Studies On Synthesis And Performance Prediction Of Azofurazan Derivatives And Furazantetrazine

Energetic compounds containing furazan ring, furoxan ring, tetrazole ring usually show high density, large positive heats of formation, good thermal stability, high oxygen balance and remarkable insensitivity. They are becoming one of the forefronts and research focus in the field of energy materials in terms of explosive parameters.3-amino-4-yl amide oxime furazan (AAOF) was synthesized with starting materials of malononitrile,glacial acetic acid and sodium nitrite, in a yield of 90.2%. the influence factors such as nitrosation temperature, oximation temperature, stirring speed, temperature and time of closure-ring reaction and pH effect were determined in order to obtain the optimized conditions; For the synthesis of 3-amino-4-cyano furazan (CNAF), AAOF was subject to the oxidation by lead oxide under acidic condition at room temperature, with a yield of 74.6%. The reaction mechanism suggested that CNAF could not be synthesized from 1-amino-2-cyanodioxime. Here, we also discussed the impacts related to the reaction as for reaction time and reaction temperature in the thinking of the product yield and achieved the optimum reaction conditions finally; Three Synthetic methods were used to prepare 3-amino-4-(1H-5-tetrazole)furazan (ATZF), the optimum reaction condition was found to be as follows: namely to use water as a solvent, and zinc bromide as a synthetic catalysts, yield 91.8%; In addition, two Synthetic methods were employed to prepare 3-nitro-4-(1H-5-tetrazole)furazan (NTZF), after comparison, the optimum reaction condition was settled down as follows:using the oxidation system of sodium tungstate, hydrogen peroxide, sulfuric acid to synthesize the target compound, with a yield of 85%; ANTZF was prepared from aqueous ammonia by using NTZF as starting material, besides, solvents and temperature were also studied so as to confirm the optimum reaction condition, i.e. taking methanol as solvent in the temperature of 25 ℃. Detonation performance parameters of partial salts of NTZF were evaluated by theoretical calculation. Results indicated that derivatives of furazan tetrazole salts were superior to furazan tetrazole. Hence, it is hopeful that salts of energetic compounds can be used to improve their crystal density and detonation performance.The synthesis of 3-amino-4-(1H-5-tetrazole)furazan (ATZF) and 1-amino-2-cyano-dioxime were optimized. ATZF was synthesized from CNAF by using water as solvent and zinc bromide as catalyst, with a yield of 91.8%, this method is environmentally friendly, low reaction temperature, simple post-treatment, the product purity and the yield are better than the traditional crafts; 1-amino-2-cyano-dioxime was synthesized from malonate, with the treatment of nitrification and oximation in one-pot which brought advantages like fewer reaction steps, relatively moderate reaction conditions,higher product yield. It is favorable for its industrial production.The structures of these compounds were confirmed by IR, NMR, MS and elemental analysis etc. Research indicates energetic compounds with furazan ring, furozxan ring and tetrazole ring exhibit excellent performances such as relatively high density, high heats of formation, detonation velocity and explosive pressure. To futher improve such performance parameters, it is possible to conjugate the furazan and tetrazole together. These energetic compounds are becoming more and more popular due to their high thermal stability, high detonation performance and environment-friendly.