Intrinsic rate constants for proton transfer from a monoketone to amine bases and electrostatic effects on the intrinsic rate constants for the deprotonation of cationic ketones by OH(super -)

Intrinsic rate constants were determined for proton transfer from monoketones to a family of amine bases. Specifically, the reaction of secondary alicyclic amines with 2-acetyl-1-methylpyridinium ion was examined. The intrinsic rate constants obtained were found to be lower than for any sterically unhindered carbon acids except for nitroalkanes. The results suggest the presence of a strong pi-acceptor character of the CO group and strong salvation in the enolate ion.