3-氨基-4-偕羟胺肟基呋咱合成、歧化与水解反应研究

Synthesis, Disproportionation and Hydrolysis Reactions of3-Amino-4-hydroxyaminoximinofurazan

以3-氨基-4-偕氨肟基呋咱(DAOF)为原料,经重氮化、肟化等反应合成了未见文献报道的含能中间体——3-氨基-4-偕羟胺肟基呋咱(DOAF),总收率为61.8%,采用核磁共振、红外光谱、质谱和元素分析进行了结构表征.重点研究了肟化合成3-氨基-4-偕羟胺肟基呋咱的主要因素,确定了适宜反应条件为:反应温度30℃,反应时间2 h,n(ACOF)∶n(NH2OH HCl)∶n(CH3ONa)为1∶2∶3,收率为86.5%.发现了3-氨基-4-偕羟胺肟基呋咱在碱性条件下可发生歧化反应,歧化产物为3-氨基-4-偕二亚硝甲基呋咱钾盐[K(DNOF)]和原料DAOF;在酸性水溶液中发生水解反应,水解产物为3-氨基-4-(N-羟基酰胺)呋咱.培养并获得了K(DNOF)H2O单晶,结构分析表明,K(DNOF)H2O为单斜晶系,空间群为P2(1)/c,晶体学参数为: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,Dc=1.870 g cm-3,μ=0.695 mm-1,F(000)=432,R1=0.0349,wR2=0.1027.

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（NH2OHoHC1） ： n（CH3ONa） was 1 ： 2 ： 3, reaction temperature 30 ℃, 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,a=90°,β=101.025（3）°,γ=90°,V=0.7573（3）nm3,Z=4,Dc=1.870g·cm-3,μ=0.695mm-1,F（000）=432,R1=0.0349,wR2=0.1027.