原人参二醇组皂苷选择性制备人参皂苷20(S)-Rg3和Rg5及其生成机理研究  

The selective preparation of ginsenoside 20(S)-Rg3 and Rg5 from protopanaxadiol group saponins and its formation mechanism

作　　者：张浩然 朱小涵 张跃伟[1] 李琳 李玲 成乐琴[1] ZHANG Haoran;ZHU Xiaohan;ZHANG Yuewei;LI Lin;LI Ling;CHENG Leqin(Department of Pharmacy and Applied Chemistry,Jilin Institute of Chemical Technology,Jilin 132022,China;Forensic Center of Changchun Public Security Bureau,Changchun 130000,China;Jilin Caisenren Biotechnology Co.Ltd.,Jilin 132022,China)

机构地区：[1]吉林化工学院化学与制药工程学院,吉林吉林132022 [2]长春市公安司法鉴定中心,吉林长春130000 [3]吉林省彩森仁生物科技有限责任公司,吉林吉林132022

出　　处：《食品与发酵工业》2023年第2期129-137,共9页Food and Fermentation Industries

基　　金：吉林省科技厅重点科技研发项目(20180201073YY);2019年吉林省人才开发资金资助项目。

摘　　要：该文以原人参二醇(protopanaxadiol,PD)型皂苷为原料,盐酸为催化剂,选择性制备稀有人参皂苷Rg5和20(S)-Rg3。主要探索了酸浓度、乙醇浓度、反应温度以及反应时间对制备人参皂苷20(S)-Rg3和Rg5的影响,并通过同位素标记法研究了人参皂苷Rg3的生成机理。结果表明,当PD型皂苷质量浓度为15 mg/mL,HCl浓度为0.02 mol/L,乙醇体积分数为99%,反应温度为60℃,反应时间为3.5 h时,20(S)-Rg3和Rg5收率分别为15.32%和50.12%,20(S)-Rg3的de值为98.28%。同位素标记法研究反应机理表明,PD皂苷在盐酸催化下高立体选择性地生成Rg3是S_(N)2机理。该方法催化剂价廉易得,操作简单,在生成Rg5的同时又能高立体选择性生成20(S)-Rg3,为一步合成多种高活性稀有人参皂苷提供新的思路。Rare ginsenosides Rg5 and 20(S)-Rg3 are selectively prepared from PD-type saponins with hydrochloric acid as a catalyst.The effects of acid concentration,ethanol concentration,reaction temperature,and reaction time on the preparation of ginsenoside 20(S)-Rg3 and Rg5 were mainly explored,and the formation mechanism of ginsenoside Rg3 was studied by the isotope labelling method.Results showed that when the concentration of PD-type saponin was 15 mg/mL,the concentration of HCl was 0.02 mol/L,the concentration of ethanol was 99%,the reaction temperature was 60℃,and the reaction time was 3.5 h,the yields of 20(S)-Rg3 and Rg5 were 15.32%and 50.12%,respectively,with a de value up to 98.28%for 20(S)-Rg3.The reaction mechanism of the isotope labelling method showed that ginsenoside Rg3 was highly stereoselectively prepared from PD saponin under the catalysis of hydrochloric acid via an S_(N)2 mechanism.Using this method,20(S)-Rg3 could be obtained with high stereoselectivity while Rg5 was obtained,which had the advantages of low-cost and easy-to-obtain catalyst,simple operation,etc.,and provided a new idea for the one-step synthesis of a variety of high-activity rare ginsenosides.

关 键 词：原人参二醇组皂苷 人参皂苷Rg5 20(S)-人参皂苷-Rg3 选择性制备 生成机理 

分 类 号：TQ464.3[化学工程—制药化工]