Pitfalls in Assessing the α-Effect: Reactions of Substituted Phenyl Methanesulfonates with HOO⁻, OH⁻, and Substituted Phenoxides in H₂O

Toward resolving the current controversy regarding the validity of the α-effect, we have examined the reactions of Y-substituted phenyl methanesulfonates <b>1a</b>−<b>1l</b> with HOO⁻, OH⁻, and Z-substituted phenoxides in the gas phase versus solution (H₂O). Criteria examined in this work are the following: (1) Brønsted-type and Hammett plots for reactions with HOO⁻and OH⁻, (2) comparison of β_lg values reported previously for the reactions of Y-substituted phenyl benzenesulfonates <b>2a</b>−<b>2k</b> with HOO⁻ (β_lg = −0.73) and OH⁻ (β_lg = −0.55), and for those of <b>1a</b>−<b>1l</b> with HOO⁻ (β_lg = −0.69) and OH⁻ (β_lg = −1.35), and (3) Brønsted-type plot showing extreme deviation of OH⁻ for reactions of 2,4-dintrophenyl methanesulfonate <b>1a</b> with aryloxides, HOO⁻, and OH⁻, signifying extreme solvation vs different mechanisms. The results reveal significant pitfalls in assessing the validity of current interpretations of the α-effect. The extreme negative deviation by OH⁻ must be due, in part, to the difference in their reaction mechanisms. Thus, the apparent dependence of the α-effect on leaving-group basicity found in this study has no significant meaning due to the difference in operating mechanisms. The current results argue in favor of a further criterion, i.e., a consistency in mechanism for the α-nucleophiles and normal nucleophiles.