【摘要】 合成了N-[(R)-α-叔丁氧基羰基苄基]甲基丙烯酰胺((R)-BCBMAM),通过自由基聚合法获得相应的光学活性聚合物(P(R-BCBMAM)),并以三氟乙酸为水解催化剂除去叔丁基而得到(P(R-CBMAM)).用1H-NMR,IR,CD和GPC对聚合物进行了结构表征,发现聚合溶剂和聚合物分子量对所得聚合物P(R-BCBMAM)的光学活性没有明显影响,P(R-BCBMAM)水解后光学活性有较大的改变.与单体相比,聚合物的比旋光度有较大的区别,且在对应于其侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明聚合物的主链可能形成了一定的二级结构.以P(R-BCBMAM)和P(R-CBMAM)制备的2种涂敷型高效液相色谱用手性固定相,对部分对映体具有一定的手性拆分能力.利用1H-NMR技术研究了上述2种聚合物与1,1’-联-2-萘酚(BINOL)的相互作用,它们对BINOL都具有良好的手性识别能力.更多还原

【Abstract】 A chiral monomer N-[(R)-α-tert-butoxycarbonylbenzyl]methacrylamide((R)-BCBMAM) was synthesized via amidation reaction between methacryloyl chloride and D-phenylglycine tert-butyl ester.Optically active polymers were prepared via free radical polymerization of((R)-BCBMAM)initiated by AIBN at 60 ℃.In the presence of catalytic amount of trifluoroacetic acid,the tert-butyl of P(R-BCBMAM) was removed to obtain poly{N-[(R)-α-hydroxylcarbonylbenzyl]methacrylamide} P(R-CBMAM).1H-NMR,IR,CD and GPC were employmed to characterize the chemical structure of the products.The results indicated that the polymerization condition had slight effects on the chiroptical properties of P(R-BCBMAM).The results from specific optical rotation and circular dichroism spectra indicated that the P(R-CBMAM) and P(R-BCBMAM) had great difference in the chiroptical properties.On the basis of the results from circular dichroism(CD),the optical activity of P(R-BCBMAM) was attributed not only to the chirality of amino acid side groups in monomeric units but also to the steric repulsion of tert-butyl groups.P(R-BCBMAM) and P(R-CBMAM) were coated onto silica gels as the chiral stationary phase(CSP) for high performance liquid chromatography(HPLC).The CSPs exhibit superior chiral recognition ability for some racemates.On the other hand,1H-NMR measurements of mixture of polymers and racemic 1,1′-bi-2-naphthol(BINOL) were conducted in chloroform-d.The characteristic hydroxyl proton signal of BINOL was split into two peaks ascribed respectively to the levo-and dextro-isomers.更多还原