Page 228 - 《精细化工》2021年第8期

第 38 卷第 8 期 精 细 化 工 Vol.38, No.8
202 1 年 8 月 FINE CHEMICALS Aug. 2021

精细化工中间体
香豆素-3-羧酸类化合物的绿色合成及

抗氧化性能测定

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金桂勇 ，程东旭 ，杜 佳 ，陈芝飞 ，赵森森 ，
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万 帅 ，赵铭钦 ，张晓平 ，席高磊
（1. 河南农业大学 烟草学院，河南 郑州 450002；2. 河南中烟工业有限责任公司 技术中心，河南 郑州
450016）
摘要：在以水为溶剂、无催化剂条件下加热促使水杨醛类化合物与米氏酸发生反应，合成了 18 种香豆素-3-羧酸
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类化合物。利用 HNMR 和 CNMR 对合成产物结构进行了表征；并通过抑制 HO•、还原型谷胱甘肽自由基（GS•）
和 2,2′-偶氮二异丁基脒二盐酸盐（AAPH）氧化 DNA 反应对其抗氧化活性进行检测，进而探究取代基种类和位
置对香豆素-3-羧酸类化合物抗氧化性能的影响。结果表明：绿色高效地合成了目标化合物，产率为 54.3%~95.6%；
18 种化合物均能够抑制 HO•、GS•和 AAPH 氧化 DNA，其相对空白组（DMSO）硫代巴比妥酸活性物质（TBARS）
吸光度百分数（TBARS 百分数）分别可达 69.42%~93.39%、75.23%~99.45%和 66.62%~97.72%；在抑制 HO•、
GS•和 AAPH 氧化 DNA 反应中，羟基取代化合物的 TBARS 百分数分别为 69.42%~77.67%、75.23%~82.87%和
66.62%~75.08%，远小于其他取代基的香豆素-3-羧酸类化合物，与水溶性维生素 E 的 TBARS 百分数相当，是
一类潜在的抗氧化剂。
关键词：香豆素-3-羧酸；无催化剂；绿色合成；抗氧化剂；自由基；精细化工中间体
中图分类号：TQ25 文献标识码：A 文章编号：1003-5214 (2021) 08-1722-07

Green synthesis and antioxidation activities of coumarin-3-carboxylic acids

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JIN Guiyong , CHENG Dongxu , DU Jia , CHEN Zhifei , ZHAO Sensen ,
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WAN Shuai , ZHAO Mingqin , ZHANG Xiaoping , XI Gaolei
（1. College of Tobacco Science, Henan Agricultural University, Zhengzhou 450002, Henan, China; 2. Technology
Center, China Tobacco Henan Industrial Co., Ltd., Zhengzhou 450016, Henan, China）
Abstract: Eighteen coumarin-3-carboxylic acids were obtained via the reaction of Meldrum's acid and
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various salicylaldehydes without catalyst in water. The products were confirmed by HNMR and CNMR,
and the antioxidant activities were evaluated by inhibiting DNA oxidation reaction by hydroxyl radical
(HO•), reductive glutathione radical (GS•) and 2,2′-azobis(2-methylpropionamidine) dihydrochloride
(AAPH). Furthermore, the effects of substituent types and positions on the antioxidant activity of
coumarin-3-carboxylic acids were investigated. The results showed that the target compounds in yields of
54.3%~95.6% were synthesized greenly and efficiently. All the compounds exhibited strong activities to
protect DNA against oxidation induced by HO•, GS• and AAPH. Their relative blank (DMSO)
thiobarbituric acid reactive substances (TBARS) absorbance percentage (TBARS percentage) were
69.42%~93.39%, 75.23%~99.45% and 66.62%~97.72%, respectively. In reaction of inhibiting HO•, GS•
and AAPH induced oxidation of DNA, the corresponding TBARS percentages of hydroxyl substituted
compounds were 69.42%~77.67%, 75.23%~82.87% and 66.62%~75.08%, far less than the other substituted
compounds, equal to that of water-soluble vitamin E, indicating they can be used as potential antioxidants.

收稿日期：2021-02-24; 定用日期：2021-04-21; DOI: 10.13550/j.jxhg.20210195
基金项目：国家自然科学基金（21801064）
作者简介：金桂勇（1998—），男，硕士生，E-mail：jinguiyong0303@sina.com。联系人：张晓平（1988—），女，副教授，E-mail：
xiaoping078@163.com；席高磊（1987—），男，博士，E-mail：xigaoleijida@126.com。