3,4-二氨基呋咱的两种催化合成新方法  

Two New Synthesis Method of 3,4-Diaminofurazan

作　　者：李春迎[1] 马洋博[1] 薛云娜[1] 杨建明[1] 王伯周[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《含能材料》2012年第2期151-154,共4页Chinese Journal of Energetic Materials

摘　　要：研究了胶束催化和负载型固体碱催化的3,4-二氨基乙二肟分子内脱水合成3,4-二氨基呋咱的两种新方法。负载型固体碱催化下,考察了反应温度、压力、物料配比等对反应收率的影响,较佳的反应条件为:150℃,0.7 MPa,3,4-二氨基乙二肟(DAG)与负载型固体碱催化剂(cat.)和H2O的质量比为13.512.5,反应时间4 h,该条件下收率为91.2%。催化剂分离后重复使用五次以上,催化活性无明显下降。与氢氧化钾催化的反应相比,催化剂用量少,反应温度及压力低,收率高,易分离。胶束催化下,阴、阳离子表面活性剂在大于临界胶束浓度下均具有良好的催化效果,升高压力不利于反应进行。110℃,DAG与KOH、H2O及十二烷基苯磺酸钠(SDBS)的质量比为11.37.10.02条件下,常压反应10 h,反应收率为46.0%。3,4-Diaminofurazan was prepared from 3,4-diaminoglyoxime by two new methods.Supported solid alkali or micelle was used as catalysts in the reaction first time.When the reaction catalyzed by supported solid alkali,the optimal conditions are： 150 ℃,3,4-diaminoglyoximesupported solid alkaliH2O（mass）=1：3.5：12.5,4 h.Under those conditions,the yield could be improved to 91.2%.The temperature,pressure and catalyst amount are lower and yield is higher than the reaction catalyzed by KOH.Moreover,the catalyst can be reused at least five times without decreasing of catalyst activity.Then,3,4-diaminofurazan synthesis catalyzed by micelle was explored.Anionic and cationic surfactants both possessed well catalytic activity when the mass ratio of surfactant and 3,4-diaminoglyoxime was 0.02.On the condition of 110 ℃,DAG：KOH：H2O：sodium dodecyl benzene sulfonate（mass）=1：1.3：7.1：0.02,when the reaction time was 10 h,the yield was 46.0%.Compared with the reaction without catalyzed by micelle,the cite reaction could react at lower temperature and pressure.

关 键 词：有机化学 3 4-二氨基呋咱 3 4-二氨基乙二肟 负载型固体碱 胶束催化 

分 类 号：TQ560.1[化学工程—炸药化工]