Syntheses And X-Ray Crystal Structures Of Aminated 4,4'-Bi-1,2,4-triazole Salts

The investigation of 4,4'-bi-1,2,4-triazole(BTr)in coordination chemistry has been largely improved since it been synthesized in 1967 for the first time,but rarely has it been applied in energetic material.1986,Los Alamos National Laboratory reported the density(1.99 g/cm3),detonation velocity(9.5 Km/s)and detonation pressure(42.2 GPa)of ideal explosive 3,3'5,5'-tetranitro-4,4'-bi-1,2,4-triazole(TNBT)through calculation.Nitrogen rich BTr was composed of many high energetic bonds meanwhile contains high positive enthalpy,due to its characteristics of compact,high stability and energy,energetic compounds derive from BTr can be with high energy and stability.Unfortunately,there isn't any report on BTr-based energetic compounds till now.In the present paper,we use 3,3'5,5'-tetrazide-4,4'-bi-1,2,4-triazole(TABT)as raw material,by means of Staudinger reaction with(Ph)3P,H2 O and the simple reaction with concentrated hydrochloric acid and aqueous TsOH,two novel energetic intermediates 3-amino-4,4'-bi-1,2,4-triazole hydrochlorate and 3,3'-diamino-4,4'-bi-1,2,4-triazole ditosylate were successfully synthesized.Through optimizing the process,yields have been improved to 70% and 80%,respectively.The structures were confirmed by IR,MS,1H NMR,13 C NMR and element analysis.The crystals(CCDC 1447005,1447006)were achieved by slow evaporation in methanol.Afterward,four novel ionic salts,hydrochlorate,ditosylate,perchlorate,nitrate of 3,3'-diamino-5,5'-dihydroxy-4,4'-bi-1,2,4-triazole were successfully synthesized and characterized by IR,MS,1H NMR,13 C NMR,through optimizing the process,the yield has been improved to 69%.Nitro derivatives and energetic salts based on monotriazole was an important source of the fourth generation of high energy density energetic materials,it contains great potential in propellent and high energy explosive.With the syntheses of six BTr based novel salts,the investigation of azole-based energetic material and the method of the synthesis of new energetic compounds can be further expanded.