Reactions of β‐nitrostyrenes with tert‐butylmercury halides in the presence of lodide lon

Photolysis of t‐BuHgCl/KI with PhC(R²)C(R¹)NO₂ forms PhC(R²)C(R¹)Bu‐t when R¹ = R² = H or in low yield when R¹ = H, R² = Ph. When R¹ ≠ H, or when R² = Ph, reactions with t‐BuHgI/KI/hv proceed mainly via PhC(R²)C(R¹)NO₂·‐, PhC(R²)C(R¹)N(OBu‐t)O⁻HgX⁺, PhC(R²)C(R¹)NO and PhC(R²)C(R¹)N(OBu‐t)HgX to form a variety of novel products including the dimeric bisnitronic esters (6) with R¹ = Me or Ph and R² = H; PhCH(R²)C(R¹) = NOBu‐t with R¹ = Me or Ph and R² = H or R¹ = H and R² = Ph; PhC(R²)(OBu‐t)C(R¹)NOH with R¹ = H or Me and R² = Ph; and 3‐phenyl‐2‐R¹‐indoles with R¹ = H, Me, Ph, PhS or t‐BuS and R² = Ph. Nitrosoaromatics react with t‐BuHgX in the dark to form ArN(OBu‐t)(OBu‐t)HgX⁺ which condenses with ArNO to form the azoxy compound. tert‐Butyl radicals will add to RNO₂ [R = Ph, Ph₂CCH, Ph₂CC(Ph)] in the presence of t‐BuHgI₂⁻ to form products derived from RN(OBu‐t)O⁻HgI⁺.