An approach to the extreme in separation science : recognition of isotopic chirality

(1)合成了具有同位素手性的苯基（五氘代苯基）甲醇（I）。独立地制备⑴的对映异构体。(2)制备填充有纤维素三苯甲酸酯涂覆的二氧化硅的60 cm柱系统。(3)首次实现了对（1）外消旋混合物以及二苯基甲醇和二（五氘代苯基）甲醇的60次循环柱分离。(4)发现固定相具有优先结合氘代苯基的结合位点。(5)（6）对各种H/D同位素化合物进行了色谱分离，并对分离效果进行了考察。(7)芳香族固定相，特别是重原子芳香族固定相，表现出很高的同位素识别能力，表明分散作用是同位素识别的主要机制。(8)结果表明，纤维素固定相具有一个极化率较低的氘代苯基结合位点和一个极化率较高的氘代苯基结合位点。(9)该研究为进一步理解疏水作用的同位素识别机理和同位素效应提供了可能。（10）类似的方法将有助于阐明手性识别机制。

(1) Phenyl(pentadeuterophenyl)methanol (I) having isotopic chirality was prepared. Enantiomers of (I) were independently prepared.(2) A 60 cm column system packed with cellulose tribenzoate-coated silica was prepared.(3) The separation of a racemic mixture of (1) as well as diphenylmethanol and di(pentadeuterophenyl)-methanol was achieved for the first time at the 60 cycle on the column system.(4) The stationary phase was found to possess a binding site which preferentially binds a deuterated phenyl group over a phenyl group.(5) Various stationary phases with functional groups for reversed-phase liquid chromatography were prepared(6) Various H/D isotopic compounds were chromatographed, and the separation examined.(7) Aromatic stationary phases, especially those having heavy atoms, showed high isotopic recognition, indicating that the dispersion interaction is the major mechanism of isotopic recognition.(8) The results suggest that the cellulose stationary phase possesses a binding site for deuterated phenyl group which has lower polarizability, and another one with higher polarizability.(9) This study made it possible to understand the mechanism of isotope recognition and the isotope effect of hydrophobic interaction.(l0)Similar approach will be useful to elucidate chiral recognition mechanisms.