FORMATION OF 3,4-DIAZABICYCLO[4,3,0]NON-2-ENE AND N,N'-AZO-3-AZABICYCLO[3,3,0]OCTANE BY OXIDATION OF AN ALICYCLIC HYDRAZINE - INFLUENCE OF PH ON THE DIAZENE REARRANGEMENT

3,4-Diazabicyclo[4,3,0]non-2-ene and N,N'-azo-3-azabicyclo[3,3,0]octan e are the main products of the oxidation of N-amino-3-azabicyclo[3,3,0 ]octane by chloramine. The reaction leads to the transient formation o f a saturated bicyclic aminonitrene (diazene). At pH > 13, the diazene undergoes an intramolecular rearrangement to afford a hydrazone. At p H < 9, a white solid is formed resulting from the dimerization of the molecular and protonated forms of the aminonitrene. At intermediate pH -values, a mixture of both species is obtained. They have been isolate d and characterized by UV, GC/MS, IR, and H-1/C-13 NMR. A reaction mec hanism is proposed.