Synthesis Of Several Azole Energetic Derivatives

Azole energetic compounds are one of five-membered nitrogen containing heterocyclic energetic materials, and widely researched in the field of single compound explosive. For the characteristics of nitrogen rich, low hydrocarbon, high energy density etc., many molecular structures satisfy the demand of new high-energy low(blunt) sense of explosive with environment friendly. This dissertation aims at the synthesis of several triazole and tetrazole energetic compounds, the contents are as follows:1 The synthesis of 3,3’,5,5’-tetramino-4,4’-bi-1,2,4-triazole was tested from 3,3’,5,5’-tetrachloro-4,4’-bi-1,2,4-triazole and 3,3’,5,5’-tetrabromo-4,4’-bi-1,2,4-triazole aminated by various ammoniation reagents respectively. The process conditions of the synthesis of 3,3’,5,5’-tetraazido-4,4’-bi-1,2,4-triazole were investigated, the optimal conditions of the process were determined: DMF as solvent, 0 oC, 2.5 h, n(3,3’,5,5’-tetrabromo-4,4’-bi-1,2,4-triazole) : n(Na N3) = 1 : 4.6. 3,3’,5,5’-tetraazido-4,4’-bi-1,2,4-triazole was reduced by various reducing reagents. Triphenylphosphine is the optimal reagent, 3,3’,5,5’-tetramino-4,4’-bi-1,2,4-triazole was obtained and confirmed by MS spectrum.2 3,3’,5,5’-tetraaminium-4,4’-bi-1,2,4-triazole salts of hydrochloride, ptoluenesulfonic acid, nitric acid, picric acid were synthesized from 3,3’,5,5’-tetrabromo-4,4’-bi-1,2,4-triazole. The structures of the products were confirmed by MS spectra. Mononitro- and dinitro- 4,4’-bi-1,2,4-triazole derivatives were obtained through the nitration of 4,4’-bi-1,2,4-triazole, 3,5-dinitro-1,2,4-triazole and 3-(difluoroboryl)-3’,5,5’-trinitro-4,4’-bi-1,2,4-triazole were prepared through the nitration of 3,3’,5,5’-tetraiodine-4,4’-bi-1,2,4-triazole, nitroso derivatives were prepared through the diazotization of 3,3’,5,5’-tetramino-4,4’-bi-1,2,4-triazole. 3,3’,5,5’-tetramino-4,4’-bi-1,2,4-triazole was oxidized with different oxidation reagents, 3,3’,5,5’-tetranitro-4,4’-bi(1,2,4-triazole) were obtained from 3,3’,5,5’-tetramino-4,4’-bi-1,2,4-triazole oxidized with ozone, the structure of the product was confirmed by MS、13C NMR spectra.3 50 grams-scale of 5,5’-bistetrazole-1,1’-diolate was synthesized from glyoxal with five steps of reactions. The process conditions of synthesis of 5,5’-bistetrazole-1,1’-diolate from 5,5’-bistetrazole-1,1’-diol dehydrate were investigated, the optimal conditions of the process were determined, the yield could be achieved in 80.1 %. The product was characterized by 1H NMR, IR, MS spectra and element analysis.