Mechanisms of Acid−Base Catalysis of β-Elimination Reactions in Systems Activated by a Pyridine Ring

Abstract

Beta-elimination reactions from 1 (in quinuclidine/quinuclidinium chloride, imidazole/imidazolium, and acetate/acetic acid buffers) and from 2 (in imidazole/imidazolium and acetate/acetic acid buffers) with formation of 4-vinylpyridine and 2-vinylpyridine, respectively, were studied. The results of a kinetic study of acid-base catalysis and H/D exchange are consistent with NH(+), the protonated substrate, as the species that undergoes carbon deprotonation with an E1cb mechanism. The comparison with previously studied reactions in acetohydroxamate/acetohydroxamic acid buffer confirms this assignment. The high proton activating factor, PAF, value observed (PAF = 1.2 x 10 (6) with isomer 1 in quinuclidine/quinuclidinium buffer) can be explained with the high stability by the resonance of the intermediate carbanion.