联萘酚在涂敷型淀粉衍生物手性固定相上拆分中的吸热保留及对映体洗脱顺序反转

Unusual Endothermic Retention and Reversal of Elution Order in Enantioseparation of Binaphthol on a Coated Amylose-derived Chiral Stationary Phase

在正相条件下,探讨了手性化合物联萘酚、联萘酚二醋酸酯、联萘酚二磺酸酯、二溴代联萘酚、氢化安息香以及萘普生在涂敷型淀粉衍生物手性固定相Lux Amylose-2上的拆分,考察了流动相中极性醇添加剂的种类及含量、柱温等对手性拆分及对映体洗脱顺序的影响。氢化安息香获得理想的拆分,分离度可达17.76;联萘酚二醋酸酯、联萘酚二磺酸酯和二溴代联萘酚得到基线或部分分离,分离度分别为3.43、2.56和1.47;萘普生未得到拆分。联萘酚拆分中观察到溶剂诱导及温度诱导对映异构体洗脱顺序反转的现象,R-联萘酚表现出少见的吸热保留特征。结合这些现象对手性识别机理进行了探讨。

Several chiral compounds,including 1,1′-bi-2-naphthol（BINOL）,binaphthol diacetate,binaphthol disulfonate,dibromobinaphthol,hydrobenzoin and naproxen,were enantioseparated on a coated amylose-derived chiral stationary phase,Lux Amylose-2,in the normal-phase mode.The effects of column temperature and polar alcohol modifier in the mobile phase on the retention,enantioseparation and elution order were investigated.Hydrobenzoin achieved an excellent enantioseparation no matter which alcohol was used as polar modifier（resolution being 17.76）.Binaphthol diacetate,binaphthol disulfonate and dibromobinaphthol achieved baseline or partial enantioseparation（resolution being 3.43,2.56 and 1.47,respectively）.Solvent-and temperature-induced reversals of elution order in the enantioseparation of BINOL were observed.An unusual endothermic characteristic was observed during the retention process of R-BINOL.The origin of the reversal of elution order and the chiral recognition mechanism were discussed.