Disappearance of the ${\alpha}$-Effect : Reaction of p-Nitrophenyl Acetate with Various Aryloxides and Benzohydroxamates in the Presence of Cetyltrimethylammonium Bromide

Disappearance of the ${\alpha}$-Effect : Reaction of p-Nitrophenyl Acetate with Various Aryloxides and Benzohydroxamates in the Presence of Cetyltrimethylammonium Bromide

The rate constants for the reactions of p-nitrophenyl acetate with 6 different aryloxides and 2 benzohydroxamates have been measured spectrophotometrically in water containing various concentrations of cetyltrimethylammonium bromide (CTAB). The reactivity of the nucleophiles has been demonstrated to be significantly enhanced as the concentration of the surfactant increases up to a certain point. When the basicities of the aryloxides are comparable, the rate enhancement is more prominent for the aryloxide having larger binding constant to the micellar aggregate. Benzohydroxamates exhibitis significantly large ${\alpha}$-effect in the absence of the surfactant, although, the ${\alpha}$-effect nucleophiles are considered to be more solvated in water than the corresponding normal nucleophile. Thus, the solvation effect does not appear to be solely responsible for the ${\alpha}$-effect. Interestingly, the large ${\alpha}$-effect disappears in the presence of the surfactant. Therefore, one might attribute the disappearance of the ${\alpha}$-effect to solvent effect. However, a structural change of the reactive ${\alpha}$ -effect nucleophile into unreactive ones would also be considered to be responsible for the absence of the ${\alpha}$-effect in the present system.