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第 36 卷第 3 期 精 细 化 工 Vol.36, No.3
201 9 年 3 月 FINE CHEMICALS Mar. 2019

医药与日化原料
咖啡酰氨基酸乙酯的合成及其抗氧化活性

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王 东，马金凤，蔡明旭，祝 钧
（北京工商大学 理学院，北京 100048）

摘要：以 L-氨基酸乙酯盐酸盐和咖啡酸为原料，1-(3-二甲基氨基丙基)-3-乙基碳二亚胺盐酸盐（EDC）及 1-羟
基苯并三唑（HOBt）为催化剂，合成咖啡酰缬氨酸乙酯、咖啡酰亮氨酸乙酯、咖啡酰蛋氨酸乙酯、咖啡酰酪氨
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酸乙酯 4 种产物。利用 HNMR、质谱及红外对产物进行了表征；通过清除 DPPH 自由基、羟基自由基及红细胞溶
血等实验分别对咖啡酰氨基酸乙酯类物质的体外抗氧化活性及刺激性进行了初步评价。结果表明，以该法合成
4 种咖啡酰氨基酸乙酯，收率在 75%~82%。咖啡酸与氨基酸结合后，4 种产物均呈现较好的抑制 DPPH 自由基、
羟基自由基活性的效果；咖啡酰缬氨酸乙酯（Ⅲa）清除 DPPH 自由基能力最强，其 IC 50 为（11.23±0.24）µmol/L；
咖啡酰蛋氨酸乙酯（Ⅲc）清除羟基自由基能力最强，其 IC 50 为（0.24 ± 0.002）mmol/L；3 种咖啡酰氨基酸乙酯
相对于咖啡酸单体对于红细胞膜具有更弱的刺激性。咖啡酰氨基酸乙酯类物质抗氧化活性明显强于 L-抗坏血酸
（V C ），可作为潜在的抗氧化剂。
关键词：咖啡酰氨基酸乙酯；咖啡酸；抗氧化性；红细胞溶血；医药与日化原料
中图分类号：TQ245 文献标识码：A 文章编号：1003-5214 (2019) 03-0494-05

Synthesis and Anti-oxidation Activity of Caffeic Acid
Amino Acid Ethyl Ester Derivatives

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WANG Dong, MA Jin-feng, CAI Ming-xu, ZHU Jun
（School of Science, Beijing Technology and Business University, Beijing 100048, China）

Abstract: Caffeylvaline ethyl ester, caffeoylleucine ethyl ester, caffeoyl methionine ethyl ester, and caffeoyl
tyrosine ethyl ester were synthesized from L-amino acid ethyl ester hydrochloride with caffeic acid in the
presence of a catalytic amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC)
and 1-hydroxybenzotrizole (HOBt). Their structures were identified by mass spectroscopy (MS), proton
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nuclear magnetic resonance ( HNMR) and Fourier transform infrared (FTIR) spectroscopy. Then, their
antioxidant activities and irritation were measured by the scavenging capability to DPPH and hydroxyl free
radicals, as well as erythrocyte hemolysis experiment. The results showed that four N-caffeoyl amino acid
ethyl esters were synthesized with yields between 75% and 82%. After the combination of caffeic acid and
amino acid, all products exhibited good inhibition effects against DPPH free radical and hydroxyl radical.
Among them, caffeoylvaline ethyl ester (Ⅲa) had the strongest ability to scavenge DPPH free radical, and
its IC 50 value was (11.23±0.24) μmol/L. Caffeoylmethionine ethyl ester (Ⅲc) had the strongest ability to
scavenge hydroxyl free radical with an IC 50 value of (0.24±0.002) mmol/L. Three synthesized caffeoyl
amino acid ethyl esters were less irritating to the erythrocyte membrane than caffeic acid monomer. The
antioxidant activities of N-caffeoyl amino acid ethyl esters derivatives were more effective than Vitamin C
and could be used as a new potent antioxidant.
Key words: caffeic acid amino acid ethyl ester; caffeic acid; antioxidation; hemolysis of erythrocytes; drug
and cosmetic materials
Foundation items: Outstanding Teachers of Beijing Colleges and Universities Supported Program
(19005753005); Graduate Research Capacity Improvement Program in 2018 (19008001491)

收稿日期：2018-08-12; 定用日期：2018-11-26; DOI: 10.13550/j.jxhg.20180592
基金项目：北京市高等学校教学名师支持项目（19005753005）；2018 年研究生科研能力提升计划项目资助（19008001491）
作者简介：王 东（1993—），男，硕士生。联系人：祝 钧（1966—），男，教授，E-mail：zhujun@btbu.edu.cn。