R&D Center, Analytical Tools BU, CPI Company, Daicel Corporation, Myoko, Niigata 944-8550, Japan.
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa 920-1192, Japan.
Molecules. 2021 Jan 18;26(2):493. doi: 10.3390/molecules26020493.
To understand the selectivity of the crown ether type chiral stationary phase (CSP), the retention selectivity for aniline and the positional isomers of substituted anilines were studied. In various substituted isomers, except nitroaniline, a remarkable decrease of retention due to steric hindrance was observed for the 2-substituted isomer. To determine the detailed molecular recognition mechanism, quantum chemical calculations were performed for the aggregates between the crown ether and the anilines. The results suggested that the 20-Crown-6, which includes a phenyl-substituted 1,1'-binaphthyl moiety, interacts with alkyl and aryl amines in an unconventional form different from the proposed one for 18-Crown-6.
为了理解冠醚型手性固定相（CSP）的选择性，研究了苯胺和取代苯胺的位置异构体的保留选择性。在各种取代异构体中，除硝基苯胺外，2-取代异构体由于空间位阻而导致保留显著降低。为了确定详细的分子识别机制，对冠醚和苯胺之间的聚集体进行了量子化学计算。结果表明，包含苯基取代的 1,1'-联萘部分的 20-冠-6 与烷基和芳基胺相互作用的形式不同于提议的 18-冠-6 的形式。
