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Synthesis and Characterization of 7H-Trifurazano-[3,4-b:3',4'-f:3",4"-d]azepine and Its Analogues
Received date: 2014-09-05
Revised date: 2014-10-11
Online published: 2014-12-15
Supported by
Project supported by the National Natural Science Foundation of China (No. 21243007).
Using 3,4-bis(4'-aminofurazano-3'-yl)furazan (BATF) as the starting material, 3,4-bis(4'-nitrofurazano-3'-yl)- furazan (BNTF) was synthesized by Caro's acid oxidation with a yield of 93%. Based on the reactivity of NO2 in BNTF, two energetic material 7H-trifurazano[3,4-b:3',4'-f:3",4"-d]azepine (HTFZA) and 7-aminotrifurazano[3,4-b:3',4'-f:3",4"-d]azepine (ATFAZ) were designed and synthesized from BNTF and NH3·H2O or NH2NH2·H2O via the nucleophilic substitution and cyclization, then HTFAZ was nitrated in the system of HNO3-Ac2O to firstly obtain a novel compound 7,7'-bis(terfurazan [3,4-b:3,4'-d:3",4"-f]azepine) (BTFZ). The above three compounds were characterized by the means of IR, 1H NMR, 13C NMR, MS and elemental analysis. The single crystal of HTFAZ was studied by X-ray single crystal diffraction. Its crystal belongs to orthorhombic, space group is P2(1)/n with a=0.7252(15) nm, b=0.6458(14) nm, c=1.6814(4) nm, V=0.7781(3) nm3, Z=4, Dc=1.871 g·cm-3, F(000)=440, R1=0.0353 and wR2=0.0895. The properties of HTFAZ, ATFAZ and BTFZ were measured and followed as: HTFAZ: the density was 1.871 g·cm-3, the enthalpy of formation was 733.7 kJ·mol-1, the melt point was 193.1 ℃, the decomposition point was 345.1 ℃, the explosion velocity was 8416.5 m·s-1, the detonation pressure was 32.9 GPa; ATFAZ: the density was 1.788 g·cm-3, the enthalpy of formation was 831.2 kJ·mol-1, the melt point was 204～207 ℃, the decomposition point was 323.7 ℃, the explosion velocity was 8300 m·s-1, the detonation pressure was 30 GPa; BTFZ: the density was 1.862 g·cm－3, the enthalpy of formation was 1752.4 kJ·mol-1, the decomposition point was 280.2 ℃, the explosion velocity was 7924.5 m·s-1, the detonation pressure was 28.42 GPa.
Jia Siyuan , Zhang Haihao , Zhou Cheng , Lai Weipen , Li Xiangzhi , Wang Bozhou . Synthesis and Characterization of 7H-Trifurazano-[3,4-b:3',4'-f:3",4"-d]azepine and Its Analogues[J]. Chinese Journal of Organic Chemistry, 2015 , 35(4) : 851 -857 . DOI: 10.6023/cjoc201409006
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