Synthesis Of A Chiral Polymer And Its Resolution Ability For Racemes

The enantiomers of chiral drugs have significant differences in pharmacology,pharmacokinetics,and toxicity.There is an enormous demand for optically pure chiral drugs with high activity,no toxicity and no side effects.Enantiomeric resolution is the major approach for the pharmaceutical industry to obtain optically pure chiral drugs.The key is designing and preparation of chiral separation media.In this paper,the chiral polymer was prepared based on the already synthesized chiral functional monomers,and the chiral discrimination ability of monomers was characterized,the structure of chiral polymer and the chiral resolution ability were evaluated.The main research contents are listed as follows:(1)Preparation of three chiral functional monomers:(1S,2S)-dimethacrylate ethyl urea-diphenyl ethylenediamine(DMEUDPEA),methacrylate ethyl urea-L-phenylalanine(MEUPA)and N-diallyl-dehydroabietylamine(DHADA)were synthesized by the phenylalanine,dehydroabietylamine and diphenylethylenedi-amine which acted as chiral raw material.Their purity was determined by High Performance Liquid Chromatography(HPLC),their chemical structure was characterized by Infrared spectrum and Nuclear Magnetic Resonance.(2)Research on the chiral recognition ability of monomers: the chiral recognition ability of the three chiral monomers to 20 racemes w studied by NMR.According to the results,DMEUDPEA had remarkable recognition effect on propranolol,mandelic acid and its derivatives,voriconazole and other enantiomers;MEUPA had chiral recognition effect on bupivacaine and naphthylethylamine;DHANDA had significant recognition effect on cyclohexane mandelic acid and camphor sulfonic acid.(3)Preparation and selective adsorption for enantiomers of the chiral adsorption material: the chiral polymer was synthesized by copolymerization of DMEUDPEA and ethylene dimethacrylate under the action of initiator.Scanning Electron Microscopy(SEM),Infrared spectroscopy(IR),Thermogravimetric Analysis(TGA)and Brunner-Emmet-Teller measurements(BET)were used to characterize the structure of the chiral adsorption material.The prepared chiral polymer was used as chiral adsorption medium,and the adsorption selectivity of the D/L-1-phenyl alcohol,D/L-mandelic acid methyl ester,D/L-1-phenyl propanol and D/L-1-(4-bromophenyl)ethanol was estimated by chiral High Performance Liquid Chromatography(HPLC).The optimum separation conditions were investigated and optimized by simple variable method,and the enantiomeric excess(e.e.)of 1-phenyl alcohol enantiomer was up to 53%.