高效液相色谱法手性分离联萘二酚苯甲酸酯对映体

Abstract

采用CHIrEX(S)-lEu&(S)-nEA、CHIrAlCElOd-H和CHIrAlPAkAd-H手性色谱柱直接拆分了2′-羟基-1,1′-联萘-2-苯甲酸酯(Hbnb)、1,1′-联萘-2,2′-二苯甲酸酯(bndb)和2′-甲氧基-1,1′-联萘-2-苯甲酸酯(Mbnb)对映体。分别考察了流动相组成、柱温和化合物结构对手性分离的影响。结果表明:3对联萘二酚苯甲酸酯对映体在CHIrAlPAkAd-H柱上的拆分效果最好。当采用正己烷/异丙醇(40/60,V/V)为流动相时,Hbnb、bndb和Mbnb对映体的分离因子(α)和分离度(rS)分别为1.76、1.74、1.40和6.47、7.81、4.75。对比联萘二酚(bn)的分离,从联萘分子中2-位取代基、对映体出峰顺序和热力学参数等方面探讨了相关手性分离机理。

The enantioseparations of 2'-hydroxy-1,1'-binaphthyl-2-yl benzoate(HBNB),1,1'-binaphthyl-2,2'-diyl dibenzoate(BNDB) and 2'-methoxy-1,1'-binaphthyl-2-yl benzoate(MBNB) were studied on Chirex(S)-LEU &(S)-NEA,cellulose tris(3,5-dimethylphenylcarbamate)(Chiralcel OD-H) and amylose tris(3,5-dimethylphenyl-carbamate)(Chiralpak AD-H) columns,respectively,using high performance liquid chromatography.The effects of mobile phase,column temperature and compound structures on the enantioseparations were discussed.The Chiralpak AD-H exhibited stronger capability of enantioseparation in comparison with those of Chirex(S)-LEU &(S)-NEA and Chiralcel OD-H for 1,1'-bi-2-naphthol benzoates.When using the mobile phase of n-hexane/2-propanol(40/60,v/v),the chiral selectivities of HBNB,BNDB and MBNB were 1.76,1.74,and 1.40,respectively.Moreover,in comparison with that of 1,1'-bi-2-naphthol(BN),the mechanisms of the enantioseparation of 1,1'-bi-2-naphthol benzoates,related to the substituted groups at 2-position,the elution orders and thermodynamic parameters were also discussed.