7H-双呋咱并[3,4-b∶3′,4′-f]氧化呋咱并[3″,4″-d]氮杂环庚三烯新法合成、晶体结构与性能  

7H-Difurazano[3,4-b∶3′,4′-f]furoxano[3″,4″-d]azepine:New Synthesis,Crystal Structure and Properties

作　　者：翟连杰[1,2] 罗义芬 李祥志[1,2] 杨凯迪 毕福强[1,2] 陈三平 王伯周 ZHAI Lian-jie;LUO Yi-fen;LI Xiang-zhi;YANG Kai-di;BI Fu-qiang;CHEN San-ping;WANG Bo-zhou(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China;State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi′an 710065,China;College of Chemistry and Materials Science,Northwest University,Xi′an 710127,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 [3]西北大学化学与材料科学学院,陕西西安710127

出　　处：《火炸药学报》2021年第2期168-174,共7页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21805224)。

摘　　要：以3,4-双(4′-硝基呋咱-3′-基)氧化呋咱和羟胺为原料,发现了高密度七元环化合物7H-双呋咱并[3,4-b:3′,4′-f]氧化呋咱并[3″,4″-d]氮杂环庚三烯(HATF)的一种新合成方法,提出并阐明了分子内环化与羟胺还原的反应机理;利用红外光谱、核磁共振、元素分析对产物结构进行了表征,结合理论模拟,完成了13C NMR和15N NMR谱的归属研究;成功培养了适合单晶X-射线衍射分析的HATF单晶,利用EXPLO5软件预估了HATF的理论爆速(D)和爆压(p),采用差示扫描量热技术(DSC)研究了HATF的热分解过程。结果表明,HATF属于单斜晶系,空间群为P212121,a=5.991(7)A,b=10.270(12)A,c=13.192(15)A,V=811.7(17)A3,Z=4,ρ=1.924g/cm^(3),F(000)=472,μ=0.166mm-1,S=1.032,R1=0.0404,wR2=0.0854;HATF的理论爆速和爆压分别为8541m/s和31.4GPa,能量水平与RDX相当。HATF的转晶峰温为183℃,熔点为227.7℃,起始分解温度为271.5℃,表明HATF是一种密度大、热稳定性好、爆轰性能优异的高能量密度化合物。Starting from bis(3-nitrofurazan-4-yl)furoxan and hydroxylamine,a new synthetic method towards the synthesis of 7H-difurazano[3,4-b:3′,4′-f]furoxano[3″,4″-d]azepine(HATF),a high density heptatomic heterocyclic compound,was achieved.The reaction mechanisms of intramolecular cyclization and NH2OH reduction were proposed and illuminated.The structure of HATF was characterized by IR,NMR and elemental analysis;meanwhile,the chemical shifts of 13C NMR and 15N NMR were assigned based on theoretical simulations.The single crystal of HATF suitable for X-ray diffraction analysis was cultivated successfully and its detonation velocity(D)and detonation pressure(p)of HATF were calculated with EXPLO5.The thermal decomposition of HATF was investigated through the differential scanning calorimetry(DSC).The results show that its crystal belongs to orthorhombic,P212121 space group,a=5.991(7)A,b=10.270(12)A,c=13.192(15)A,V=811.7(17)A3,Z=4,ρ=1.924g/cm^(3),F(000)=472,μ=0.166mm-1,S=1.032,R1=0.0404,wR2=0.0854.The detonation velocity and detonation pressure of HATF are 8541m/s and 31.4GPa,respectively,which are comparable to those of RDX.Moreover,the crystal transformation point,melting point and onset decomposition temperature of HATF are 183,227.7 and 271.5℃,respectively.These results indicate that HATF is a high-energy-density compound with high density level,good thermal stability and superior detonation performances.

关 键 词：有机化学 高能量密度材料 HATF 晶体结构 热分解 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]