紫胶桐酸光学异构体的制备拆分及立体化学构成分析

doi:10.3969/j.issn.0253-2417.2019.03.010

林产化学与工业 ›› 2019, Vol. 39 ›› Issue (3): 72-78.doi: 10.3969/j.issn.0253-2417.2019.03.010

紫胶桐酸光学异构体的制备拆分及立体化学构成分析

李坤(),张雯雯,李凯,徐涓,马金菊,刘兰香,张弘*()

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 650224

收稿日期:2019-01-24 出版日期:2019-06-28 发布日期:2019-06-26
通讯作者: 张弘 E-mail:likunkm@163.com;kmzhhong@163.com
作者简介:李坤(1987-),男,河南信阳人,助理研究员,博士生,研究方向为天然产物化学及结构修饰; E-mail:likunkm@163.com
基金资助:
中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2017MA012);中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2018SY024)

Preparative Resolution and Stereochemical Composition of Aleuritic Acid Optical Isomers

Kun LI(),Wenwen ZHANG,Kai LI,Juan XU,Jinju MA,Lanxiang LIU,Hong ZHANG*()

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 650224, China

Received:2019-01-24 Online:2019-06-28 Published:2019-06-26
Contact: Hong ZHANG E-mail:likunkm@163.com;kmzhhong@163.com
Supported by:
中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2017MA012);中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2018SY024)

摘要/Abstract

摘要：

以前期建立的紫胶桐酸HPLC-ELSD手性检测拆分条件为基础，开发了超临界流体色谱（SFC）法制备紫胶桐酸对映异构体的拆分条件：CHIRALPAK AY-H色谱柱（25 cm×3.0 cm，5 μm），流动相组成为V（CO₂）:V（EtOH）=70:30，流速为70 mL/min，柱温35℃，检测波长为208 nm，进样质量浓度为77.78 g/L（溶剂为甲醇），进样体积为3.0 mL/次。通过以上方法从化学纯紫胶桐酸中分离制备得到A、B两种样品，以（±）-紫胶桐酸混旋体标准品为对照，采用红外光谱（FT-IR）、核磁共振（¹H NMR和¹³C NMR）、差示扫描量热法（DSC）、热重（TG）和X射线衍射（XRD）等表征，证实了样品A、B均为紫胶桐酸的立体异构体；通过比旋光度和振动圆二色谱（VCD）测试，确定了A、B互为对映体关系。依据前人采用化学合成方法所得苏式和赤式构型的熔点测定结果，并结合本研究结果可以得出：强碱皂化法从紫胶树脂中提取所得的紫胶桐酸为苏式构型的一组对映体，即9R，10R，16-三羟基十六烷酸与9S，10S，16-三羟基十六烷酸组成的混旋体。

关键词: 紫胶桐酸, 光学异构, 制备拆分, 立体构成

Abstract:

Based on the established detection method for chiral resolution of aleuritic acid by HPLC-ELSD, the resolution condition of stereoisomerism of aleuritic acid was established by supercritical fluid chromatography(SFC) method and the optimum conditions were as follows:CHIRALPAK AY-H(25 cm×3.0 cm, 5 μm)column, carbon dioxide-alcohol(70:30, volume ratio) as the mobile phase, the flow rate 70 mL/min, column temperature 35℃, detection wavelength 208 nm, sample injection concentration 77.78 g/L, injection volume 3 mL each time. Two compounds(A and B) were prepared by above SFC method. The result indicated that A and B were stereoisomers of aleuritic acid by characterization of FT-IR, ¹H NMR, ¹³C NMR, DSC, TG and XRD as well as by comparison with the authentic samples. Furthermore, A and B compounds were confirmed as enantiomers of aleuritic acid by specific rotation and vibrational circular dichroism(VCD) spectra. According to melting point of synthetic threo and erythro aleuritic acid previously reported, the stereochemical compositions of aleuritic acid extracted by strong alkali saponification process from lac resin were a couple of enantiomers with threo configuration and possibly composed by 9R, 10R, 16-trihydroxyhexadecanoic acid and 9S, 10S, 16-trihydroxyhexadecanoic acid.

Key words: aleuritic acid, stereoisomerism, preparative resolution, stereochemical composition

中图分类号:

TQ35
TS202.3

李坤,张雯雯,李凯,徐涓,马金菊,刘兰香,张弘. 紫胶桐酸光学异构体的制备拆分及立体化学构成分析[J]. 林产化学与工业, 2019, 39(3): 72-78.

Kun LI,Wenwen ZHANG,Kai LI,Juan XU,Jinju MA,Lanxiang LIU,Hong ZHANG. Preparative Resolution and Stereochemical Composition of Aleuritic Acid Optical Isomers[J]. Chemistry and Industry of Forest Products, 2019, 39(3): 72-78.

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紫胶桐酸光学异构体的制备拆分及立体化学构成分析

Preparative Resolution and Stereochemical Composition of Aleuritic Acid Optical Isomers

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