Direct Amination of Nitro(pentafluorosulfanyl)benzenes through Vicarious Nucleophilic Substitution of Hydrogen

1‐Nitro‐4‐(pentafluorosulfanyl)benzene underwent direct amination with 1,1,1‐trimethylhydrazinium iodide in the presence of tBuOK in DMSO to give 2‐nitro‐5‐(pentafluorosulfanyl)aniline in good yield. 1‐Nitro‐3‐(pentafluorosulfanyl)benzene, under similar conditions, gave 2‐nitro‐4‐(pentafluorosulfanyl)aniline, also in good yield. Reduction of either product with hydrogen in the presence of Raney nickel provided 4‐(pentafluorosulfanyl)benzene‐1,2‐diamine, which served as a precursor for the efficient synthesis of SF5‐containing benzimidazoles, quinoxalines, and benzotriazoles. Direct regioselective vicarious nucleophilic amination of para‐ and meta‐nitro(pentafluorosulfanyl)benzenes was achieved giving SF5‐containing 2‐nitroanilines in high yield. Catalytic reduction provided SF5‐benzenediamine, which served as a precursor for the efficient synthesis of new SF5‐containing nitrogen heterocycles such as benzimidazoles, quinoxalines, and benzotriazoles.