摘要
以3,3'-二氰基-4,4'-偶氮呋咱为原料,经加成、重氮化以及硝化等反应得到3,3'-二(偕二硝基甲基)-4,4'-偶氮呋咱(4)及其钾盐(3),四步反应的收率分别为93.3%、91.2%、24.5%和63.1%。在反应过程中分离得到一种未见报道的呋咱化合物——3,3'-二偕氨肟基-4,4'-联氨呋咱(1),推测在羟氨与氰基发生加成反应的过程中,过量羟氨同时将偶氮基还原为联氨基,从而生成1。通过~1H NMR、^(13)C NMR、IR以及质谱等手段对反应中间体及产物结构进行表征。利用差示扫描量热法-热重法研究1、3和4的热分解过程,结果表明:1的热分解包括一个脱结晶水吸热过程和两个热分解放热过程,热失重率分别为5.1%、53.5%和36.3%,吸热峰温为83.7℃,放热分解峰温分别为241.1℃和336.2℃;3的热分解过程仅有一个明显的分解放热阶段,热失重率为86.6%,峰值温度为258.1℃;4的热分解过程也仅有一个明显的分解放热阶段,热失重率为71.8%,其峰值温度为156.0℃。
4,4 ＇-Bis（ dinitromethyl ） -3,3 ＇-azofurazan （4） and potassium 4,4 ＇-bis（ dinitromethyl ） -3,3 ＇-azofurazanate （ 3 ） were syn- thesized from 4,4＇-dicyano-3,3＇-azofurazan through addition, diazotization and nitration with yield for each step reaction of 93.3 %, 91.2 %, 24.5 % and 63.1%, respectively. In addition, a new furazan, 4,4 ＇-aminoxim-3,3 ＇-hydrazinefurazan （ 1 ）, was obtained in the synthesis process of 4. This synthesis of I may proceed first with hydroxylamine addition of 4,4＇-dicyano-3,3＇-azo- furazan followed by reduction of excessive hydroxylamine. The intermediates and product were analyzed by1 H NMR,13C NMR,IR and mass spectrum. The thermal behavior of 1 , 3 and 4 were studied by DSC-TG method. The thermal behavior of 1 includes one dehydration endothermal stage and two obvious decomposition stages with mass loss of 5.1%, 53.5% and 36.3%, respectively. The peak temperature of each stage is 83.7 ℃, 241.1 ℃ and 336.2 ℃. The thermal behavior of 3 and 4 include only one obvious decomposition stage. The mass loss and the peak temperature are 86.6% and 258.1 ℃, 71.8% 156.0 ℃, respectively.
作者
黄晓川
王子俊
秦明娜
郭涛
刘敏
邱少君
HUANG Xiao-chuan WANG Zi-jun QIN Ming-na GUO Tao LIU Min QIU Shao-jun(Xi＇an Modern Chemistry Research Institute, Xi＇an 710065, China)
出处
《含能材料》
EI
CAS
CSCD
北大核心
2017年第10期843-847,共5页
Chinese Journal of Energetic Materials
关键词
偶氮呋咱
二硝基甲基
有机合成
热性能
含能材料
azofurazan
dinitromethy
organic synthesis
thermal behavior
energetic material
