摘要
以3,4-二羟基苯甲醛为原料,经Knoevenagel缩合、水解反应合成β-（3,4-二羟基苯基）丙酮酸,利用对甲基苯磺酸催化β-（3,4-二羟基苯基）丙酮酸和冰片反应合成了β-（3,4-二羟基苯基）丙酮酸冰片酯,最后利用面包酵母生物催化不对称合成了丹参素冰片酯（DBZ）。系统考察了葡萄糖加入量、反应时间、pH及β-环糊精加入量等因素对面包酵母生物催化合成不对称丹参素冰片酯的影响,结果表明：在底物β-（3,4-二羟基苯基）丙酮酸冰片酯加入量为0.5 g时,其最佳反应条件为：葡萄糖30 g、β-环糊精1.5 g、pH为7、反应时间24 h,此条件下对映体过量值（e.e.）高达84.9%,产物主要为S构型的丹参素冰片酯。该工艺条件温和、成本较低,是一条极具价值的丹参素冰片酯生产工艺。
β-（3,4-dihydroxyphenyl） pyruvic acid was first synthesized by Knoevenagel condensation and hydrolysis reactions of 3,4-dihydroxybenzaldehyde. Then,β-（3,4-dihydroxyphenyl） pyruvate borneol ester was prepared from β-（3,4-dihydroxyphenyl） pyruvic acid with borneol in the presence of a catalytic amount of p-toluenesulfonic acid. Finally,biocatalytic synthesis of target product Danshensu borneol ester（DBZ） catalyzed by bread＇s yeast was obtained. The factors affecting synthesis of DBZ such as amount of glucose,reaction time,pH valve and amount of β-cyclodextrin were systematacially investigated. The results showed that when the amount of β-（3,4-dihydroxyphenyl） pyruvate borneol ester was 0.5 g,the optium reaction conditions were as follows： amount of glucose 30 g,reaction time 24 h,pH 7,amount of β-cyclodextrin 1.5 g. Under these conditons,enantiomeric excess（e.e.） valve of the target product was as high as 84.9%,and S enantiomer was the predominant component. The process in this paper is mild and low cost,and is a very valuable process for the production of DBZ.
作者
匡新谋
孙颖
白亚军
南叶飞
郑晓晖
KUANG Xin-mou;SUN Ying;BAI Ya-jun;NAN Ye-fei;ZHENG Xiao-hui(School of Chemical Engineering, Ningbo Polytechnic, Ningbo 315800, Zhejiang, China;College of Life Sciences Northwest University, Xi＇an 710069, Shaanxi, China;College of Chemistry and Chemical Engineering, Xi＇an Shiyou University, Xi＇ an 710065, Shaanxi, China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2018年第6期987-991,共5页
Fine Chemicals
基金
国家重大仪器设备开发专项(2013YQ17052509)
中国长江学者课程和教育部大学创新研究团队(IRT_15R55)~~
关键词
面包酵母
生物催化
不对称还原
Β-环糊精
丹参素冰片酯
催化技术
baker＇s yeast
biocatalysis
asymmetric reduction
fl-cyclodextrin
danshensu bomeol ester
catalysis technology
