氨基呋咱氧化为氨基硝基呋咱的合成研究

研究开发了将氨基呋咱转化为氨基硝基呋咱新的高收率氧化方法. 采用甲烷磺酸为介质, 以过氧化氢、碱或碱土金属和胺为基的氧化物(如钨酸钠或过硫酸铵)混合物的新氧化体系H2O2/CH3SO3H/Na2WO4或(NH4)2S2O8]代替以硫酸为介质的过氧化氢和过硫酸铵混合物氧化体系, 分别对3,4-二氨基呋咱(DAF)、3,3’-二氨基-4,4’-氧化偶氮呋咱(DAAF)和3,3’-二氨基-4,4’-偶氮呋咱(DAAzF)进行氧化, 以高于65%的产率获得了3-氨基-4-硝基呋咱(ANF)和3-氨基-3’-硝 基-4,4’-氧化偶氮呋咱(ANAF), 并以15%的收率合成得到新化合物3-氨基-3’-硝基-4,4’-偶氮呋咱(ANAzF). 研究表明甲烷磺酸/过氧化氢/碱或碱土金属和胺为基的氧化物混合物是制备同时含有氨基和硝基基团的系列呋咱化合物非常有效的氧化体系.

Synthesis of Aminonitrofurazan by Oxidizing Aminofurazan

The new general synthetic method has been developed for the convenient preparation of aminonitrofurazans. The synthesis of 3-amino-4-nitrofurazan (ANF), 3-amino-3’-nitro-4,4’-azoxyfurazan (ANAF) and 3-amino-3’-nitro-4,4’-azofurazan (ANAzF) were achieved by oxidizing 3,4-diaminofurazan (DAF), 3,3’-diamino-4,4’-azoxyfurazan (DAAF) and 3,3’-diamino-4,4’-azofurazan (DAAzF) respectively, with the oxidizing mixtures of hydrogen peroxide, sodium tungstate or ammonium persulfate and methanesulfonic acid H2O2/CH3SO3H/Na2WO4 or (NH4)2S2O8] with reduced acidity to give above 65% yield of ANF and ANAF, and 15% yield of ANAzF. The experiments showed that the mixture of H2O2 and Na2WO4 or (NH4)2S2O8) in CH3SO3H media is a new kind of efficient oxidant for the synthesis of one or more furazan rings with amino and nitro groups.