Study On The Functionalization Reaction Study Of 4,4?-bis-1,2,4-triazole(BTz)

Energetic compound based on 4,4'-bis-1,2,4-triazole(BTz) hasn't been reported. For the excellent thermal stability(on-set decomposition temperature of BTz is 274.6 oC) and the high heat of formation(multiple of N-N chemical bond) of BTz, it was noticed as the skeleton of energetic compounds in pursuing for high-energy low-sensitivity energetic materials. Michael has reported the calculating data of 3,3',5,5'-tetranitro-4,4'-bis-1,2,4- triazole(TNBT) in 1986. The results reveal excellent energetic properties with density of 1.99 g/cm, detonation velocity of 9500 m/s, and detonation pressure 42 GPa, all of which are superior to HMX and TATB. Hence, energetic compounds with 4,4'-bis-1,2,4-triazole(BTz) as the skeleton have the promising research value. This paper studied the group transformation in the C position of BTz deeply, for the purpose of TNBT and TNBT's derived compounds.Firstly, optimized the synthesis of BTz. Toluene was employed as solvent for it's low toxicity property. Reaction temperature in the synthesis of BTz was rised from 50 oC to 90 oC in the rate of 10 oC/30 min. And the yield of BTz was increased to 90%. Multi-methods have been used to nitrify BTz, and result in a salt formed by one BTz and one HNO3, rather than the expectant compound TNBT.In the next place, improved the synthesis of 3,3?,5,5?- tetraiodo-4,4?-bis-1,2,4- triazole(TIBT) and 3,3?,5,5?- tetrabromo-4,4?-bis-1,2,4- triazole(TBBT). The reaction time of TIBT was extend to 2.5 d. And the bromination reaction of BTz was treated with aqueous solution of KOH(5 M) to light yellow after the reaction lasted 2 d. And the yield of TIBT and TBBT were increased to 80% and 87% respectively. Further research of the functional-group conversion has been carried out. 3,5-di(methylamine)-3?,5?-dibromo-4,4?-bis-1,2,4-triazole(DMaDBBT) and 3,3?,5,5?-tetra(methylamine)-4,4?-bis-1,2,4-triazole(TMaBT) have been synthesized successfully in the way of methylamination to TBBT with the aqueous solution of methylamine. The thermal stability of DMaBBT and TMaBT have been measured with DSC. The DSC spectrograms reveal the excellent thermal stability of DMaBBT and TMaBT(Decomposition temperature of DMaBBT and TMaBT are 266 oC and 324 oC respectively). Various methods have been employed in the study of nitration to TIBT and TBBT. Nitration to TIBT with HNO3 result in a salt formed by one BTz and one HNO3, while the nitration to TBBT didn't happen. Nitration to TIBT with N2O5 and concentrate HNO3 result in I2 and the salt formed by one BTz and one HNO3, rather than TNBT.Finally, optimized the synthesis of 3,3?,5,5?-tetraazido-4,4?-bis-1,2,4-triazole(TABT). The mixed solvent of DMSO and H2O(V:V=10:1) was used in the synthesis of TABT, which contribute to the solubility of NaN3, lead to the yield of TABT increased to 68%. The reduction reaction of TABT has been studied systematically. Finally, 3,3',5,5'- tetra(tertbutylO-formamido)-4,4'-bis-1,2,4-triazole(TABocBT) was reached with a yield of 68% in the way of hydrogenation reduction with Pd/C(8%) as catalyst and protect amidogen with Boc2 O. Oxidation-reaction, diazo-reaction and cyclization reaction with the reduction product of TABT have been studied. A variety of cyano reagents have been used in the study of the cyclization reaction with TABT.