联苯类对映体在纤维素类手性固定相上的高效液相色谱法直接拆分

Direct Optical Resolution of the Enantiomers of Biphenyl Compounds by High-Performance Liquid Chromatography on Cellulose Tris-(3,5-dimethylphenylcarbamate) Stationary Phase

涂敷纤维素-三(3,5-二甲基苯基氨基甲酸酯)于自制的球形氨丙基硅胶上,制备了手性固定相.用该固定相直接拆分了一系列外消族联苯类保肝药物.考察了柱温和流动相中乙醇含量对样品的保留和立体选择性的影响,升高柱温或增大流动相中乙醇含量都会使对映体的保留因子和分离因子降低.所考察样品的分离因子的对数与温度的倒数成线性关系.确定了对映体从流动相传递到固定相的吉布斯自由能变之差值、焓变之差值及熵变之差值.

A chiral stationary phase ( CSP) was prepared by coating cellulose - tris (3,5-dimethylphenylcarbamate) onto aminopropylated spherical silica gel. The enantioselective separation of a series of biphenyl compounds with antihepatitis activity was achieved for the first time on the CSP, using the normal -phase mode. The effects of temperature and concentration of ethanol in the mobile phase on the chiral separation were studied. The retention factors and separation factors for the enantiomers of all investigated compounds decreased with increasing temperature or increasing ethanol concentration in the eluent. The natural logarithms of the separation factors (lnα) of the investigated compounds depended linearly on the reciprocal of temperature ( 1 / T ) . The thermodynamic parameters , such as the difference in enthalpy △(△H°) , entropy △(△S°) and Gibbs free energy △(△G°) for the transfer of analyte from the mobile phase to the CSP were calculated.