3,4-双(5-氢-1-四唑基)呋咱的合成及理论计算  

Synthesis and Theoretical Calculation of 3,4-Bis(5H-1-tetrazolyl) furazan

作　　者：万新军[1] WAN Xin-jun(College of Chemistry and Material Engineering,Chaohu University, Chaohu Anhui 238000,Chin)

机构地区：[1]安徽巢湖学院化学与材料工程学院,安徽巢湖238000

出　　处：《火炸药学报》2017年第2期60-64,共5页Chinese Journal of Explosives & Propellants

基　　金：巢湖学院自然科学基金资助项目(No.XLY-201507)

摘　　要：以3-氨基-4-硝基呋咱(ANF)为原料,与原甲酸三乙酯、叠氮化钠反应,得到3-硝基-4-(5-氢-1-四唑基)呋咱(化合物1),然后低温下经氨水胺化得到3-氨基-4-(5-氢-1-四唑基)呋咱(化合物2),化合物2与原甲酸三乙酯、叠氮化钠反应,最终得到3,4-双(5-氢-1-四唑基)呋咱(化合物3)。采用IR、~1 H NMR、^(13) C NMR及元素分析对3种化合物的结构进行了表征;采用密度泛函理论B3LYP/6-311+G**方法预估了化合物1~3的标准生成焓、密度、爆速、爆压。结果表明,通过控制反应条件,确定了制备化合物2的最佳工艺条件为:化合物1与氨水摩尔比为1∶2,反应时间3h,反应温度-10℃。化合物2的收率为70%。四唑环的引入使化合物1~3都具有较高的正生成焓,其中化合物3最高,达到1 090.07kJ/mol。化合物1的爆速、爆压与RDX相当。除化合物2密度略低于TNT外,化合物1~3各性能均优于TNT。与化合物2和3综合比较,化合物1的性能最佳,密度为1.76g/cm^3,爆速为8 590m/s,爆压为32.3GPa。3-Nitro-4-（5H-1-tetrazolyl）-furazan（compound 1） was synthesized with 3-amino-4-nitrofurazan（ANF） as raw material reacted with triethyl orthoformate and sodium azide,then compound 1 reacted with ammonia spirit via amination at a low temperature to get 3-amino-4-（5H-1-tetrazolyl）furazan （compound 2）,finally,3,4-bis（5H-1-tetrazolyl）furazan （compound 3） was obtained by the reaction of compound 2 with triethyl orthoformate and sodium azide.The structures of the three compounds were characterized by IR,^1H NMR,^13C NMR and elemental analysis.The standard enthalpy of formation,theoretical density,detonation velocity and detonation pressure of compounds 1-3 were predicted by density functional theory B3LYP/6-311＋G^＊＊ method.The results show that by controlling the reaction conditions,the optimal conditions for preparing compound 2 are determined as： reaction time 3h,molar ratio of compound 1 and ammonia 1：2,reaction temperature-10℃.The total yield of compound 2 is 70%.Compounds 1-3 have higher positive enthalpy of formation because of the introduction of tetrazole ring.In which,compound 3 has the highest enthalpy of formation,reaching 1090.07kJ/mol.Compound 1 has equal detonation velocity and detonation pressure as RDX.Compounds 1-3 have better detonation properties than TNT except compound 2 has a lower density.Comprehensively compared with compounds 2 and 3,the performance of compound 1 is the best,with density of 1.76g/cm^3,detonation velocity 8590m/s and detonation pressure 32.3GPa.

关 键 词：有机化学 3 4-双(5-氢-1-四唑基)呋咱 呋咱四唑类含能化合物 胺化 生成焓 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ226[化学工程—有机化工]