N,N’-二硝基-N,N’-二(3-(1,2,3-三唑并4,5-c呋咱-4,5-内盐-5-基)呋咱-4-基)二氨基甲烷的合成与表征

摘要

Starting from diaminofurazan(DAF) , 5 , 5'-[metbanedinitramino-bis(1, 2 , 5-oxadiazol-4, 3-diyl)] bis[lH-[l,2,3]triazolo[4,5-c]-[l,2,5]oxadiazolium]-bis(innersalt) (MNOTO) was synthesized by oxidation with Caro's acid, reduction with Zn dust, cyclization, condensation reaction and nitration with condense nitrate acid/acetic anhydride in 32. 7% yield. The structures of intermediates and MNOTO were characterized by elemental analyses,IR and NMR. Condense nitrate acid with acetic anhydride was employed in the nitration of 5,5 '-[Methanediamino-bis (1,2,5-oxadiazol-4,3-diyl)] bis[lH-[l, 2, 3] triazolo[4, 5-c] [1,2, 5]oxadiazolium]-bis (innersalt) ( MAOTO). The effects of reaction temperature,reaction time and molar ratio of condense nitrate acid to acetic anhydride on the conversion of MAOTO to MNOTO were studied. The optimal reaction conditions obtained were:reaction temperature, 15 - 20°C ; reaction time,5h;the molar ratio of condense nitrate acid to acetic anhydride,1. 5 ∶ 1.%以二氨基呋咱(DAF)为起始原料,经Caro's acid氧化、锌粉还原、环化、缩合和硝化五步反应得到N,N’-二硝基-N,N ’-二(3-([1,2,3]-三唑并[4,5-c]呋咱-4,5-内盐-5-基)呋咱-4-基)二氨基甲烷(MNOTO),总收率为32.7％(以DAF计).用元素分析、核磁共振、红外光谱等进行了结构表征.用浓硝酸和醋酐作为硝化体系硝化N,N’-二(3-([1,2,3]-三唑并[4,5-c]呋咱-4,5-内盐-5-基)呋咱-4-基)二氨基甲烷(MAOTO),考察了反应温度、反应时间以及浓硝酸与醋酐摩尔比对反应收率的影响,硝化体系中硝酸和醋酐的最佳摩尔比为1.5∶1,反应温度15～20℃,反应时间为5h.