键合型纤维素-苯基氨基甲酸酯手性固定相的制备及用于对映异构体拆分

Preparation of the Chemically Bonded Cellulose Phenylcarbamates Chiral Stationary Phases for the Separation of Enantiomers

采用化学键合法，利用４，４’－二苯基甲基二异氰酸酯作间隔臂，通过纤维素葡萄糖单元上２、３或６－位上的羟基将纤维素衍生物键合在氨丙基硅胶上，制备了键合型纤维素．苯基氨基甲酸酯手性固定相。同时，以微晶纤维素和苯基异氰酸酯为原料，合成了纤维素－三苯基氨基甲酸酯，并以未修饰的硅胶为载体，制备了涂敷型纤维素－三苯基氨基甲酸酯手性固定相。分别对键合型和涂敷型两类手性固定相进行了表征，并首次在纤维素－苯基氨基甲酸酯手性柱上拆分了安息香。

Phenylcarbamates of cellulose (CTPC) were chemically bonded to 3-aminopropyl silica gel with 4,4'-diphenylmethane diisocyanate as a spacer through the carboxyl of the glucose unit of cellulose. Their optical resolution abilities were evaluated as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). It was found that CTPC regioselectively bonded at 6-position to silica gel possessed a higher chiral recognition than that either regioselectively bonded at the 2-,3-positions to silica gel or non - regioselectively handed at 2-,3- and 6-positions to silica gel. On the other hand, the CTPC was dissolved in tetrahydrofuran (THF) and coated on underivatised silica gel by evaporation under vacuum to prepare the coated-type CSP in order to compare the optical resolution abilities with the bonded-type CSPs. It was observed that handed-type CSPs usually showed a lower resolving abilities than those of coated-type CSPs. However, the handed-ac CSPs were able to be used with eluents such as THF in which the coated-type CSPs were not able to be used because the cellulose derivatives were soluble or swollen. Benzoin was firstly separated on bonded cellulose phenylcarbamate CSP in our experiments using THF as a component of the mobile phase, which indicated that some racemates which were not or poorly separated on coated-type CSPs might be more efficiently resolved on bonded-type CSPs using THF as a component of the mobile phase.