An investigation of some radical–anion radical reactions

The reactions of thiolate anions with α-substituted 2-nitropropanes have been studied. The products of these reactions are the corresponding disulphides, α-nitrothioethers, and 2,3-dimethyl-2,3-dinitropropane. The ratio of the products in relation to the structure of the starting materials is discussed. The α-nitrothioethers are formed by the SRN1 mechanism, while the available evidence suggests that the disulphides are formed by a non-radical mechanism. Some α-nitrothioethers have been reacted with a series of anions. Several of these reactions have been shown to proceed by the SRN1 mechanism, with displacement of thiolate anion. The reaction of nitronate anions with aromatic disulphides has been shown to give α-nitrothioethers under mild conditions. The reaction has been shown by kinetic studies to be second order overall.