The specific rates of solvolysis of ethyl fluoroformate have been measured at 24.2 degrees C in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation is applied. The sensitivities to changes in the N(T) solvent nucleophilicity scale and the Y(Cl) solvent ionizing power scale, and the k(F)/k(Cl) values are very similar to those for solvolyses of n-octyl fluoroformate, consistent with the addition step of an addition-elimination pathway being rate-determining. For methanolysis, a solvent deuterium isotope effect of 3.10 is compatible with the incorporation of general-base catalysis into the substitution process. For five representative solvents, studies were made at several temperatures and activation parameters determined. The results are also compared with those reported earlier for ethyl chloroformate and mechanistic conclusions are drawn.
Keywords: Ethyl fluoroformate; Grunwald–Winstein equation; addition–elimination; solvent isotope effect.