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化学学报
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化学学报 ›› 2003, Vol. 61 ›› Issue (10): 1635-1640. 上一篇    下一篇

研究论文

外消旋萘普生酯类在(S,S)-Whelk-O1与CDMPC手性柱上的对映体分离及手性识别机理的比较

邵保海;徐秀珠;吕建德;蔡小军;邹莉;傅小芸   

  1. 浙江大学化学系
  • 发布日期:2003-10-15

Comparison of Enantioseparation and Chiral Recognition Mechanism of Racemic Naproxen Esters on (S,S)-Whelk-O 1 and CDMPC Chiral Columns

Shao Baohai;Xu Xiuzhu;Lu Jiande;Cai Xiaojun;Zou Li;Fu Xiaoyun   

  1. Department of Chemistry, Zhejiang University
  • Published:2003-10-15

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593

被引次数

40 | 9

在Pirkle型的(S,S)-Whelk-O 1与纤维素衍生物型的CDMPC两种手性柱上对六种 外消旋萘普生酯进行了对映体分离，通过研究烷氧基结构上的差异以及流动相中不 同的醇类添加剂对手性识别的影响，探讨和比较了外消旋萘普生酯在两种手性固定 相上手性识别的机理。对于 (S,S)-Whelk-O 1， 溶质与固定相之间的吸引作用于 手性识别的主要因素，而对于CDMPC，溶质在手性空腔中的空间适应性很可能是手 性识别的关键。

关键词: 固定相, 萘普生酯, 纤维素, 流动相

Among various types of chiral stationary phases (CSPs), (S, S)- Whelk-0 1 and cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC) have been proven to be two of the most useful CSPs because of their versatility and capability. ( S, S)-Whelk-0 1 belongs to Pirkle type small molecular CSP. Its chiral recognition mechanism is relatively better understood. However, the chiral recognition mechanism on CDMPC (one kind of cellulose derivative CSPs) has not been adequately elucidated due to the presence of multiple chiral and achiral sites in or near the chiral cavity of CDMPC. In this paper, six kinds of racemic naproxen ester (methyl, ethyl, 71-propyl, n-butyl, ￡so-propyl and .sec-butyl) were successfully enantioseparated on (S,S)-Whelk-0 1 and CDMPC chiral columns. The influence of structure of alkoxy group and different alcohol modifier in the mobile phase on the chiral recognition was studied and the difference between chiral recognition mechanism of racemic naproxen esters on CDMPC and that on (S, S)-Whelk- 0 1 was compared. The results show that the size especially the space structure of the alkoxy far from the chiral center of the esters greatly influences the enantioseparation of racemic naproxen esters on both (5,5)-Whelk-0 1 and CDMPC CSPs. On (S, S)-Whelk-0 1, the retention and the chiral selectivity of racemic naproxen esters are systematically changed as the size of the alkoxy group became larger or the steric structure became more bulkier, suggesting that the attractive interactions between CSP and solute are the key factor for retention and chiral recognition. However, the influence of alkoxy group structure on enantioselectivity does not follow any particular trend on CDMPC, indicating that the steric fit of the solute into the chiral cavity maybe the predominant factor for the chiral recognition of naproxen esters on CDMPC chiral stationary phase and the hydrogen bond interaction or π-π interaction is important for solute retention but not for the chiral recognition.

Key words: STATIONARY PHASE, nproxen ester, CELLULOSE, MOBILE PHASE

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