Resonance and field/inductive substituent effects on the gas‐phase acidities of <i>para</i>‐substituted phenols: a direct approach employing density functional theory

Abstract

Abstract Relative gas‐phase acidities of para ‐substituted phenols ( 1 , Sub—C 6 H 4 —OH) and their ω‐substituted para ‐alkylphenol analogs [ 2 , Sub—(CH 2 ) n —C 6 H 4 —OH] were calculated at the B3LYP/6–31+G* and AM1 levels of theory. The acidity of a substituted molecule of 2 is compared with that of the unsubstituted molecule of 2 to determine the field/inductive effect of the substituent on the acidity of 2 . This field/inductive effect was extrapolated to n = 0, yielding the field/inductive effect of the substituent on the acidity of 1 . The derived field/inductive effect in 1 was subtracted from the difference in acidity between 1 and phenol in order to determine the resonance effect of the substituent on the acidity of 1 . Our results are compared with the field/inductive and resonance substituent parameters empirically derived from previous experimental solution studies. Copyright © 2004 John Wiley &amp; Sons, Ltd.