Nitration of aromatic hydrocarbons and ipso-nitrosodemetallation of arylmetal compounds in sodium nitrite–trifluoroacetic acid

Abstract

Treatment of aromatic hydrocarbons with sodium nitrite in trifluoroacetic acid affords nitroarenes in high yields in sharp contrast to a report in which aromatic nitration occurred only slightly in almost the same reaction system. Nitrosodemetallation at the ipso-position occurs to give nitrosoarenes in good yields by similar treatment of various arylmetal compounds (metal = Hg, Tl, Si, Sn, Pb, or Bi), nitrodemetallation hardly occurring in this case. The former reaction proceeds through attack of NO₂⁺, while NO⁺ or its carrier N₂O₃ is the attacking species in the latter reaction.