A density functional study of propylene glycol conversion to propanal and propanone of various acid‐catalyzed reaction models: A water‐addition effect

Abstract The acid‐catalyzed models on reaction mechanisms of pinacol rearrangement of propylene glycol conversion to propanal and propanone have been investigated using the density functional method at 298.15 K. Thermodynamic quantities of activation steps of four water‐addition models were obtained. The number of added water interacting with the transition states of three concerted pathways has obviously affected the product ratio. The relative energetic profiles of the conversion reactions of all solvation models have been comparatively displayed. Estimation of the percent ratio of product composition computed from activation free energies of each acid‐catalyzed reaction model was carried out. The percent ratios of propanal and propanone were decreased as the number of added water increased. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1592–1599, 2005