Synthesis Of N₅^- Energetic Ionic Salts Containing Nitro Cations

Total nitrogen substances refer to a class of ionic,covalent or polymeric compounds composed entirely of N elements through N-N and N=N bonds.The molecules contain huge energy,with high density,high enthalpy of formation,and super High energy and detonation products are clean and pollution-free.N₅^-（pentaazole anion）is an important material for constructing total nitrogen substances.This article optimizes the synthesis process of the pentaazole anion intermediate,improves the yield of the pentaazole anion intermediate,and scales up the target process.On this basis,high-energy N₅^-ion energetic materials are constructed,and a series of N₅^-energetic ion salts containing nitro cations are designed and synthesized.The main contents of this paper are as follows:（1）The reaction temperature and reaction time of the reduction stage in the synthesis of 2,6 dimethyl-4 hydroxyaniline hydrochloride were optimized,and on this basis,the scale-up experiment of 100 grams of aniline hydrochloride was carried out.The material ratio in the reduction stage was optimized,and the optimal ratio of sodium hydroxide and dithionite was obtained.The reaction conditions during the cleavage of the C-N bond were optimized:through orthogonal experiments,the effects of reaction temperature,reaction time and the amount of reaction solvent on the reaction were studied.The optimal reaction conditions are:reaction temperature-25,reaction time 24 h,methanol 150 m L.Through research,it is found that the order of reaction conditions affecting the reaction is:reaction temperature﹥reaction time﹥reaction solvent dosage.On this basis,the synthesis process of PHAC,an intermediate of pentaazole anion,was scaled up.The output of PHAC,an intermediate of azole anion,increased from 576 mg to 10.8 g in the laboratory.But the yield dropped from 14.6%to 9.8%.It shows that in the process of cutting off,the amplification effect is more obvious.（2）Using FOX-7 as the starting material,through condensation,acetylation,and further ring closure with guanidine sulfate,a new type of fused ring compound7-（gemethylene dinitromethylene）-2,4,6,8-Tetraazabicyclo[3.3.0]octane sulfate,and the structure was characterized;on this basis,the pentaazole anion was assembled to obtain the highest density pentaazole non-metallic salt with a density of 1.802 g·cm-3.Through infrared（IR）,thermal analysis（TGA and DSC）characterization and detonation performance research,the compound has excellent detonation performance.（3）Synthesis of 4-nitro-（3,4-diamino-1,2,4-triazol-5-yl）-1H-pyrazole pentaazole salt and dinitrocyclobutylamine pentaazole salt Nitro-containing pentaazole salt.Characterized by single crystal X-ray diffraction,infrared（IR）,1H and 13CNMR spectroscopy,thermal analysis（TGA and DSC）and elemental analysis.These two salts show good detonation performance,low sensitivity and good thermal stability.