Development of Practical Resolution System

1.合成了苯基上含氯、氟和甲基的纤维素和直链淀粉的氨基甲酸苯酯类化合物，考察了它们作为手性固定相的手性识别能力。在间位和对位含有卤素和甲基的纤维素衍生物显示出比邻位和间位二取代衍生物更高的拆分能力。另一方面，邻位取代的直链淀粉衍生物的手性识别能力略低于间位和对二取代的衍生物。我们发现，三(5-氟-2-甲基苯基氨基甲酸酯)纤维素溶于氯仿，在~1H和~(13)C核磁共振中能够分辨1，1‘-双-2-萘酚的对映体，对映体的化学位移变化很大，在伴随大分离因子(α&gt；3)的高效液相色谱中也能分辨。基于层析和核磁共振数据的分子模拟揭示了纤维素苯氨基甲酸酯衍生物的手性识别原理。我们还用Quanta/Charmm或Cerius2对纤维素的三(苯基氨基甲酸酯)或三(3，5-二甲基苯基氨基甲酸酯)与反式二苯乙烯氧化物的相互作用能进行了力场计算。(MSI)。计算结果与高效液相色谱结果吻合较好。将苯氨基甲酸酯包覆在硅胶上，制备了基于苯氨基甲酸酯的CSPs。但是，四氢呋喃等溶剂不能用作洗脱剂，因为衍生物在溶剂中溶解或溶胀。为了改善这一缺陷，在减少残留物的末端将直链淀粉键合到硅胶上。以马铃薯中的磷酸酶为原料，将α-D-葡萄糖-1-磷酸二钾盐与功能化的低聚麦芽糖进行聚合，制得具有所需链长的直链淀粉。CSP表现出优异的分辨能力和对THF等溶剂的高耐久性。

1. Phenylcarbamate derivatives of cellulose and amylose having chloro or fluoro and methyl groups on the phenyl moieties were synthesized, and their chiral recognition abilities were evaluated as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). The cellulose derivatives with halogen and methyl groups at the meta and para positions showed higher resolving power than the ortho- and meta-disubstituted derivative. On the other hand, the ortho-substituted derivative of amylose showed slightly lower chiral recognition than those of the meta- and para-disubstituted derivatives.2. We have found that cellulose tris (5-fluoro-2-methylphenylcarbamate) is soluble in chloroform and is capable of discriminating enantiomers of 1,1'-bi-2-naphthol in ^1H and ^<13>C NMR with large chemical shift changes of the enantiomers as well as in HPLC accompanying the large separation factors (alpha>3). The molecular modeling on the basis of the chromatography and NMR data reveals the chiral discrimination rationale for a cellulose phenylcarbamate derivative. We also carried out force-field calculations of the interaction energies between tris (phenylcarbamate) or tris (3,5-dimethylphenylcarbamate) of cellulose and trans-stilbene oxide using Quanta/Charmm or Cerius2. (MSI). The calculation results were well consistent with the HPLC results.3. Phenylcarbamate-based CSPs have been prepared by coating the phenylcarbamates on silica gel. However, solvents such as THF can not be used as the eluents, because the derivatives are dissolved or swollen in the solvents. To improve this defect, amylose was bonded to silica gel at the reducing terminal residue. Amylose with desired chain length was prepared by polymerization of alpha-D-glucose 1-phosphate dipotassium salt with functionalized maltooligosaccharides using a phosphorylase from potato. The CSP showed excellent resolving ability and high durability against solvents such as THF.