• Bulletin of the Korean Chemical Society
• /
• 제26권8호
• /
• pp.1246-1250
• /
• 2005

We have evaluated the hydroxyl group-solvent specific interactions by using a Lichrosorb RP18 stationary phase and by measuring the retention data of carefully selected solutes in 50/50, 60/40, 70/30, 80/20, and 90/10(v/v%) methanol/water eluents at 25, 30, 35, 40, 45, and 50 ${^{\circ}C}$. The selected solutes are 3 positional isomers of phenylpropanol, that is, 1-phenyl-1-propanol, 1-phenyl-2-propanol, and 3-phenyl-1-propanol. There exist clear discrepancies in ${\Delta}H^o$ (solute transfer enthalpy from the mobile to the stationary phase) and $T{\Delta}S^o$ (solute transfer entropy) among positional isomers. The difference in ${\Delta}H^o$ and $T{\Delta}S^o$ between secondary alcohols (1-phenyl-1-propanol and 1-phenyl-2-propanol)is negligible compared to the difference between the primary alcohol (1-phenyl-3-propanol) and secondary alcohols. The $T{\Delta}S^o$ values of 3-phenyl-1-propanol are close to those of butylbenzene while the $T{\Delta}S^o$ values of secondary alcohols are close to those of propylbenzene. The difference in ${\Delta}{\Delta}H^o$ (specific solute-mobile phase interaction enthalpy) between the primary alcohol and the secondary alcohol decreases with increase of methanol content in the mobile phase. A unique observation is an extremum for 1-phenyl-3-propanol in the plot of $T{\Delta}{\Delta}S^o$ vs. methanol volume %. The positive sign of $T{\Delta}{\Delta}S^o$ of 3-phenyl-1-propanol implies that the entropy of 3-phenyl-1-propanol is greater than that of the hypothetical alkylbenzene (the same size and shape as phenylpropanol) in the mobile phase.

• 문화기술의 융합
• /
• 제7권2호
• /
• pp.389-394
• /
• 2021

본 연구에서는 알콕시-아민-알루미늄 유도체인 DPHMP-AlH와 프로피오페논, 부티로페논과의 분자구조 및 경계궤도함수의 특성을 알아보았다. 또한, 전이상태의 입체구조 및 열역학적 파라미터를 계산하여 최종 생성물인 (R),(S)-페닐프로판올과 (R),(S)-페닐부탄올의 선택적 환원에 미치는 영향을 조사하였다. 그 결과 입체 분자구조적 안정성을 고려해 볼 때 (S)형 DPHMP-AlH와 알킬페논의 전이상태가 더 안정한 것으로 나타났으며, 이 결과로부터 DPHMP-AlH와 알킬페논의 선택적 환원으로 얻어진 최종 결과물은 (S)-(1)-페닐프로판올과 (S)-(1)-페닐부탄올의 형성이 유리한 것을 확인하였다.