Page 104 - 201812

第 35 卷第 12 期 精 细 化 工 Vol.35, No.12
2018 年 12 月 FINE CHEMICALS Dec. 2018

医药与日化原料
2-叠氮肉桂酸苄酯催化加氢制备 α-氨基酸

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范娜娜，李 锐 ，马丹丹，李学强
（宁夏大学 化学化工学院，宁夏 银川 750021）

摘要：以叠氮乙酸乙酯与芳香醛为原料，通过醛酯缩合反应、皂化反应及苄酯化反应，合成了 10 个 2-叠氮肉桂
酸苄酯类化合物。对 2-叠氮肉桂酸苄酯加氢反应的条件进行了考察，筛选出最优反应条件为：Pd/C（Pd 质量分
数 10%）用量为底物质量的 30%、甲醇为溶剂、加氢压力为 3 MPa。通过上述反应条件，可以一步实现底物中
3 个位点（叠氮基团、碳碳双键以及苄基酯）的加氢反应，以 76%~89%的收率合成了一系列 α-氨基酸。核磁监
控体系表明：该转化的反应历程虽较为复杂，但最终产物单一。反应后处理简单，只需过滤去除 Pd/C，即可得
到纯净的 α-氨基酸产物。
关键词：氨基酸；苯丙氨酸；催化加氢反应；多位点反应；叠氮化合物；医药与日化原料
中图分类号：O629.71 文献标识码：A 文章编号：1003-5214 (2018) 12-2072-06

Catalytic Hydrogenation of Benzyl -Azidocinnamates to -Amino Acids

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FAN Na-na, LI Rui , MA Dan-dan, LI Xue-qiang
（College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China）

Abstract: A new method for the preparation of -amino acids was designed and realized by using a
hydrogenation reaction. Ten benzyl -azidocinnamates were prepared from ethyl 2-azidoacetate with
aromatic aldehydes through the following combined processes of condensation of aldehyde and ester,
saponification of methyl -azidocinnamates and esterification of -azidocinnamic acids with benzyl
alcohol. Then, the hydrogenation of benzyl -azidocinnamates was investigated. The optimized conditions
were obtained as follows: Pd/C (mass fraction of Pd is 10%) dosage 30% of the substrate mass, using
methanol as solvent, hydrogen gas pressure 3 MPa. Under these conditions, the three-site conversion was
featured with the combination of the reduction of azido group, the hydrogenation of C==C bond and the
hydrogenolysis of benzyl ester, efficiently affording the corresponding -amino acids in 76%~89% yields.
The NMR analysis of the reaction mixture indicated that although the hydrogenation process complicated,
the ultimate product was clearly delivered. The pure -amino acids were obtained by a very simple
filtration to remove the Pd/C catalyst.
Key words: -amino acid; phenylalanine; catalytic hydrogenation; multisite conversion; azides; drug and
cosmetic materials
Foundation items: National Nature Science Foundation of China (21762035, 21662026); Science and
Technology Innovation Leading Talent Training Program of Ningxia Province (KJT2015002)

[3]
[2]
-氨基酸（结构如下所示）中含有 3 个要素， 对称 Aldol 反应 ，Michael 加成 等转化。
即：氨基、羧基以及氨基碳的立体化学中心。-氨
基酸不仅在生命活动中有重要作用，且被广泛应用
于食品、饲料、药物及生物降解塑料的生产中。在
合成化学领域，此类化合物也有特别广泛的应用，
[1]
是重要的合成砌块 ，可用作手性小分子来催化不

收稿日期：2018-06-08; 定用日期：2018-11-23; DOI: 10.13550/j.jxhg.20180424
基金项目：国家自然科学基金（21762035、21662026）；宁夏回族自治区 “科技创新领军人才培养计划”（KJT2015002）
作者简介：范娜娜（1991—），女，硕士生。联系人：李 锐（1980—），女，副教授，博士，电话：0951-2062274，E-mail：ruili@nxu.edu.cn。