Two new heat-resistant explosives of 1-picryl-3-amino-5-nitro-1,2,4-triazole(TNTA-TNB) and 4-picryl-3,5-dinitro-1,2,4-triazole (DNT-TNB) were synthesized via condensation of 3-amino-5-nitro-1,2,4-triazole (ANTA) (or ammonium 3,5-dinitro-1,2,4-triazole (ADNT)) with 2,4,6-trinitrochlorobenzene. The condensation mechanism was explored and discussed. The effects of some key reaction conditions,such as media,temperature,time and catalysts,on condensation were investigated. The explosive synthesis was carried out at 70 ℃,8 h in DMF and NaF as catalyst. IR, NMR and elemental analysis confirmed the synthesized compound structures. In addition,we imroved the synthetic process of 2,4,6-tris(3-amino-5-nitro-1,2,4-triazole-1-yl)-1,3,5-triazine by means of direct reaction of ANTA with 2,4,6-trichloro-1,3,5-triazine omitting the preparation of ANTA-Na and without using phase transfer catalyst,lowering the production cost,simplifing the procedure,and improving the reaction safety.