Rates of Base-Catalyzed Hydrogen Exchange of Terminal Acetylenes in Aqueous Solution. Absence of Resonance Interaction

Article abstract of DOI:10.1021/jo00356a011

Rates of detritiation of 13 monosubstituted acetylenes labeled at the acetylenic hydrogen position were measured in aqueous amine buffer solution at 25 deg C, and hydroxide ion catalytic coefficients were evaluated.These rate constants, plus a few additional values from the literature, give a good correlation against inductive or field substituent constants: log(k_HO^-/M^-1s^-1) = 1.46+/-0.12 + (8.00+/-0.50)?_I.This correlation is not improved by addition of resonance substituted constants, and the coefficients of the resonance term in two different dual parameter (resonance plus field) treatments of the data are in fact zero.