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

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℃。

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

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,1H NMR,13C 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=0.54504(15)nm,b=3.1462(9),c=0.7546(2),β =103.612(5)°,V=1.257 7(6)nm3,Z=2,Dc=1.554g/cm3,F(000)=608,ωR1 =0.1387 and ωR2 =0.3306.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.