Comparative Study of the Water-Catalyzed Hydrolysis of methyl Perchlorate in 1,4-Dioxane-Water and in 1,3-Dioxane-Water

Article abstract of DOI:10.1021/jo00330a034

Pseudo-first-order rate constants (k_obsd) and thermodynamic activation parameters have been compared for the water-catalyzed hydrolysis of <(p-nitrophenyl)sulfonyl)methyl perchlorate (1) in 1,4-dioxane-water and in 1,3-dioxane-water.Characteristic differences in the kinetic basicities of both reaction media are only observed below n_H2O = 0.80 and most likely reflect the specific hydrogen bonding interactions between water and the organic cosolvent.The structural properties of both aqueous binaries are critically discussed, and it is concluded that the maxima ink_obsd at about n_H2O = 0.80 in both solvent mixtures do not reflect an enhanced degree of water structure at this solvent composition.