5-Amino-1-naphthol undergoes ionic hydrogenation with cyclohexane and condenses with benzene when reacted in the presence of excess of aluminum halides to give 5-amino-1-tetralone (10) and 5-amino-3-phenyl-1-tetralone, respectively. In CF 3 SO 3 H as well as CF 3 SO 3 H-SbF 5 superacidic media 5-amino-1-naphthol gave N,C-diprotonated dication that can be considered as the superelectrophilic intermediate in the reactions with cyclohexane and benzene. The mechanism of these reactions is discussed.