Kinetic and thermodynamic parameters for the alcoholysis of 2,2,2-trichloro-1-arylethanones

Abstract

The reactions of 2,2,2-trichloro-1-phenylethanone (1a) and 2,2,2-trichloro-1-(p-chlorophenyl)-ethanone (1b) with MeOH, EtOH, PrⁿOH, and BuⁿOH in the presence of ethylamine resulted in the formation of the corresponding esters ArCOOR. When the process is carried out in the absence of ethylamine the reaction does not proceed beyond formation of the hemiacetal intermediate. The former reaction occurs through an addition-elimination process and the order of reactivity of the alcohols is MeOH > EtOH > PrⁿOH > BuⁿOH. If (1a or b) is treated with ethylamine in dioxane the corresponding amide ArCONHEt is the only reaction product.