Kinetics of the autocatalytic oxidation of N-amino-3-azabicyclo[3,3,0]octane by chloramine in aqueous medium

The kinetics of the degradation of N-amino-3-azabicyclo3,3,0]octane by chloramine has been studied by GC and HPLC in stoichiometric conditions in a solution buffered with NaOH/KH₂PO₄ and Na₂B₄O₇.10 H₂O between pH = 10.5 and 13.5. The second-order reaction exhibits specific acid catalysis which indicates competitive oxidation between the haloamine and the neutral and ionic forms of the bicyclic hydrazine. The enthalpy and entropy of activation were determined at pH = 12.89. In a nonbuffered solution, the interaction is autocatalyzed due to acidification of the mixture by the ammonium ions. In basic medium, the reaction forms an endocyclic hydrazone. A mathematical treatment based on an implicit equation allows a quantitative interpretation of all the phenomena observed over the above pH interval. This takes both the acid/base dissociation equilibria and the alkaline hydrolysis of the chloro-derivative into account. © 1995 John Wiley & Sons, Inc.