| 4,4’-bi-1,2,4-triazole(BTr)was synthesized for the first time in 1976.It was widely used in the fields of catalytic chemistry,coordination chemistry and material science etc.,however,not in energetic material.In 1986,theoretical studies of the United States Los Alamos laboratory showed that BTr based 3,3’,5,5’-tetranitro-4,4’-bi-1,2,4-triazole(TNBT)was an ideal potential energetic compound,its density of 1.99 g/cm3,detonation velocity of 9.5 Km/s and detonation pressure of 42.2 GPa.Nevertheless,the synthesis of TNBT and its analogues has not been reported.The main work of this paper focus on the synthesis and technological of various aminated 4,4’-bi-1,2,4-triazole ionic salts including the following aspects:(1)In this work,three novel ionic salts were successfully synthesized with reducing 3,3’,5,5’-tetraazide-4,4’-bi-1,2,4-triazole(TABT)by(Ph)3P/H2 O and then reacted with concentrated HBr,HCl O4,HNO3,respectively.The structures of these ionic salts were characterized by IR,MS,1H NMR,13 C NMR and elemental analyses.(2)The single crystal of 3-amino-4,4’-bi-1,2,4-triazole hydrobromide(CCDC: 1516993)was successfully cultivated through the slow volatilization method with methanol as solvent,and its single crystal was characterized by X-ray single crystal diffraction.The results showed that the crystal of 3-amion-4,4′-bi-1,2,4-triazole hydrobromide is orthorhombic,space group is Pbca with crystal parameters of a = 1.54741(13)nm,b = 1.34743(12)nm,c = 1.57331(14)nm,α = 90°,β = 90°,γ = 90°,Z = 16,F(000)= 1824.0.Moreover,the crystal packing of 3-amion-4,4′-bi-1,2,4-triazole hydrobromide was stable due to the existence of intermolecular hydrogen bond,electrostatic attraction,supramolecular interactions and aromatic π···π packing interactions.(3)The effects of time,temperature,and acid dosage on the reaction yield were investigated.The optimum synthesis conditions were determined by single factor experiment. |
