The Synthesis And Enantioseparation Abilities Of Some New Type Cellulose Derivatives As Chiral Stationary Phases For High Performance Liquid Chromatography

The resolution of enantiomers is important to contemporary synthetical chemistry, pharmacognosy and agricultural chemistry etc by HPLC.In the direct separation of chirality,the preparation of chiral stationary phase is the key of the separation method.The polysaccharide stationary phase of cellulose derivatives has been identified as versatile and useful CSP for the separation of enantiomers.The purpose of the study is to investigate the synthesis and application of new cellulose derivatives as stationary phase on resolution of enantiomers,and the separable mechanism is studied. The work can be divided into three parts:Firstly, after reviewing the importance of cellulose derivatives as stationary phase in HPLC and the advance in separation of chiral chemicals.we design and prepare eight new cellulose derivatives as CSP in HPLC according to the fundamental design principle for chiral stationary phase.Secondly, eight CSPs by coating method have been prepared and investigated their chromatographic performances.The results are as follows:(l)The aromatic compounds were separated on six CSPs, such as nitroaniline, chloroaniline,bromoaniline,dimethylbenzene.But another compounds couldn't be separeated such as aminophenol, nitrobenzophenone, phenylene diamine, hydroxybenzophenone, phenylene diol, benzene dicarbonic acid,amino phenylformate, methyl phenol, nitrobenzenemethylal. The compounds of not separation have more hydroxy and strong reciprocity,so they couldn't be separated.(2)The CSP's resolution of enantiomers has been investigated. In mang enantiomers, metala-xyl, diniconazole, ethofumesate were separated on fourth CSP (cyclododecyl amino carboxy allyl -carbonyl and acetylated cellulose). Methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carbo-xylate was separated on third CSP (cyclododecyl amino carboxy propiono and acetylated cellulose). 2-4-chlorobenzyl propanenitrile,a-(4-fluobenzyl)phenylethanol,p-t-butylphenoxy-2-propyl alcohol, 2-p-chlorobenzyl hexylnitrile, triadimenol, ethofumesate were separated on seventh CSP(cyclodo-decyl amino carboxy propiono and benzoylated cellulose), Tradimefon,2-4-chlorobenzyl propanenitrile ,a-(4-fluobenzyl) phenylethanol were separated on eighth CSP(cyclododecyl amino carboxy allyl carbonyl and benzoylated cellulose).(3)The influence of 2-propanol content has been investigated. Capability factor(k') becomes increasing as the content of 2-propanol diminishes,But the stereochemistry selection (a) has two trends: (1) the stereochemistry selection become bigger;(2) The stereochemistry selection become bigger firstly and then becomes smaller.The change range of stereochemistry selection is smaller than that of capability factor.Thirdly, the commercial cyclodextrin devivatives stationary phase in capillary gas chromatography has been used to determine four chiral chemicals ,such as methyl 2-chloro-propionate, 2-4-chlorobenzylpropanenitrile,2-p-chlorobenzylhexylnitrile,(E)-(3-N-t-butyloxyl-carboxylamido)2,2-dimethylcyclopropane formate.