Synthesis Of1,2-Dinitroguanidine,Multi-nitroacetyleneguanidine And Theirs Derivatives

1,2-Dinitroguanidine and multi-nitroacetyleneguanidine is an interesting class of energetic materials that exhibit high nitrogen content, excellent oxygen balance, high-density and good thermal stability. From a chemical standpoint, the compounds are the interesting mother skeleton because of their primary nitramine and nitroguanyl groups in the molecule. Besides,1,2-dinitroguanidine and2-iminium-5-nitriminooctahydroimidazo[4,5-d]imidazole(nitroacetyleneguanidine) are able to form salts which will also be explosives.In the presented thesis,1,2-nitroguanidine was synthesized via nitration reaction using nitroguanidine under three nitrating systems. The affecting factors such as mole ratio of material, reaction temperature and reaction time were studied. The stable geometry of the compound was completely optimized at the B3LYP/6-31+G(d, p) theoretical level of density functional theory(DFT), and the reason why it is more difficult to be nitrified than the urea was also discussed. Finally, the thermal stability and decomposion properties of1,2-dinitroguanidine were investigated according to TG and DSC curves.Eight energetic ionic salts, aminoguanidine salt,4-amino-1,2,4-triazole salt, diaminoguanidinium salt, triaminoguanidinium salt,3,6-diguanidine-1,2,4,5-tetrazine di(1,2-dinitrogua-nidine),3,6-dihydrazine-1,2,4,5tetrazine salt and nitroacetyleneguanidine salt were synthesized based on1,2-dinitroguanidine and the corresponding amines.4,5-Dihydroxy-2-nitroiminoimidazolidine was prepared by the condensation reaction of commercially available nitroguanidine and glyoxal. The nitroacetyleneguanidine chloride and nitrate were easily synthesized followed by the reaction of4,5-dihydroxy-2-nitroiminoimidazolidine with guanidinium chloride and guanidinium nitrate, respectively. nitroacetyleneguanidine chloride was converted to the bis(nitroimino) compound using nitric acid in acetic anhydride. And the affecting factors were discussed.The nitration and nitrosation reaction of octahydro-2,5-bis(nitroimino)imidazo[4,5-d]imidazole were investigated. The stable geometry of the compounds were completely optimized at the B3LYP/6-31+G(d, p) theoretical level of density functional theory, and the reason why the nitration and nitrosation reactions are diffcult to occur were also discussed.