2-叠氮肉桂酸苄酯催化加氢制备α-氨基酸  

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

作　　者：范娜娜 李锐 马丹丹[1] 李学强[1] FAN Na-na;LI Rui;MA Dan-dan;LI Xue-qiang(College of Chemistry and Chemical Engineering,Ningxia University,Yinehuan 750021,Ningxia,China)

机构地区：[1]宁夏大学化学化工学院

出　　处：《精细化工》2018年第12期2072-2077,共6页Fine Chemicals

基　　金：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)~~

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。A new method for the preparation of α-amino acids was designed and realized by using a hydrogenation reaction.Ten benzyl α-azidocinnamates were prepared from ethyl 2-azidoacetate with aromatic aldehydes through the following combined processes of condensation of aldehyde and ester, saponification of methyl α-azidocinnamates and esterification of a-azidocinnamic acids .with benzyl alcohol.Then,the hydrogenation of benzyl α-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 α-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 α-amino acids were obtained by a very simple filtration to remove the Pd/C catalyst.

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 

分 类 号：O629.71[理学—有机化学]