7H-三呋咱并[3,4-b:3',4'-f:3″,4″-d]氮杂环庚三烯及新型含能衍生物合成及性能的理论计算

Synthesis and Theoretical Calculation of Properties for 7H-Trifurazano[3,4-b: 3',4'-f: 3″,4″-d]azepine and Its Novel Energetic Derivatives

以3,4-双(3'-硝基呋咱-4'-基)氧化呋咱(DNTF)为原料,经亲核取代、环化、还原反应得到7H-三呋咱并[3,4-b:3',4'-f:3″,4″-d]氮杂环庚三烯(HTFAZ);利用HTFAZ的反应活性,自主设计合成了两种新型含能化合物7-(2,4,6-三硝基苯基)-三呋咱并[3,4-b:3',4'-f:3″,4″-d]氮杂环庚三烯(化合物1)和7-(2,4,6-三硝基-3,5-二氨基苯基)-三呋咱并[3,4-b:3',4'-f:3″,4″-d]氮杂环庚三烯(化合物2),并采用红外、核磁(1H NMR、13C NMR)、元素分析等进行了结构表征;采用DSC方法研究了化合物1和化合物2的热性能;采用Kamlet-Jacobs方程预估了两种化合物的爆轰性能。结果表明,改进HTFAZ的合成路线后,HTFAZ的收率达到63. 2%;化合物1和化合物2的热分解温度分别为371. 7℃和296. 3℃,表现出良好的热稳定性;化合物1的密度为1. 90 g/cm^3,理论爆速为8033 m/s,理论爆压为30. 11 GPa,其爆轰性能优于TNT,密度和热稳定性高于TNT和RDX。

7H-Trifurazano[3,4-b:3′,4′-f:3″,4″-d]azepine(HTFAZ)was synthesized via the reactions of nucleophilic substitution,cyclization and reduction using 3,4-bis(3′-nitrofurazano-4′-yl)furoxan(DNTF)as starting material.Based on the reactivity of HTFAZ,the two novel energetic compounds 7-(2,4,6-trinitrophenyl)-trifurazano[3,4-b:3′,4′-f:3″,4″-d]azepine(compound 1)and 7-(2,4,6-trinitro-3,5-diaminophenyl)-trifurazano[3,4-b:3′,4′-f:3″,4″-d]azepine(compound 2)were self-designed and synthesized.The structures of the target compounds were characterized by IR,1H NMR,13 C NMR and elemental analysis.The thermal behaviors of compounds 1 and compound 2 were investigated by DSC and the detonation performances of the two compounds were predicted by Kamlet-Jacobs equations.The results show that the yield of HTFAZ reaches 63.2%after improving synthetic route.The thermal decomposition temperatures of compound 1 and compound 2 are 371.7℃and 296.3℃,respectively,showing good thermal stability.The density of compound 1 is 1.90g/cm^3,the peak temperature of thermal decomposition is 371.7℃,the theoretical detonation velocity is 8033m/s and theoretical detonation pressure is 30.11GPa,The detonation performance of compound 1 is better than that of TNT,and the density and thermal stability are greater than those of TNT and RDX.