液相色谱手性固定相的制备及其性能研究
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摘要
在查阅、分析和总结国内外大量的高效液相色谱手性分离文献的基础上，设计合成了八种新的液相色谱刷型手性键合相，分别是R-(+)-2-甲基-1-对氯苯基-1-丙胺和S-(-)-2-甲基-1-对氯苯基-1-丙胺通过二酸酐、二异氰酸酯与氨丙基硅胶相连制备的固定相(-Ⅺ，Ⅸ)，或二者之一与L-异亮氨酸、L-亮氨酸、L-缬氨酸共价键合后通过间隔臂再与氨丙基硅胶相连制备的手性固定相(Ile-Ⅶ，-Ile-Ⅶ；Leu-Ⅶ，-Leu-Ⅶ；Val-Ⅶ，-Val-Ⅶ)。合成过程的中间体中有十几个新化合物，对其中13个关键的中间体新化合物通过熔点、旋光度、元素分析、红外光谱、核磁共振等方法进行了表征；八种新的手性固定相通过元素分析、显微红外光谱等方法进行了表征，测定了柱效。这八种新的固定相用于液相色谱分离，研究结果证明它们都有手性分离能力。除直接键合氨丙基硅胶的-Ⅺ，Ⅸ固定相手性分离能力不强而外，其余六种固定相或它们的串联组合对苯甲酰基亮氨酸甲酯、苯甲酰基丙氨酸甲酯、乙酰基苯丙氨酸甲酯外消旋化合物显示出较好的拆分能力。基于色谱分离实验数据，对其中一些外消旋化合物在这些新手性固定相上的拆分机理作了初步探讨，认为L-氨基酸部分对手性分离有较大贡献，手性胺部分的引入，与氨基酸部分的某种协同作用对手性分离也有重要影响。八种新的液相色谱手性键合相的应用还有待进一步研究。
本文的另一部分合成了纤维素-三(3，5-二甲基苯基氨基甲酸酯)，并将其涂敷于氨丙基硅胶的表面，制备出涂敷型高效液相色谱手性固定相(CDMPC)，在该固定相上对除草剂氯氟草醚乙酯对映体、麦草伏甲酯对映体的分离进行了研究；在此色谱固定相上还对戊唑醇及其杂质、三唑酮及其杂质、甲霜灵系列化合物、苯并咪唑衍生物、杀螨剂尼索朗等对映体进行了手性分离研究，除三唑酮、甲霜灵和甲霜灵中间体而外其余均为在此类固定相上首次拆分。这些生物活性物质及其相关化合物的手性分离，纤维素-三(3，5-二甲基苯基氨基甲酸酯)涂敷型手性固定相拆分机理的探讨，不仅实现了外消旋农药的手性分离，而且分离度一般较大，这为其制备性分离，光学异构体活性差异研究、代谢及残留等课题打下了坚实的基础；也将为其单体的不对称合成等研究提供重要的检测手段。
In order to develop Pirkle Type chiral stationary phases (CSPs) of High-Performance Liquid Chromatography(HPLC), eight kinds of amino acid derivatives including chiral amines of (R-(+)-2-methyl-1 -(p-chlorobenphyl)-1 -propanamine and
S-(-)-2-2-methyl-1-(p-chlorobenphyl)-l-propanamine) covalated chiral stationary phases have been designed and synthesized, and their application in resolution of enantiomers by HPLC was studied. This eight kinds of novel chiral stationary phases were Ile-VII,-Ile-VII; Leu-VII,Leu-VII; Val-VII, -Val-VII, -XIand IX. The Ile-VII and -Ile-VII CSPs were derivatives of L-isoleucine prepared by covalently bonding to R-(+)amine or S-(-)-amine; The Leu-VII and-Leu-VII CSPs were derivatives of L-leucine prepared by covalently bonding to R-(+)amine or S-(-)-amine; The Val-W and -Val-VII CSPs were derivatives of L-valine prepared by covalently bonding to R-(+)amine or S-(-)-amine; The -XI and IX were derivatives of S-(-)-amime and R-(+)amine directly bonding to aminopropylated mesopore spherical silica gel.
These CSPs have been successfully applied to resolve the enantiomers of N-benzoyl-DL-amino acid-methylesters(i.e. DL-leucine, DL-alaline) and DL-acetylphenyalaline-methylester. After comparing the resolution results on those eight of CSPs, it can be concluded that enantioselectivity depend mainly on the interactions of the enantiomers with the chiral selectors of hydrogen bonding and interactions.
The cellulose derivative CDMPC of cellulose tris(3,5-dimethylphenylcarbamate) was synthesized under heterogeneous conditions using microcrystalline cellulose (MC). The CDMPC was dissolved in solution and coated on aminopropylated mesopore spherical silica gel by evaporation to prepare the chiral stationary phases for high-performance liquid chromatography.
HPLC on a CDMPC column has enabled excellent separation of the enantiomers of sixteen racemic compounds using 2-propanol and hexane as mobile phase, among which the pesticides of ethoxyfen-ethyl, flamprop-methyl, tebuconazole and four impurities, twe impurities of triadimefon arising from its synthesis, twe impurities of metalaxyl, nissorun, 2-(l-hydroxyethyl)-l H-benzimidazole were resolved for the first time. No derivatization of the compounds was required. The results obtained suggest that chiral resolution on CDMPC occurred because the chiral 'grooves' on the CSP provide the chiral environment for enantiomers. Temporary partial inclusion complexes are formed between enantiomers and the CSP, and the stability of these complexes is affected by hydrogen bonding and n-n interactions between the enantiomers and the CSP. Resolution of enantiomers depends on a combination of the steric fit in the chiral grooves of the CSP and the effect of the other interactions.
本文的另一部分合成了纤维素-三(3，5-二甲基苯基氨基甲酸酯)，并将其涂敷于氨丙基硅胶的表面，制备出涂敷型高效液相色谱手性固定相(CDMPC)，在该固定相上对除草剂氯氟草醚乙酯对映体、麦草伏甲酯对映体的分离进行了研究；在此色谱固定相上还对戊唑醇及其杂质、三唑酮及其杂质、甲霜灵系列化合物、苯并咪唑衍生物、杀螨剂尼索朗等对映体进行了手性分离研究，除三唑酮、甲霜灵和甲霜灵中间体而外其余均为在此类固定相上首次拆分。这些生物活性物质及其相关化合物的手性分离，纤维素-三(3，5-二甲基苯基氨基甲酸酯)涂敷型手性固定相拆分机理的探讨，不仅实现了外消旋农药的手性分离，而且分离度一般较大，这为其制备性分离，光学异构体活性差异研究、代谢及残留等课题打下了坚实的基础；也将为其单体的不对称合成等研究提供重要的检测手段。
In order to develop Pirkle Type chiral stationary phases (CSPs) of High-Performance Liquid Chromatography(HPLC), eight kinds of amino acid derivatives including chiral amines of (R-(+)-2-methyl-1 -(p-chlorobenphyl)-1 -propanamine and
S-(-)-2-2-methyl-1-(p-chlorobenphyl)-l-propanamine) covalated chiral stationary phases have been designed and synthesized, and their application in resolution of enantiomers by HPLC was studied. This eight kinds of novel chiral stationary phases were Ile-VII,-Ile-VII; Leu-VII,Leu-VII; Val-VII, -Val-VII, -XIand IX. The Ile-VII and -Ile-VII CSPs were derivatives of L-isoleucine prepared by covalently bonding to R-(+)amine or S-(-)-amine; The Leu-VII and-Leu-VII CSPs were derivatives of L-leucine prepared by covalently bonding to R-(+)amine or S-(-)-amine; The Val-W and -Val-VII CSPs were derivatives of L-valine prepared by covalently bonding to R-(+)amine or S-(-)-amine; The -XI and IX were derivatives of S-(-)-amime and R-(+)amine directly bonding to aminopropylated mesopore spherical silica gel.
These CSPs have been successfully applied to resolve the enantiomers of N-benzoyl-DL-amino acid-methylesters(i.e. DL-leucine, DL-alaline) and DL-acetylphenyalaline-methylester. After comparing the resolution results on those eight of CSPs, it can be concluded that enantioselectivity depend mainly on the interactions of the enantiomers with the chiral selectors of hydrogen bonding and interactions.
The cellulose derivative CDMPC of cellulose tris(3,5-dimethylphenylcarbamate) was synthesized under heterogeneous conditions using microcrystalline cellulose (MC). The CDMPC was dissolved in solution and coated on aminopropylated mesopore spherical silica gel by evaporation to prepare the chiral stationary phases for high-performance liquid chromatography.
HPLC on a CDMPC column has enabled excellent separation of the enantiomers of sixteen racemic compounds using 2-propanol and hexane as mobile phase, among which the pesticides of ethoxyfen-ethyl, flamprop-methyl, tebuconazole and four impurities, twe impurities of triadimefon arising from its synthesis, twe impurities of metalaxyl, nissorun, 2-(l-hydroxyethyl)-l H-benzimidazole were resolved for the first time. No derivatization of the compounds was required. The results obtained suggest that chiral resolution on CDMPC occurred because the chiral 'grooves' on the CSP provide the chiral environment for enantiomers. Temporary partial inclusion complexes are formed between enantiomers and the CSP, and the stability of these complexes is affected by hydrogen bonding and n-n interactions between the enantiomers and the CSP. Resolution of enantiomers depends on a combination of the steric fit in the chiral grooves of the CSP and the effect of the other interactions.
引文
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