SPECIFIC ACID CATALYSIS IN THE DECOMPOSITION OF TRIALKYLTRIAZENES.

Article abstract of DOI:10.1021/ja00316a040

The acid-catalyzed decomposition of 1,3-di-n-butyl-3-methyltriazene (1) in aqueous buffer was investigated. Determination of the kinetics over a pH range of 10. 4 to 12 indicated that the reaction is acid catalyzed. Variation of buffer concentration, at constant ionic strength, produced an insignificant variation in the rate constant. The determination of kinetics of the decomposition of 1 in nine different buffers, ranging in pK//a from 9. 6 to 12. 7, also gave negligible variation in the rate constants. The solvent isotope effect for the reaction, k//H/k//D, was 0. 62. These data strongly support the conclusion that the reaction is specific acid catalyzed. This implies that the reaction involves fast, reversible protonation of the triazene followed by the rate-determining heterolysis of the protonated species to n-butyldiazonium ion and n-butylmethylamine.