Energetics of hydrate and hemiketal formation for highly fluorinated ketones

Abstract

Heats of hydration for a series of fluoroketones have been calculated at the HF/6-31G **//6-31G ** level, and equilibrium constants for hemiketal formation with trifluoroethanol have been measured for a related series. These reactions were found to be considerably more favorable in cyclic than in corresponding acyclic systems. Quantum mechanical calculations indicate that this difference can be traced to steric hindrance in the acyclic adducts.