Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Fluoroformate and a Consideration of Leaving Group Effects

摘要

Reactions of n-propyl fluoroformate in a variety of pure and binary solvents have been studied at 40.0 °C. The extended (two-term) Grunwald-Winstein equation has been applied to the specific rates of solvolysis of n-propyl fluoroformate. The sensitivities (Z = 1.80 ± 0.17 and m = 0.96 ± 0.10) to changes in solvent nucleophili-city and solvent ionizing power and the k_F/k_(Cl) values are similar to those for solvolyses of n-octyl fluoroformate over the full range of solvents, suggesting that the addition step of an addition-elimination mechanism is rate-determining. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.