The possibility of obtaining 1,2,4-triazines with residue of unsubstituted (1,2,4-triazol-3-yl)amine at position C5 as a result of the solvent-free ipso -amination reaction between 1,2,4-triazine-5-carbonitriles and 3-amino-5 H - or 3-amino-5-mercapto-1,2,4-triazoles has been shown. In the latter case, during the transformation, the reaction of desulfurization of the 1,2,4-triazole fragment occurs.