Synthesis of 3-amino-4-nitrofurazan and 3,3′-dinitro-4,4′- azofurazan

3-Amino-4-nitrofurazan (ANF) and its derivatives are a new kind of important energetic materials. ANF was synthesized in three steps. The first two steps involved the synthesis of diaminoglyoxime (DAG) from aqueous glyoxal and hydroxylamine and 3,4-diaminofurazan (DAF) from DAG dehydration. Then DAF was oxidized using the mixture of hydrogen peroxide, sodium tungstate and methanesulfonic acid (H₂O₂/CH₃SO ₃H/Na₂WO₄) in place of the mixture of hydrogen peroxide, ammonium persulfate and sulfuric acid [H₂O ₂/H₂SO₄/(NH₄)₂S ₂O₈] to give a 67% yield of ANF. Treatment of ANF with potassium permanganate and concentrated hydrochloric acid afforded 3,3′-dinitro-4,4′-azofurazan (DNAzF) in a 54.7% yield. The experiments showed that the mixture of H₂O₂/CH ₃SO₃H/Na₂WO₄ was a new kind of efficient oxidant for the synthesis of mono- or multi-furazan rings with amino and nitro groups.