Some observations relating to substituent effects in halogenation. Part V. Reaction of t-butylbenzene with chlorine acetate in aqueous acetic acid

Abstract

The reaction of t-butylbenzene in 75 %(v/v) acetic acid with chlorine acetate in the presence of perchloric acid at 25° was examined. The results show that the 2-, 3-, and 4-positions are activated towards reaction with the reagent. Both the ½o: p and½m : p ratios are higher than those recorded for the other electrophilic reactions of the compound, and fall in the expected order Cl⁺, (ClOACH⁺) > Br⁺, NO₂⁺ > Cl₂. In 75 % acetic acid the chlorinating species derived from chlorine acetate in presence of perchloric acid are shown to be the chloro-oxonium ion, the chlorine cation, and chlorine acetate and its protonated form. A certain amount of chlorodebutylation accompanies the reaction.