Structure-Reactivity Correlations in the Dissociative Hydrolysis of 2',4'-Dinitrophenyl 4-Hydroxy-X-benzenesulfonates |
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Authors: | Cevasco Giorgio Thea Sergio |
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Affiliation: | C.N.R., Centro di Studio per la Chimica dei Composti Cicloalifatici ed Aromatici, Via Dodecaneso 31, 16146 Genova, Italy, and Dipartimento di Chimica, Via Vienna 2, Università di Sassari, 07100 Sassari, Italy. |
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Abstract: | The hydrolysis reactions of several title esters in water at 60 degrees C follow the rate law k(obs) = (k(a) + k(b)[OH(-)])/(1 + a(H)/K(a)), where K(a) is the ionization constant of the hydroxy group of the ester and k(b) is the second-order rate constant for the S(N)2(S) attack of hydroxide ion on the ionized ester. Hammett and Br?nsted correlations are consistent with a previous proposal that the mechanism related to k(a) is dissociative. An unusual relationship between k(a) values and redox equilibrium constants for substituted quinones is found to hold: this finding further supports the dissociative nature of the pathway related to k(a). |
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