Elimination Reactions of Aryl Furylacetates Promoted by R2NH in MeCN: Effects of Base Solvent and beta-Aryl Group on the Ketene-forming Transition State

Abstract

Ketene-forming elimination from C4H3(O)CH2C(O)OC6H3-2-X-4-NO2 (1) promoted by R2NH in MeCN has been studied. The reactions produced elimination products and exhibited second-order kinetics with Bronsted beta = 0.51, and vertical bar beta(lg)vertical bar = 0.47-0.53, indicating that the reaction proceeds by the E2 mechanism via an E2-central transition state. Comparison of beta, vertical bar beta(lg vertical bar), Delta H-not equal, and Delta S-not equal values for R2NH-promoted eliminations from ArCH2C(O)OC6H3-2-X-4-NO2 reveals that the transition-state structures for Ar = furyl and thienyl are similar and more symmetrical than that for Ar = Ph. This outcome has been attributed to the greater double bond stabilizing ability of the former than that of the latter.