501660-63-5Relevant articles and documents
The α-effect in hydrazinolysis of 4-chloro-2-nitrophenyl x-substituted-benzoates: Effect of substituent x on reaction mechanism and the α-effect
Kim, Min-Young,Kim, Tae-Eun,Lee, Jieun,Um, Ik-Hwan
, p. 2271 - 2276 (2014/09/29)
Second-order rate constants (kN) have been measured spectrophotometrically for the reaction of 4-chloro-2- nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % H2O/20 mol % DMSO at 25.0°C. The Bronsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with βnuc = 0.74 when hydrazine is excluded from the correlation. Such a linear Bronsted-type plot is typical for reactions reported previously 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 ?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.
Kinetic study on nucleophilic displacement reactions of 2-chloro-4-nitrophenyl x-substituted-benzoates with primary amines: Reaction mechanism and origin of the a-effect
Um, Tae-Il,Kim, Min-Young,Kim, Tae-Eun,Um, Ik-Hwan
, p. 436 - 440 (2014/03/21)
Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % H2O/20 mol % DMSO at 25.0 °C. The Bronsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa- Tsuno plots exhibit excellent linearity with ρX = 1.22-1.35 and r = 0.57-0.59, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The α-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent α-effect but stabilization of the transition state is also a plausible origin of the α-effect.
Effects of amine nature and nonleaving group substituents on rate and mechanism in aminolyses of 2,4-dinitrophenyl x-substituted benzoates
Um, Ik-Hwan,Kim, Kyung-Hee,Park, Hye-Ran,Fujio, Mizue,Tsuno, Yuho
, p. 3937 - 3942 (2007/10/03)
Second-order rate constants have been measured for the reactions of 2,4-dinitrophenyl X-substituted benzoates (1a-f) with a series of primary amines in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The Bronsted-type plot for the reactions of 1d with primary amines is biphasic with slopes β1 = 0.36 at the high pKa region and β2 = 0.78 at the low pKa region and the curvature center at pKa° = 9.2, indicating that the reaction proceeds through an addition intermediate with a change in the rate-determining step as the basicity of amines increases. The corresponding Bro nsted-type plot for the reactions with secondary amines is also biphasic with β1 = 0.34, β2 = 0.74, and pKa° = 9.1, indicating that the effect of amine nature on the reaction mechanism and pKa° is insignificant. However, primary amines have been found to be less reactive than isobasic secondary amines. The microscopic rate constants associated with the aminolysis have revealed that the smaller k 1 for the reactions with primary amines is fully responsible for their lower reactivity. The electron-donating substituent in the nonleaving group exhibits a negative deviation from the Hammett plots for the reactions of 1a-f with primary and secondary amines, while the corresponding Yukawa-Tsuno plots are linear. The negative deviation has been ascribed to stabilization of the ground state of the substrate through resonance interaction between the electron-donating substituent and the carbonyl functionality.
An unusual ground-state stabilization effect and origins of the α- effect in aminolyses of Y-substituted phenyl X-substituted benzoates
Um, Ik-Hwan,Chung, Eun-Kyung,Lee, So-Mi
, p. 729 - 737 (2007/10/03)
Second-order rate constants have been measured spectrophotometrically for the reactions of X-C6H4CO2C6H4-Y with a series of primary amines in H2O containing 20 mol% DMSO at 25.0 ± 0.1°C. The reactivity increases as the substituent (X and Y) becomes a stronger electron-withdrawing group. The σ+ constants give better Hammett correlation than σ constants for the reactions of 4-nitrophenyl X-substituted benzoates with glycylglycine (glygly) and hydrazine (NH2NH2), indicating that the ground-state stabilization effect is unusually significant on the reaction rates. The reactions of X-C6H4CO2C6H4-Y with glygly and NH2NH2 appear to proceed through the same mechanism, but the degree of leaving-group departure and the negative charge developed in the acyl moiety at the rate-determining TS is considered to be more significant for the glygly system than the NH2NH2 system based on β(1g) and ρ(x) values. The magnitude of the α-effect is observed to be not always dependent on the β(nuc) value but dependent on the electronic nature of the substituent X and Y, i.e., an electron-donating substituent increases the α-effect, while an electron-withdrawing one decreases the α-effect. The present study has led to the conclusion that the ground-state effect is important for the reaction rates but it is not solely responsible for the α-effect, and the intramolecular H-bonding interactions (4) are proposed for the cause of the increasing or decreasing α-effect trends observed in the present system.
