Synthesis And VNS Amination Of DNPP

DNPP (3,6-ditropyrazolo[4,3-c]pyrazoles) is a new heterocyclic amine of energetic material. It is also the key intermediate in synthesis of LLM-119 (1,4-diamino-3,6-dinitropyrazolo[4,3-c]pyrazole).This thesis took acetyl acetone and hydrazine hydrate as the primary substance and prepares 3,6-ditropyrazolo[4,3-c]pyrazoles (DNPP) via reactions of cyclization, reduction, diazotization, double loop construction, nitration, oxidation, oxime, decarboxylation and nitration. The overall yield of DNPP was 13.3%. The products were confirmed by elemental analysis, NMR and IR. By calculating the detonation performance of DNPP, the paper obtained heat of formation for 359.1kJ/mol, detonation velocity for 8.20km/s, detonation pressure for 30.0Gpa, C-NO2 bond dissociation energy for 290.5kJ/mol. The thesis considered three factors on diazotization. The factors included the amount of nitrite, amount of nitrite and reaction temperature. Then the diazotization conditions were optimized, and the optimum conditions were as follows, the mole ratio of sodium nitrite to 4-amino-3,5-dimethylpyrazole was 1:1:1, the mole ratio of acetic acid to 4-amino-3,5-dimethylpyrazole was 3:1, the reaction temperature varied from 0℃to 5℃. The loop conditions were optimized also. And the optimum conditions were as follows, the mole ratio of 4-diazo-3,5-dimethylpyrazole to acetic acid was 4:1, ethyl acetate as solvent, and the yield was 78.8%. The decarboxylation and nitration was optimized, and the yield was 68.1%.The paper synthesized intermediate 4-amino-3,5-dimethylpyrazole by one pot and obtained optimized synthetic process. The yield increased by 12.9% compared with literature. And in the process, the use of mixed acid and iron the waste emissions were reduced.Furthermore, this thesis tried to take 1,1,1-Trimethylhydrazinium iodide(TMHI), 4-amino-1,2,4-triazole(ATA) and NH2-O-SO2OH as VNS agents in different alkali environment and different reaction time to get a new heterocyclic energetic material of 1,4-diamino-3,6-dinitropyrazolo[4,3-c]pyrazole(LLM-119). The paper also obtained by calculating the detonation performance of LLM-119. By calculating the detonation performance of LLM-119, the paper obtained heat of formation for 592.8kJ/mol, detonation velocity for 8.39km/s, detonation pressure for 30.0Gpa, N-NO2 bond dissociation energy for 290.5 kJ/mol and C-NO2 bond dissociation energy for 290.5 kJ/mol.