3-氨基-4-硝基呋咱和3,3’-二硝基-4,4’-偶氮呋咱的合成研究

3-氨基-4-硝基呋咱(ANF)及其衍生物是一类重要的含能材料. ANF的制备首先以乙二醛、盐酸羟胺和氢氧化钠为原料, 经过两步反应制得3,4-二氨基呋咱(DAF), 采用新的氧化体系过氧化氢/甲烷磺酸/钨酸钠混合物(H2O2/CH3SO3H/ Na2WO4)代替原氧化体系过氧化氢/硫酸/过硫酸铵混合物H2O2/H2SO4/(NH4)2S2O8]氧化DAF以67%的产率获得了ANF. 然后在单电子氧化体系高锰酸钾/盐酸混合物作用下ANF发生氧化反应以54.7%的产率得到3,3’-二硝基- 4,4’-偶氮呋咱(DNAzF). 研究表明过氧化氢/甲烷磺酸/钨酸钠混合物是制备氨基硝基单/多呋咱非常有效的氧化体系.

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/CH3SO3H/Na2WO4) in place of the mixture of hydrogen peroxide, ammonium persulfate and sulfuric acid H2O2/H2SO4/(NH4)2S2O8] to give a 67% yield of ANF. Treatment of ANF with potassium permanga-nate 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/CH3SO3H/Na2WO4 was a new kind of efficient oxidant for the synthesis of mono- or multi-furazan rings with amino and nitro groups.