A KINETIC STUDY OF THE MECHANISM OF ESTERIFICATION OF 1-ARYLETHANOLS IN TRIFLUOROACETIC ACID

Article abstract of DOI:10.1016/S0040-4039(01)90166-2

Aryl substituent effects upon the rate constants for the esterification of a series of 1-arylethanols in trifluoroacetic acid are in accordance with a reverse A_AL1 mechanism, for wich the Hammett reaction constant ρ=-3.69 has been determined by correlation with ?⁺ substituent constants.The rates of reaction are ca. 50-fold faster than those for corresponding benzyl alcohols which bear an electron-donating aryl substituent and which are also believed to undergo esterification in trifluoroacetic acid by the reverse A_AL1 mechanism; the reverse A_AC2 mechanism applies to benzyl alcohols which bear an electron-withdrawing aryl substituent.