Collect. Czech. Chem. Commun. 1990, 55, 2701-2706

Reactivity of proton and general acid with 1,3-bis-(4-methylphenyl)triazene in aqueous methanol

Oldřich Pytelaa, Taťjana Nevěčnáb and Jaromír Kaváleka

a Department of Organic Chemistry, Institute of Chemical Technology, 532 10 Pardubice
b Department of Inorganic and Physical Chemistry, Palacký University, 771 46 Olomouc


The effect of concentration of benzoic acid and composition of the binary solvent water-methanol on the rate of decomposition of 1,3-bis(4-methylphenyl)triazene has been studied. It has been found that both general acid catalysis by undissociated benzoic acid and catalysis by the proton are significant. The rate constant kHA of general acid catalysis decreases monotonously with decreasing amount of water in the mixture due to preferred solvation of the activated complex as compared with the educts. The rate constant kH of the catalysis by proton in its dependence on methanol concentration exhibits a minimum for 80% (by wt.) of methanol in the mixture. This phenomenon is caused by formation of the conjugated acid from more basic methanol and proton with simultaneous solvation by water and methanol; the particle thus formed is a weaker acid as compared with the complexes existing in water or in methanol. The kH value is higher in methanol than in water due to preferred solvation of the educts as compared with that of the transition state.