The α-Effect in Hydrazinolysis of 4-Chloro-2-Nitrophenyl X-Substituted-Benzoates: Effect of Substituent X on Reaction Mechanism and the α-Effect

Min-Young Kim, Tae-Eun Kim, Jieun Lee, Ik-Hwan Um
2014 Bulletin of the Korean Chemical Society (Print)  
Second-order rate constants (k N ) have been measured spectrophotometrically for the reaction of 4-chloro-2nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % H 2 O/20 mol % DMSO at 25.0 o C. The Brønsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with β nuc = 0.74 when hydrazine is excluded from the correlation. Such a linear Brønsted-type plot is typical for reactions reported previously to proceed
more » ... ly to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with ρ X = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the α-effect). The α-effect increases as the substituent X in the benzoyl moiety becomes a stronger electronwithdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent α-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the α-effect observed in this study.
doi:10.5012/bkcs.2014.35.8.2271 fatcat:5gvv6fd7lzexjprp333k33kfea