7622-07-3Relevant articles and documents
Nonlinear Hammett plots in pyridinolysis of 2,4-dinitrophenyl X-substituted benzoates: Change in RDS versus resonance contribution
Um, Ik-Hwan,Im, Li-Ra,Kim, Eun-Hee,Shin, Ji Hye
experimental part, p. 3801 - 3806 (2010/09/06)
Second-order rate constants (kOH-) have been measured for nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzoates (1a-j) with Z-substituted pyridines in 80 mol% H2O/20 mol% DMSO at 25.0 ± 0.1 °C. The Hammett plots for the reactions of 1a-j with pyridines consist of two intersecting straight lines, i.e., a large ρ value for the reactions of substrates (1a-c) possessing an electron-donating group (EDG) in the benzoyl moiety and a small one for substrates (1e-j) bearing an electron-withdrawing group (EWG). The nonlinear Hammett plots have been attributed to stabilization of the ground state of substrates 1a-c through resonance interactions between the electron-donating substituent and the carbonyl functionality, since the corresponding Yukawa-Tsuno plots exhibit excellent linear correlations with large r values. It has been shown that substrates 1e-j are not unusually more reactive than would be expected from the Hammett substituent constants, but rather, substrates 1a-c exhibit lower reactivity than would be predicted. The Bronsted-type plots for pyridinolysis of 1a-j are linear with βnuc = 0.74-0.98, indicating that the reaction proceeds through a stepwise mechanism in which the second step is the RDS. It has been concluded that the electronic nature of the substituent X in the benzoyl moiety does not influence the RDS, but the degree of bond formation (or the effective charge on the nucleophilic site) in the transition state becomes more significant as the substituent X changes from a strong EDG to a strong EWG.
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.