Studies On Synthesis Of Energetic Compounds Derived From Triazole And Tetrazole

In contrast to traditional energetic materials, owing to their higher nitrogen content, higher formation enthalpy and environmental-friendly properties, high nitrogen energetic compounds are the major research directions in the field of energetic materials. There are certain difficulties in the synthesis of high nitrogen energetic compounds because of their bad stabilities. Some novel high nitrogen energetic compounds are designed and synthesized in this paper, three sections are involved.1. Studies on the high nitrogen energetic compouds based on the aromatic triazole-based hydrazine group structureTriaminoguanidinium chloride is synthesized using guanidinium chloride and 80% hydrazine hydrate as raw materials.3-hydrazino-4-amino-1,2,4-triazolium chloride is synthesized by cycloaddition reaction of triaminoguanidinium chloride and formic acid then protonated by hydrochloric acid.2,4,6-trinitrobenzaldehyde is prepared by hydrolysis of methylene amine bound of the intermediates under heating with hydrochloric acid which was synthesized by the reaction of 2,4,6-trinitrobenzaldehyde and N,N-dimethyl-4-nitrosoaniline. The nucleophilic reactivity based on the hydrazine group of AHTA is studied in energetic materials area for the first time. 1,1-(2,4,6-trinitrobenzal)-methylene-2,2-(4-anmino-1,2,4-triazole-5,5methylene)hydrazine (PMAH) is synthesized by the reaction of AHTA with 2,4,6-trinitro-benzaldehyde.Some reaction conditions are optimized and the reaction mechanism of AHTA, trinitrobenzaldehyde and PMAH are also discussed. The products are characterized by IR,1H NMR,13C NMR and MS. The parameters of the detonation properties are calculated by DFT/B3LYP method. The densities are promoted and positive effects on the detonation properties are also obtained by introducing the trinitromethyl group. The heats of formation are significantly enhanced by the structure of long nitrogen chain.2. Studies on tetrazole high nitrogen energetic compouds based on amino diazo coupling reaction5-aminnotetrazole is prepared by diazotization, intramolecular cycloaddition using aminoguanidinium chloride as the raw materials. The diazotization conditions of 5-aminnotetrazole and coupling with different amine such as 1-anmino-1,2,4-trizole,4-anmino-1,2,4-trizole,1,5-diaminnotetrazole and 3,4-diaminofuzan are explored. The couping products of 1,5-diaminnotetrazole and 3,4-diaminofuzan are obtained. The N7 nitrogen chain product 17 is prepared based on the diazotization of the amino group, the mechanism was speculated. The diazotization of the amino group provides new method for the discovery of long nitrogen chain compounds. The effect of pH on the couping reaction is also studied. The products are characterized by 1H NMR,13C NMR and MS. The parameters of the detonation properties are calculated.3. Studies on triazole and tetrazole high nitrogen compounds based on active hydrogen3-nitro-1,2,4-trizole ammonium is prepared by oxidation of the anmino group and convertion to corresponding ammonium using 3-anmino-1,2,4-trizole as raw material. 2-(nitro-1,2,4-trizole-l-)acetonitrile is obtained by electrophilic substitution of 3-nitro-1,2,4-trizole ammonium with bromoacetonitrile.5-(3-nitro-1,2,4-trizole-l-)methyl)-1-H-tetrazole is prepared by [3+2] cycloaddition reaction from 2-(3-nitro-1,2,4-trizole-1-) acetonitrile and sodium azide using zinc bromide as the catalyst. The effects of the reaction temperature and solvent is studied. The products are characterized by 1H NMR,13C NMR and MS. The parameters of the detonation properties are calculated.