合成了Ⅳ-[(R)-a-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(尺一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’H—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.
A chiral monomer N-[ ( R)-a-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) -a-hydroxylcarbonylbenzyl ] methacrylamide t P ( R-CBMAM ). ' H-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,' H-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.