 38(4): 227-236.

Figures/Tables 16

References 11

1	Zhang Z. ; Bai Z. W. ; Ling Y. ; He Q. L. ; Huang P. ; Gu H. X. ; Hu R. F. Med. Chem. Res. 2018, (27), 1198.
2	王积涛; 胡青眉; 张宝申; 王永梅. 有机化学第1版. 天津: 南开大学出版社, 2000, 518.
3	Cao D. X. ; Liu Z. Q. ; Verwilst P. ; Koo S. Y. ; Jangjili P. ; Kim J. S. ; Lin W. Y. Chem. Rev. 2019, 119, 10403. doi: 10.1021/acs.chemrev.9b00145
4	王清廉; 李瀛; 高坤; 许鹏飞; 曹小平. 有机化学实验第3版. 北京: 高等教育出版社, 2010, 308- 309.
5	徐雅琴; 姜建辉; 王春. 有机化学实验第2版. 北京: 化学工业出版社, 2019, 109- 110.
6	马祥梅; 兰艳素; 刘青. 有机化学实验第1版. 北京: 化学工业出版社, 2020, 97- 99.
7	马军营; 顾少华; 李平. 有机化学实验第1版. 北京: 化学工业出版社, 2010, 146- 147.
8	邹碧群; 张业; 覃雯. 桂林师范高等专科学校学报, 2010, 24 (3), 190.
9	杨文生. 化学工程师, 2016, (11), 82.
10	Syed S. S. ; Amir A. K. ; Misbahul A. K. ; Shanti F. S. ; Mohd S. J. ; Pang S. C. Asian J. Chem. 2017, 29 (2), 261. doi: 10.14233/ajchem.2017.20142
11	Brijesh M. S. ; Ranjit S. A. ; Amol A. K. Green Chem. 2019, 21, 5639. doi: 10.1039/C9GC02447F

序号	催化剂	催化剂用量/% ^a	加热方式	溶剂	反应时间/min	分离产率/%
1	氯化胆碱	10	回流	乙醇	120	0
2	氨基磺酸	10	回流	乙醇	120	0
3	L-赖氨酸	10	回流	乙醇	120	0
4	DL-色氨酸	10	回流	乙醇	120	0
5	甘氨酸	10	回流	乙醇	120	0
6	二乙胺	10	回流	乙醇	120	26
7	碳酸钾	10	回流	乙醇	120	32
8	L-脯氨酸	10	回流	乙醇	90	85

序号	催化剂	催化剂用量/%	温度/℃	溶剂	反应时间/min	分离产率/%
1	L-脯氨酸	10	80	乙醇	90	85
2	L-脯氨酸	10	80 ^a	乙醇	90	16
3	L-脯氨酸	10	100	离子液体	90	0
4	L-脯氨酸	10	100	二甲基亚砜	90	89
5	L-脯氨酸	10	80	无	120	56
6	L-脯氨酸	10	90	无	90	87
7	L-脯氨酸	10	100	无	60	95
8	L-脯氨酸	10	110	无	40	87

序号	催化剂	催化剂用量/%	温度/℃	溶剂	反应时间/min	分离产率/%
1	L-脯氨酸	10	100	无	60	95
2	L-脯氨酸	5	100	无	60	82
3	L-脯氨酸	15	100	无	60	95

反应方式	香豆素-3-羧酸乙酯质量/g	香豆素-3-羧酸质量/g	总产率/%
分步合成	2.07	1.54	81
“一锅煮”	无	1.76	92

改进项目	改进前	改进后
实验类型	验证性实验	综合、研究性实验
催化剂	六氢吡啶/冰醋酸	L-脯氨酸
温度/℃	80	100
溶剂	乙醇	无
反应时间/h	2.0	1.0
合成方法	两步法	一锅煮
产率/%	81	92
绿色化	无	催化剂环境友好，无溶剂
实验拓展	无	光谱性质研究
研究性内容	无	催化剂种类、用量，反应时间、温度，加热方式，溶剂种类，分离提纯方法
实验内容	合成	合成，结构表征，光谱性质
文献查阅及阅读能力	未涉及	能够查阅中外文文献，并归纳总结
团队合作与交流能力	较弱	讨论设计实验方案，合理安排步骤，交流分析数据等方面有较大提高
数据整理、分析能力	弱	熟练运用软件绘制图表，综合理论知识分析、处理数据等能力有很大提高
创新、严谨的科研思维能力	弱	提出多个实验优化方案，多种手段表征结构，多次补充完善测试数据
实验成果表达	实验报告	实验报告，小论文，PPT汇报

Green Synthesis and Spectroscopic Properties of Coumarin-3-carboxylic Acid

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