title: Curved Hammett plot in alkaline hydrolysis of O-aryl thionobenzoates: change in rate-determining step versus ground-state stabilization.
abstract: Second-order rate constants have been measured for alkaline hydrolysis of O-aryl thionobenzoates (X-C(6)H(4)-CS-OC(6)H(4)-Y) in 80 mol % H(2)O-20 mol % DMSO at 25.0 +/- 0.1 degrees C. The Hammett plot for the reaction of O-4-nitrophenyl X-substituted thionobenzoates (X-C(6)H(4)-CS-OC(6)H(4)-NO(2), 1a-e) exhibits a downward curvature. However, a possible traditional explanation in terms of a change in the rate-determining step (RDS) has been considered but rejected. The proposed explanation involves stabilization of the ground-state (GS) through-resonance interaction between the electron-donating substituent X and the thionocarbonyl functionality on the basis of the linear Yukawa-Tsuno plot obtained for the same reaction. The Brønsted-type plot for the reaction of O-aryl thionobenzoates (C(6)H(5)-CS-OC(6)H(4)-Y, 2a-i) is linear but exhibits many scattered points with a small beta(lg) (-0.35). The Hammett plot for the same reaction shows rather poor correlation with sigma(-) constants but much better correlation with sigma(o) constants. The alkaline hydrolysis of O-aryl thionobenzoates (1a-e and 2a-i) has been proposed to proceed through an addition intermediate in which bond formation is the RDS.
authors.affiliation: Department of Chemistry, Ewha Womans University, Seoul 120-750, Korea. ihum@mm.ewha.ac.kr
authors.forename: Ik-Hwan
authors.initials: IH
authors.lastname: Um
authors.forename: Ji-Youn
authors.initials: JY
authors.lastname: Lee
authors.forename: Han-Tae
authors.initials: HT
authors.lastname: Kim
authors.forename: Sun-Kun
authors.initials: SK
authors.lastname: Bae