Synthesis Of High-nitrogen Energetic Compounds Derived From Tetrazine

Tetrazine ring is a hexatomic heterocycle with 68.3% of nitrogen, as a high-energy backbone. It is a very useful construction unit to design high-energy and low-sensitivity explosives, deriving most of the energy from the large number of N=N, N-N, C=N,C-N bonds and high strain. Forming a unique class of energetic materials, tetrazine compounds are researched actively in recent years, subsequent to furazan and tetrazole compounds.In this thesis, as an important precursor to synthesize tetrazine compounds,3,6-bis (3, 5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (BT) was synthesized with guanidine nitrate, hydrazine hydrate and acethylacetone by hydrazinolysis, condensation and oxidation. Several compounds derived from 1,2,4,5-tetrazine were synthesized by nucleophilic substitution reactions, including 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (ADMPT),3, 6-diamino-1,2,4,5-tetrazine (DAT),3-hydrazino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4, 5-tetrazine (HDMPT),3,6-dihydrazino-1,2,4,5-tetrazine (DHT), and 3,6-diguanidino-1,2, 4,5-tetrazine (DGTZ). Their structures were characterized.The novel energetic compounds derived from 1,2,4,5-tetrazine were synthesized and studied in this thesis. ADMPT, HDMPT and DHT were reacted with cyanuric chloride.2,4, 6-tris (2-(6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazin-3-yl) hydrazinyl)-1,3,5-triazine and 3,6-bis (2-(4,6-dichloro-1,3,5-triazin-2-yl) hydrazinyl)-l,2,4,5-tetrazine were synthesized. The reactions of NaN3, hydrazine hydrate,5-aminotetrazole,2-nitroaniline and 2, 4-dinitroaniline with 3,6-bis (2-(4,6-dichloro-1,3,5-triazin-2-yl) hydrazinyl)-1,2,4, 5-tetrazine, were explored.3,6-bis (2-(4-azido-6-chloro-1,3,5-triazin-2-yl) hydrazinyl)-1,2, 4,5-tetrazine and 3,6-bis (2-(4,6-diazido-1,3,5-triazin-2-yl) hydrazinyl)-1,2,4,5-tetrazine were synthesized. The four novel compounds were characterized by MS,1H NMR,13C NMR and IR. In addition, the single crystal of 3,6-bis (2-(4,6-dichloro-1,3,5-triazin-2-yl) hydrazinyl)-1,2,4,5-tetrazine was obtained by controlling the evaporation of solvent.The energetic performance parameters of 3,6-bis (2-(4,6-dichloro-1,3,5-triazin-2-yl) hydrazinyl)-1,2,4,5-tetrazine and its derivatives by substitution and oxidiation were predicted theoretically.