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-azabicyclo[3,3,0]octane b y chloramine has been studied by GC and HPLC in stoichiometric conditi ons 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 enthalp y and entropy of activation were determined at pH = 12.89. In a nonbuf fered solution, the interaction is autocatalyzed due to acidification of the mixture by the ammonium ions. In basic medium, the reaction for ms an endocyclic hydrazone. A mathematical treatment based on an impli cit equation allows a quantitative interpretation of all the phenomena observed over the above pH interval. This takes both the acid/base di ssociation equilibria and the alkaline hydrolysis of the chloro-deriva tive into account. (C) 1995 John Wiley and Sons, Inc.