Chemistry of the 2-Pinanols. 1. Pinanoxide Basicities

Article abstract of DOI:10.1021/jo01293a025

The basicities of the alkoxides of cis- and trans-2-pinanol were examined colorimetrically and conductimetrically.The colorimetric measurements gave the following pKa values for the conjugate acids in dimethyl sulfoxide (Me2SO): 30.4, tert-butoxide; 32.5, tricyclohexylmethoxide; 32.6, cis-pinanoxide; 32.8, trans-pinanoxide.The pinanoxides are the most basic alkoxides yet measured.Conductivity measurements of Me2SO solutions containing these bases revealed that very complex equilibria processes were operative.A study of the elimination of 2-iodobutane in Me2SO with the pinanoxide bases showed a good correlation with base strength.No steric effects such as those observed with tricyclohexylmethoxide were apparent for the pinanoxide bases.