7-羟基三呋咱并[3,4-b:3′,4′-f:3″,4″-d]氮杂环庚三烯的合成与性能  

Synthesis and Properties of 7-Hydroxytrifurazano[3,4-b:3′,4′-f:3″,4″-d]azepine

作　　者：翟连杰[1,2] 霍欢 吴敏杰[1] 张家荣[1] 毕福强[1,2] 王伯周[1,2] ZHAI Lian-jie;HUO Huan;WU Min-jie;ZHANG Jia-rong;BI Fu-qiang;WANG Bo-zhou(Modern Chemistry Research Institution,Xi′an 710065,China;State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《含能材料》2020年第11期1043-1047,I0002,共6页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(21805224)。

摘　　要：以3,4-双(4′-硝基呋咱-3′-基)呋咱为原料,与羟胺溶液一步法合成了一种新型七元环化合物7‑羟基三呋咱并[3,4-b:3′,4′-f:3″,4″-d]氮杂环庚三烯(HYTF),并利用红外光谱、核磁共振、元素分析对产物进行了表征。通过规范不变原子轨道方法完成了HYTF的13C NMR和15N NMR理论模拟,结合实验数据实现了HYTF的13C NMR和15N NMR的准确归属。发现3,4-双(4′-硝基呋咱-3′-基)呋咱与羟胺在不同反应温度条件下可分别生成HYTF和7H-三呋咱并[3,4-b:3′,4′-f:3″,4″-d]氮杂环庚三烯(HATF),提出了HYTF与羟胺作用生成HATF的反应机理。基于实测密度(ρ=1.86 g·cm-3)和预估生成焓(ΔfH(s)=573.8 kJ·mol-1),利用Explo5(V6.04)软件预估HYTF的爆速和爆压分别为8181 m·s^-1和28.0 GPa。采用差示扫描量热仪(DSC)研究了HYTF的热分解过程,其热分解峰温为161.8℃。A new seven-membered cyclic compound 7-hydroxytrifurazano[3,4-b:3′,4′-f:3″,4″-d]azepine(HYTF)was synthesized using bis(3-nitrofurazan-4-yl)furazan and hydroxylamine solution as starting materials.The structure of HYTF was characterized by IR,13C and 15N NMR and elemental analysis.The chemical shifts of 13C and 15N NMR for HYTF were assigned based on the experimental results and theoretical simulation(Gauge Independent Atomic Orbital).7-Hydroxytrifurazano[3,4-b:3′,4′-f:3″,4″-d]azepine(HYTF)and 7H-trifurazano[3,4-b:3′,4′-f:3″,4″-d]azepine(HATF)could be synthesized by controlling the reaction temperature,and their formation mechanism were proposed and illuminated.Based on the experimental density(ρ=1.86 g·cm-3)and calculated enthalpy of formation(ΔfH(s)=573.8 kJ·mol-1),the detonation velocity(8181 m·s^-1)and detona-tion pressure(28.0 GPa)of HYTF were calculated by Explo5(V6.04).In addition,the thermal stability(Tdec=161.8℃)was analyzed by differential scanning calorimetry(DSC).

关 键 词：7-羟基三呋咱并[3 4-b:3′ 4′-f:3″ 4″-d]氮杂环庚三烯 含能材料 呋咱 七元环化合物 爆轰性能 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]