Page 181 - 《精细化工》2021年第4期

第 38 卷第 4 期 精 细 化 工 Vol.38, No.4
202 1 年 4 月 FINE CHEMICALS Apr. 2021

医药与日化原料
构型转换法制备赤式紫胶桐酸及反应机理分析

1
1
3
1*
1*
石小娟 1,2 ，唐保山 ，张雯雯 ，李 坤 ，涂行浩 ，张 弘
（1. 中国林业科学研究院资源昆虫研究所，国家林业和草原局特色森林资源工程技术研究中心，云南 昆明
650233；2. 南京林业大学 化学工程学院，江苏 南京 210037；3. 中国热带农业科学院南亚热带作物研
究所，农业部热带果树生物学重点实验室，广东 湛江 524091）
13
1
摘要：以苏式紫胶桐酸为原料，通过构型转换法制备赤式紫胶桐酸。采用 FTIR、质谱、核磁（ HNMR / CNMR）、
TG、DSC、XRD、手性拆分、比旋光度等表征手段对所得产物进行了分析确证。对紫胶桐酸苏式到赤式构型的
转换机理进行了初步探究。结果表明：FTIR、质谱、核磁显示，产物与苏式紫胶桐酸结构一致；XRD、DSC、
TG 结果表明，苏式紫胶桐酸与产物具有相同晶型，但产物熔点更高，晶胞尺寸更小；手性拆分结果显示，产物
为紫胶桐酸的光学异构体，从而确定产物为赤式紫胶桐酸。对中间产物的结构表征表明，苏式紫胶桐酸到赤式
紫胶桐酸构型转换的机理为卤素和羟基之间双分子亲核取代（S N 2）和双分子消除反应（E2）同时发生的反应，
羟基和卤素间的两次 S N 2 反应是发生构型转换反应（Walden 转换）的关键；羟基/卤素间的 E2 反应是苏式紫胶
桐酸能够彻底转化为赤式紫胶桐酸的原因。
关键词：紫胶桐酸；苏式；赤式；构型转换；机理；医药原料
中图分类号：TQ351.7；TQ225.4；TQ465.5；S713 文献标识码：A 文章编号：1003-5214 (2021) 04-0815-08

Preparation of erythro aleuritic acid by configuration transformation
method and analysis of reaction mechanism

1
1
1*
1,2
3
1*
SHI Xiaojuan , TANG Baoshan , ZHANG Wenwen , LI Kun , TU Xinghao , ZHANG Hong
（1. Research Center of Engineering and Technology on Characteristic Forest Resources, National Forestry and
Grassland Administration, Research Institute of Resources Insects, Chinese Academy of Forestry, Kunming 650233,
Yunnan, China; 2. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China;
3. Key Laboratory of Tropical Fruit Biology, Ministry of Agriculture, South Subtropical Crops Research Institute,
Chinese Academy of Tropical Agricultural Sciences, Zhanjiang 524091, Guangdong, China）
Abstract: Erythro aleuritic acid was prepared by configuration transformation method from thero aleuritic
1
acid. The products were characterized by FTIR, mass spectrometry, nuclear magnetic resonance ( HNMR
13
and CNMR), TG, DSC, XRD, chiral resolution and specific rotation. The transformation mechanism of
thero aleuritic acid into erythro aleuritic acid was primary explored. FTIR, mass spectrometry and nuclear
magnetic resonance results showed that the structure of the product was consistent with thero aleuritic acid.
XRD, DSC and TG results suggested that thero aleuritic acid and the product had the same crystal type, but
the product had higher melting point and smaller crystal cell structure. The chiral resolution result showed
that the product was an optical isomer of aleuritic acid, which was determined to be erythro aleuritic acid.
Based on the structural characterization of the intermediates, the mechanism of configuration
transformation from thero aleuritic acid to erythro aleuritic acid was the simultaneous reaction of
nucleophilic substitution (S N2) and elimination reaction (E2) between the halogens and hydroxyl. The twice
S N2 reactions between the hydroxyl and halogens were the key to the configuration transformation reaction
(Walden transformation). The E2 reaction of hydroxyl/halogen was the reason for the complete

收稿日期：2020-08-22; 定用日期：2020-11-16; DOI: 10.13550/j.jxhg.20200787
基金项目：中央级公益性科研院所基本科研业务费专项资金（CAFYBB2018SY024、CAFYBB2017MA012）；国家高技术研究发展计
划（863 计划）项目（2014AA021801）
作者简介：石小娟（1993—），女，硕士生，E-mail：shixiaojuan414@163.com。联系人：李 坤（1987—），男，助理研究员，博士，
E-mail：likunkm@163.com；张 弘（1963—），男，研究员，博士，E-mail：kmzhhong@163.com。