取代基结构对螺旋聚乙炔高效液相色谱手性固定相对映选择性分离性能的影响

李悦; 史歌; 康舒铭; 曾华; 张洁; 宛新华

doi:10.11777/j.issn1000-3304.2022.22429

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取代基结构对螺旋聚乙炔高效液相色谱手性固定相对映选择性分离性能的影响

研究论文 | 更新时间：2024-01-18

- 取代基结构对螺旋聚乙炔高效液相色谱手性固定相对映选择性分离性能的影响
  增强出版
- Effect of Substituent on the Enantioseparation Property of Helical Polyacetylene-based Chiral Stationary Phases for High-performance Liquid Chromatography
- 高分子学报 2023年54卷第5期页码：612-621
- 作者机构：
  
  1.北京分子科学国家研究中心北京大学化学与分子工程学院高分子化学与物理教育部重点实验室北京 100871
  2.郑州大学材料科学与工程学院河南省活性聚合与功能纳米材料国际联合实验室河南省先进尼龙材料及应用重点实验室郑州 450001
- 作者简介：
  
  E-mail: xhwan@pku.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣51833001;52273002);51921002,22105179┫
- DOI：10.11777/j.issn1000-3304.2022.22429
  中图分类号：
- 纸质出版日期：2023-05-20，
  
  网络出版日期：2023-02-24，
  
  收稿日期：2022-12-13，
  
  录用日期：2023-01-16
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李悦,史歌,康舒铭等.取代基结构对螺旋聚乙炔高效液相色谱手性固定相对映选择性分离性能的影响[J].高分子学报,2023,54(05):612-621.

Li Yue,Shi Ge,Kang Shu-ming,et al.Effect of Substituent on the Enantioseparation Property of Helical Polyacetylene-based Chiral Stationary Phases for High-performance Liquid Chromatography[J].ACTA POLYMERICA SINICA,2023,54(05):612-621.
李悦,史歌,康舒铭等.取代基结构对螺旋聚乙炔高效液相色谱手性固定相对映选择性分离性能的影响[J].高分子学报,2023,54(05):612-621. DOI： 10.11777/j.issn1000-3304.2022.22429.

Li Yue,Shi Ge,Kang Shu-ming,et al.Effect of Substituent on the Enantioseparation Property of Helical Polyacetylene-based Chiral Stationary Phases for High-performance Liquid Chromatography[J].ACTA POLYMERICA SINICA,2023,54(05):612-621. DOI： 10.11777/j.issn1000-3304.2022.22429.

摘要

基于(

)-2-乙炔基吡咯烷、炔丙胺和炔丙醇合成了5种乙炔基单体——(

-对氯苯基氨基甲酰基-2-乙炔基吡咯烷(I)、(

-对氯苯甲酰基-2-乙炔基吡咯烷(II)、

-对氯苯基-

'-炔丙基脲(III)、

-炔丙基氨基甲酸对氯苯酯(IV)和

-对氯苯基氨基甲酸炔丙酯(V)；通过Rh(nbd)BPh

催化的配位共聚合反应制备了单体I分别与单体II~V构成的光学活性螺旋共聚物——I

ran

-II

、I

ran

-II

、I

ran

-III

、I

ran

-IV

和I

ran

-V

. 研究了共聚物的结构和组成对旋光性质的影响，并用高效液相色谱评估了其作为涂敷型手性固定相对9种标准底物的对映选择性分离性能. 研究结果表明，I

ran

-II

的光学活性最佳，表现出优于其他共聚物的手性识别性能，对安息香(

=1.40)与乙酰丙酮钴(

=1.88)展现出良好的分离能力. 手性单体II的引入对共聚物主链螺旋手性的影响较小，但明显干扰侧基的不对称有序排列，降低对映选择性分离性能；不论连接基团的结构和方向，非手性炔丙基单体的引入都显著降低共聚物的光学活性和对映选择性分离性能.

Abstract

Based on (

)-ethynylpyrrolidine

propargylamine and propargyl alcohol

five monosubstituted ethynyl monomers

including (

)

-N-

[(4-chlorophenyl)carbamoyl]-2-ethynyl pyrrolidine (Ⅰ)

(

)

-N-

(4-chlor robenzoyl)-2-ethynyl pyrrolidine (Ⅱ)

1-(

-chlorophenyl)-3-(2-propynyl)urea (Ⅲ)

-chlorophenyl

-propargylcarbamate (Ⅳ) and propargyl

-(4'-chlorophenyl)carbamate (Ⅴ) were synthesized. Optically active helical copolymers

ran

-II

ran

-II

ran

-III

ran

-IV

and I

ran

-V

were prepared through coordination polymerization catalyzed by Rh(nbd)BPh

of I with II to V

respectively. The effect of the structure and composition of the copolymers on the optical activity were studied

and the enantioseparation performance of the copolymers as coated chiral stationary phase toward 9 standard racemates were evaluated by high performance liquid chromatography. I

ran

-II

has the highest optical activity

showing better chiral recognition performance than other copolymers

and exhibited well chiral resolution ability for benzoin (

=1.40) and cobalt acetylacetonate (

=1.88). The introduction of chiral monomer II has little effect on the helicity of the copolymer backbone

but obviously interferes with the asymmetric arrangement of side groups and reduces the enantioseparation performance. The introduction of achiral propargyl monomers significantly reduces the optical activity and enantioseparation of copolymers regardless of the bond orientation.

关键词

螺旋聚乙炔手性固定相取代基结构高效液相色谱对映选择性分离

Keywords

Helical polyacetyleneChiral stationary phaseSubstituent structureHigh performance liquid chromatographyEnantioseparation

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