气相色谱法拆分扁桃酸甲酯对映体及手性识别机理探讨  

Enantiomeric separation of methyl mandelate by gas chromatography and discussion the chiral recognition mechanism

作　　者：施介华[1] 程向炜[1,2] 严巍[1] 

机构地区：[1]浙江工业大学药学院,杭州310032 [2]浙江公安高等专科学校,杭州310053

出　　处：《药物分析杂志》2009年第10期1681-1684,共4页Chinese Journal of Pharmaceutical Analysis

摘　　要：目的:采用气相色谱法拆分扁桃酸甲酯对映体,并通过对映体分离过程中的热力学参数计算,探讨扁桃酸甲酯对映体分离过程中的驱动力及其拆分机理。方法:在β-环糊精(CyclodexB)手性毛细管柱上分离扁桃酸甲酯对映体。结果:在柱温为118℃,载气流速为1mL·min-1时,扁桃酸甲酯对映体在β-环糊精(CyclodexB,30m×0.25mm×0.25μm)手性毛细管柱上具有较好的分离效果,其分离因子(α)和分离度(R)分别为1.02和1.55。扁桃酸甲酯对映体lnk′与1/T和lnα与1/T之间具有较好的线性关系。并从VantHoff曲线求得(R)-扁桃酸甲酯和(S)-扁桃酸甲酯焓变(ΔH)分别为-59.29kJ.mol-1和-60.64kJ·mol-1,两者的焓变差[Δ(ΔH)]和熵变差[Δ(ΔS)]分别为-1.34kJ·mol-1和-3.25J.mol-1.K-1。结论:扁桃酸甲酯对映体的拆分过程主要是一个焓控过程,且β-环糊精外表面与扁桃酸甲酯之间的相互作用在其分离过程中起了重要作用。Objective ：To separate the enantiomers of methyl mandelate by gas chromatography and investigate the process of the enantiomers separation and the chiral recognition mechanism by calculation of thermodynamic parameters in process of enantiomeric separation. Methods： The enantiomers of methyl mandelate had been separated on fl -cyclodextrin （Cyclodex B） ehiral capillary chromatographic column. Results：The enantiomers of methyl mandelate can be baseline separated at fl -cyclodextrin （Cyclodex B ,30 m×0.25mm×0.25μm） chiral capillary chromatographic column under column temperature 118 ℃ and 1 mL · min ^- 1 of flow rate of carrier gas. The separation factor （ct） and separation degree （R） of enantiomers of methyl mandelate were 1.02 and 1.55, respectively. There was good linearity relation between enantiomeric lnk＇ or lnct and 1/T. Enthalpy -change （AH） of （R） -and （S） - methyl mandelate calculated from Van＇t Hoff curve were - 59.29 kJ · mol^ - 1 和- 60.64 kJ · mol^ - l, respectively. The differential enthalpy - change [ △（△H）] and differential entropy - change [ △（△S） ] between （S） - and （R） - methyl mandelate calculated from Vant＇t Hoff curve were - 1.34 kJ · mol ^-1和 - 3.25 J · mol ^- 1 ·K^ - 1, respectively. Conclusion ： The separation of enantiomers of methyl mandelate was enthalpy - driven process and the interaction between surfaces out of the cavity ofβ - cyclodextrin and methyl mandelate might mainly contribute to the separation.

关 键 词：扁桃酸甲酯 射映体 手性分离 衍生化 Β-环糊精 手性识别 

分 类 号：R917[医药卫生—药物分析学]