Reactions of thioxanthylium tetrafluoroborate with pharmacophoric heterocyclic amines, pyrimidin-2-amine, 4,6-dimethylpyrimidin-2-amine, 2-aminopyrimidine-4,6-diol, and 1,3,4-thiadiazole-2,5-diamine, gave stable products of electrophilic substitution of one hydrogen atom per amino group. The product structure was confirmed by 1H NMR and mass spectra and X-ray analysis of N-(9H-tmoxanthen-9-yl)pyrimidin-2-amine.