96953-69-4Relevant academic research and scientific papers
Reaction mechanism studies involving the correlation of the rates of solvolysis of benzoyl and p-nitrobenzoyl p-toluenesulfonates
Kevill, Dennis N.,Ryu, Zoon Ha
, p. 387 - 395 (2014/08/05)
The solvolyses of benzoyl and p-nitrobenzoyl p-toluenesulfonates (tosylates) are considerably slower than those of the previously studied mixed anhydride of acetic and p-toluenesulfonic acids (acetyl tosylate), which, even with application of rapid-response conductivity, could only be studied at considerably reduced temperatures. For the presently studied compounds, the specific rates over a wide variety of solvents could be conveniently studied at -10 °C. For solvolyses of benzoyl tosylate, application of the extended (two-term) Grunwald-Winstein equation gives sensitivities to changes in solvent nucleophilicity and solvent ionising power consistent with an ionisation (S Nl) pathway. Indeed, a good correlation is obtained against only solvent ionising power. For the solvolyses of the p-nitro-derivative, very different sensitivities are obtained, with an appreciable dependence on solvent nucleophilicity, and a dominant biomolecular pathway for the substitution is proposed for all of these solvolyses, except for those in solvents rich in fluoroalcohol. Studies of solvent deuterium isotope effects in methanolysis, of leaving-group effects relative to a halide and of temperature variation effects are consistent with the proposed mechanistic pathways.
Kinetic investigation on the reactions of p-toluenesulfonyl chloride with p-substituted benzoic acid(s) in the presence of triethylamine in aprotic solvents
Ananthalakshmi, Subbiah,Nallu
experimental part, p. 303 - 308 (2009/10/17)
Second-order rate constants of the reactions of p-toluenesulfonyl chloride with p-substituted benzoic acids in the presence of triethylamine in acetonitrile/acetone under equimolar and pseudo-first-order conditions have been determined by the conductometric method using the Guggenheim principle at 25, 30, 35, and 40°C. The reactions follow second order with respect to the whole and first order with respect to each of the reactants. The order of reactivity of the substituents in benzoic acid is rationalized. Activation parameters are obtained by applying the usual methods. The Hammett plot has been found nonlinear, whereas the Bronsted plot shows good correlation. This may be explained on the basis of electronic effects of substituents on the reaction center. Kinetic data and the product analyses indicate that the reaction proceeds through direct nucleophilic attack on the sulfur center. Int J Chem Kinet 41: 303-308, 2009
