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  

Effect of Substituent on the Enantioseparation Property of Helical Polyacetylene-based Chiral Stationary Phases for High-performance Liquid Chromatography

作　　者：李悦 史歌 康舒铭 曾华 张洁[1] 宛新华[1] Yue Li;Ge Shi;Shu-ming Kang;Hua Zeng;Jie Zhang;Xin-hua Wan(Beijing National Laboratory for Molecular Sciences,Key Laboratory of Polymer Chemistry and Physics of Ministry of Education,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871;School of Materials Science and Engineering,Henan Joint International Research Laboratory of Living Polymerizations and Functional Nanomaterials,Henan Key Laboratory of Advanced Nylon Materials and Application,Zhengzhou University,Zhengzhou 450001)

机构地区：[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

出　　处：《高分子学报》2023年第5期612-621,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号51833001,52273002,51921002,22105179)资助项目.

摘　　要：基于(S)-2-乙炔基吡咯烷、炔丙胺和炔丙醇合成了5种乙炔基单体——(S)-N-对氯苯基氨基甲酰基-2-乙炔基吡咯烷(Ⅰ)、(S)-N-对氯苯甲酰基-2-乙炔基吡咯烷(Ⅱ)、N-对氯苯基-N'-炔丙基脲(Ⅲ)、N-炔丙基氨基甲酸对氯苯酯(Ⅳ)和N-对氯苯基氨基甲酸炔丙酯(Ⅴ);通过Rh(nbd)BPh_(4)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_(50)-ran-Ⅱ_(50)、Ⅰ_(80)-ran-Ⅱ_(20)、Ⅰ_(95)-ran-Ⅲ_(5)、Ⅰ_(95)-ran-Ⅳ_(5)和Ⅰ_(95)-ran-Ⅴ_(5).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_(80)-ran-Ⅱ_(20)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(α=1.40)与乙酰丙酮钴(α=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.Based on(S)-ethynylpyrrolidine,propargylamine and propargyl alcohol,five monosubstituted ethynyl monomers,including(S)-N-[(4-chlorophenyl)carbamoyl]-2-ethynyl pyrrolidine(Ⅰ),(S)-N-(4-chlor robenzoyl)-2-ethynyl pyrrolidine(Ⅱ),1-(p-chlorophenyl)-3-(2-propynyl)urea(Ⅲ),p-chlorophenyl N-propargylcarbamate(Ⅳ)and propargyl N-(4'-chlorophenyl)carbamate(Ⅴ)were synthesized.Optically active helical copolymers,Ⅰ_(50)-ran-Ⅱ_(50),Ⅰ_(80)-ran-Ⅱ_(20),Ⅰ_(95)-ran-Ⅲ_(5),Ⅰ_(95)-ran-Ⅳ_(5) and Ⅰ_(95)-ran-Ⅴ_(5),were prepared through coordination polymerization catalyzed by Rh(nbd)BPh_(4) 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_(80)-ran-Ⅱ_(20) has the highest optical activity,showing better chiral recognition performance than other copolymers,and exhibited well chiral resolution ability for benzoin(α=1.40)and cobalt acetylacetonate(α=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 

分 类 号：TQ317[化学工程—高聚物工业] O652.63[理学—分析化学]