Ilisz István, Gecse Zsanett, Szatmári István, Fülöp Ferenc, Péter Antal
Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720, Szeged, Dóm tér 7, Hungary.
Biomed Chromatogr. 2014 Jan;28(1):142-51. doi: 10.1002/bmc.3002. Epub 2013 Jul 30.
The stereoisomers of 15 naphthol-substituted tetrahydroisoquinoline analogs were separated on chiral stationary phases containing the chiral selectors cellulose tris-(3,5-dimethylphenyl carbamate) (Cellulose 1), cellulose tris-(3-chloro-4-methylphenyl carbamate) (Cellulose 2), cellulose tris-(4-methylbenzoate) (Cellulose 3) and cellulose tris-(4-chloro-3-methylphenyl carbamate) (Cellulose 4). Experiments were performed in normal-phase mode with n-heptane(n-hexane)-alcohol-diethylamine mobile phases in the temperature range 5-40 °C. Thermodynamic parameters were calculated from plots of lnk or lnα vs 1/T. On the Cellulose 1 column, Δ(ΔH°) ranged from -6.8 to 5.9 kJ/mol, Δ(ΔS°) from -16.7 to 21.0 J/mol/K and the Gibbs energy, -Δ(ΔG°) from 0.2 to 1.5 kJ/mol; on the Cellulose 2 column, Δ(ΔH°) ranged from -7.8 to 2.5 kJ/mol, Δ(ΔS°) from -16.1 to 13.2 J/mol/K and - Δ(ΔG°) from 0.7 to 3.0 kJ/mol. Both enthalpy- and entropy-controlled enantioseparations were observed. The latter was advantageous with regard to the shorter retention and greater selectivity at high temperature.
15种萘酚取代的四氢异喹啉类似物的立体异构体在含有手性选择剂三（3,5-二甲基苯基氨基甲酸酯）纤维素（纤维素1）、三（3-氯-4-甲基苯基氨基甲酸酯）纤维素（纤维素2）、三（4-甲基苯甲酸酯）纤维素（纤维素3）和三（4-氯-3-甲基苯基氨基甲酸酯）纤维素（纤维素4）的手性固定相上进行分离。实验在正相模式下进行，使用正庚烷（正己烷）-醇-二乙胺流动相，温度范围为5-40℃。根据lnk或lnα对1/T的图计算热力学参数。在纤维素1柱上，Δ(ΔH°)范围为-6.8至5.9 kJ/mol，Δ(ΔS°)范围为-16.7至21.0 J/mol/K，吉布斯自由能-Δ(ΔG°)范围为0.2至1.5 kJ/mol；在纤维素2柱上，Δ(ΔH°)范围为-7.8至2.5 kJ/mol，Δ(ΔS°)范围为-16.1至13.2 J/mol/K，-Δ(ΔG°)范围为0.7至3.0 kJ/mol。观察到了焓控和熵控的对映体分离。后者在高温下具有保留时间短和选择性高的优势。
