Synthesis Of Poly-Nitrogen Compound Of Triazine And Tetrazine

The new nitrogen heterocycles energetic compounds have recently attracted significant attention from many researchrs in the field of energetic materials.The rings of triazine, tetrazine,tetrazole and pyrazole have currently been extensively studied as the typical structural units of nitrogen-containing.Various kinds of poly-nitrogen energetic compounds have high application potential when energetic groups such as -NH2,-NO; or-N3 were introducted at the structure of those parent rings.In this paper,3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine(BT) which is the useful intermediate of 1,2,4,5-tetrazines was synthesized by amination, cyclization and oxidation with guanidine nitrate as the raw materials. The synthesis process was optimized and the optimum conditions were obtained.3,6-diazido-1,2,4,5-tetrazine (DiAT) was then synthesized from 3,6-di(hydrazino)-1,2,4,5-tetrazine by diazotization which was synthesized from hydrazine hydrate and BT. The azido-tetrazolo tautomerizations of DiAT in different solvents were investigated with HPLC and 13C NMR to improve its sensitivity. 6-Amino-tetrazolo[1,5-b]-1,2,4,5-tetrazine was irreversibly formed as the final product by azido-cyclization at room temperature in DMSO.1,4-diamino-3,5-dinitropyrazole (DADNP) was synthesized by amination of the useful intermediate 4-chloro-3,5-dinitropyrazole (CDNP) in which CDNP was obtained from pyrazole via halogenation and nitration.The synthesis process was optimized and the optimum conditions were obtained. The ring enlargement to form 1,2,3-triazine from the parent ring of DADNP has been studied using several oxidation reagents such as NaI04. Instead of 1,2,3-triazine,4-amino-3,5-dinitropyrazole was obtained as the final product with N-NH2 elimination.