Studies On The Synthesis Of Tetrazole

Energetic tetrazole compounds and their derivatives with a high nitrogen content, high enthalpy of formation andgood stability, belong to the scope ofgreen energy materials containing. They have been widely applied in many areas, for example military science, chemistry, medicine, agriculture and so on, with thegreat potential for development.5-ATZ was synthesized by three different reaction routes which were obtained in high yields. The main raw material of the three routes were aminoguanidine inorganic salts:NaN3 and NH2CN, N2H4·H2O and NH2CN. By comparing the results of three methods, when using N2H4·H2O and NH2CN as raw material, one-pot synthesis of the product was superior to the other. The reaction process was simple, safe operation and to be high yield. The optimum reaction conditions are determined by a large number of experiments. The molar ratio of the materials:n(N2H4-H2O):n(HCl):n(NH2CN):n(NaNO2)= 1:1:1:1, diazotization procedure: pH=2-3, T=20～30 ℃, t=0.5 h, cyclization procedure:pH=7-8, T=95℃, t=4.0 h. The yield and purity were 85.2% and 99%.In the methylation reaction of 5-ATZ, when using MeI as the methylating agent, the yield of 1-methyl-5-amino tetrazole was high. The optimum reaction conditions:n(MeI):n(5-ATZ): n(NaOH)= 1:1:1, V(CH3COCH3)=90 mL, T=40～45 ℃, t=4 h. The yield was 45.7%. DMC was chosen in the synthesis of 2-methyl-5-amino-tetrazole, And the yield was improved by optimizing the experimental conditions. The optimum reaction conditions:n(DMC): n(5-ATZ):n(NaOH)=1:2:2, V(DMF)=100 mL, T=135℃, t=5 h. The yield was 35.6%。BTA was synthesized by different experimental methods. Sodium dicyandiamide was determined to be the raw material in the experiment, and the yield could be higher. The one-pot synthesis method was relatively simple operate. The optimal conditions was obtained by many experiments. The molar ratio of the material:n(NaN(CN)2):n(NaN3):n(H+)=1:2:1, T=100 ℃, t=24 h. The yield and purity were 89.5% and 99%. The structure of the products were confirmed by NMR, MS and DR..