【摘要】 以(S)-2,2′-二羟基-1,1′-联萘基-3,3′-二醛和1,2-苯二胺通过一步缩合反应合成了一种手性多亚胺大环(BINOL-CPM),将其修饰后利用巯基-烯点击反应键合到巯基硅胶表面,制得了一种高效液相色谱手性固定相(CSP).该CSP填充的色谱柱在正相(NP)和反相(RP)洗脱模式下均具有较好的手性拆分性能,有12种外消旋体在NP洗脱模式下实现了拆分, 6种外消旋体在RP洗脱模式下实现了拆分.将该柱对这些外消旋体的拆分效果与两种常用的商品柱(Chiralpak AD-H和Chiralcel OD-H)进行了比较. NP洗脱模式下拆分的12种外消旋体中有1-(3-氟苯基)乙醇、 1-苯乙醇、 3-羟基-2-丁酮和1-(4-氟苯基)乙醇4种不能在Chiralpak AD-H柱上获得拆分,有1-(3-氟苯基)乙醇、 3-羟基-2-丁酮和1-(4-氟苯基)乙醇3种外消旋体不能在Chiralcel OD-H柱上获得拆分;RP洗脱模式下拆分的6种外消旋体中1-苯乙醇不能在Chiralpak AD-H柱上获得拆分,一些手性化合物在该柱上的分离度(R_s)也高于这两种商品柱.因此,该制备柱与两种商品柱之间具有良好的手性拆分互补性,可拆分它们不能拆分或不能很好拆分的一些手性化合物.此外,该柱还表现出优秀的拆分重现性和稳定性,在经历数百次进样使用后,对扁桃酸乙酯拆分的两个对映体色谱峰的保留时间(t_R)和R_s与柱使用之初无显著变化,其色谱峰t_R的相对标准偏差RSD(n=5)<0.49%, R_s的RSD(n=5)<2.88%.此外,该色谱柱的柱间重现性也较好,不同批次制备的柱对扁桃酸乙酯拆分的两个对映体色谱峰的t_R和R_s的RSD(n=3)分别小于1.09%和5.75%.研究结果表明BINOL-CPM是一种良好的HPLC手性分离材料,具有重要的研究价值,也为新型高效液相色谱CSP的研究提供了参考.更多还原

【Abstract】 In this study, a chiral polyimine macrocycle, BINOL-CPM, was synthesized via a one-step condensation of(S)-2,2′-dihydroxy-[1,1′-binaphthalene]-3,3′-dialdehyde and 1,2-phenylenediamine. After modification, it was bonded to the surface of thiolated silica via thiol-ene click reaction to fabricate a chiral stationary phase(CSP) for high-performance liquid chromatography(HPLC). The CSP-packed column exhibits good chiral separation performance in both normal-phase(NP) and reversed-phase(RP) elution modes, with 12 racemates resolved in the NP mode and 6 racemates resolved in the RP mode. The chiral separation performance of this column for these resolved racemates was compared with two commonly used commercial columns, Chiralpak AD-H and Chiralcel OD-H. Among the 12 racemates resolved in the NP mode, 4 racemates, [1-(3-fluorophenyl)ethanol, 1-phenylethanol, 3-hydroxy-2-butanone and 1-(4-fluorophenyl)ethanol], could not be resolved on the Chiralpak AD-H column, and 3 racemates, [1-(3-fluorophenyl)ethanol, 3-hydroxy-2-butanone and 1-(4-fluorophenyl)ethanol], could not be resolved on the Chiralcel OD-H column. Among the 6 racemates resolved in the RP mode, one racemate(1-phenylethanol), could not be resolved on the Chiralpak AD-H column. Moreover, the resolution values(R_s) of some racemates on this column were higher than those on the two commercial columns. Therefore, this prepared column demonstrates good complementarity in chiral separation, enabling the separation of some chiral compounds that cannot be resolved or be well resolved by these two commercial columns. In addition, the column also demonstrates excellent reproducibility and stability in chiral separation. After hundreds of injections, the retention time(t_R) and R_s of the two enantiomeric peaks for the separation of ethyl mandelate show no significant changes compared to the initial use of the column. The relative standard deviation(RSD, n=5) of t_R for the chromatographic peaks of the two enantiomers was less than 0.49%, and the RSD of R_s(n=5) was less than 2.88%. Moreover, the column-to-column reproducibility was also good, with the RSD(n=3) of t_R and R_s for the two enantiomeric peaks of ethyl mandelate separation on columns prepared from different batches being less than 1.09 % and 5.75 %, respectively. This study indicates that BINOLCPM is a promising chiral separation material for HPLC and has good research significance and value. It also provides a reference for the development of novel HPLC CSP.更多还原