Synthesis, disproportionation and hydrolysis reactions of 3-amino-4-hydroxyaminoximinofurazan

A novel energetic intermediate 3-amino-4-hydroxyaminoximinofurazan (DOAF) was synthesized from 3-amino-4-amidoximinofurazan (DAOF) via diazotisation and oximation reactions with a total yield of 61.8%, and its structure was characterized by NMR, IR, MS and elemental analysis. The main factors for the oximation reaction were thoroughly studied, and the optimum reaction conditions were found to be as follows: the materials ratio n(ACOF):n(NH₂OH·HCl):n(CH3ONa) was 1:2:3, reaction temperature 30°C, and reaction time 2 h with a yield of 86.5%. It was found that 3-amino-4-hydroxyaminoximinofurazan (DOAF) was disproportionated to obtain two compounds under alkaline condition, which were identified as 3-amino-4-nitrosoximinofurazan potassium salt and DAOF. Moreover, DOAF was hydrolyzed to give a new product in acidic aqueous solution, which was identified as 3-amino-4-(N-hydroxyamido)furazan. The single crystal of K(DNOF)·H₂O was obtained and its crystal belong to monoclinic system, space group is P2(1)/c, cell parameters are a=0.7639(19) nm, b=0.7034(17) nm, c=1.436(4) nm, α=90°, β=101.025(3)°, γ=90°, V=0.7573(3) nm³, Z=4, D_c=1.870 g·cm^-3, μ=0.695 mm^-1, F(000)=432, R₁=0.0349 and wR₂=0.1027.