3,3′-双(2,2-二甲基-5-硝基-1,3-二氧杂环己烷-5-ONN-氧化偶氮基)氧化偶氮呋咱(BDDAF)的合成、晶体结构与热行为  

Synthesis,Crystal Structure and Thermal Behavior of 3,3′-Bis(2,2-dimethyl-5-nitro-1,3-dioxan-5-yl-ONN-azoxy) azoxyfurazan(BDDAF)

作　　者：张家荣 毕福强[1,2] 王伯周 张俊林[1,2] 贾思媛 

机构地区：[1]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 [2]西安近代化学研究所,陕西西安710065

出　　处：《火炸药学报》2017年第5期45-50,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金资助(No.21243007)

摘　　要：以三羟甲基硝基甲烷(TN)和丙酮为原料,通过缩合、碱催化、亚硝化反应合成了2,2-二甲基-5-硝基-5-亚硝基-1,3-二氧杂环己烷(DMNNDO),然后以DMNNDO与二氨基氧化偶氮呋咱(DAOAF)为原料,经氧化偶联反应合成了含能中间体3,3′-双(2,2-二甲基-5-硝基-1,3-二氧杂环己烷-5-ONN-氧化偶氮基)氧化偶氮呋咱(BDDAF),4步反应总收率为40%;采用IR、1 H NMR、13 C NMR、15 N NMR和元素分析对目标化合物进行了结构表征;培养并获得了BDDAF的单晶,利用X-射线单晶衍射仪对其结构进行了表征;利用差示扫描量热(DSC)法和热重分析(TG)法研究了BDDAF的热行为。结果表明,BDDAF为单斜晶系,空间群为P2(1)/n,晶胞参数为a=0.545 04(15)nm,b=3.146 2(9),c=0.754 6(2),β=103.612(5)°,V=1.257 7(6)nm3,Z=2,Dc=1.554g/cm3,F(000)=608,wR1=0.138 7,wR2=0.330 6;优化了氧化偶联反应条件,收率达到85%;改进了氧化偶联的后处理方法,采用溶剂-非溶剂法代替柱层析分离法,产品纯度大于99%;BDDAF的熔点为117℃,热分解温度为248℃。Taking tri（hydroxymethyl）nitromethane（TN）and acetone as raw materials,2,2-dimethyl-5-nitro-5-nitroso-1,3-dioxane（DMNNDO）was synthesized via.condensation,alkaline hydrolysis and nitrosation reactions.The energetic intermediate 3,3′-bis（2,2-dimethyl-5-nitro-1,3-dioxan-5-yl-ONN-azoxy）azoxyfurazan（BDDAF）was synthesized via.oxidative-coupling reaction taking DMNNDO and DAOAF as starting materials,and the total yield of this four-step reactions was 40%.The structure of target compound was characterized by IR,1 H NMR,13 C NMR,15 N NMR and elemental analysis.The single crystal of BDDAF was cultured and its structure was characterized by X-ray single crystal diffractometer.The thermal behavior of BDDAF was investigated by differential scanning calorimetry（DSC）and thermogravimetric analysis（TG）method.The results show that the crystal belongs to monoclinic system,space group is P2（1）/n,cell parameters are a=0.545 04（15）nm,b=3.146 2（9）,c=0.754 6（2）,β=103.612（5）°,V=1.257 7（6）nm3,Z=2,Dc=1.554 g/cm3,F（000）=608,wR1=0.138 7 and wR2=0.330 6.The oxidative coupling reaction conditions are optimized and the yield can reach 85%.The solvent-nonsolvent method is used instead of column chromatography,the purity of BDDAF is more than 99%,and the melting point and decomposition temperature are 117℃ and 248℃,respectively.

关 键 词：有机化学 三羟甲基硝基甲烷 氧化偶氮呋咱 含能化合物 BDDAF 

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]