Radical-nucleophilic substitution (S(RN)1) reactions. Part 7. Reactions ofaliphatic alpha-substituted nitro compounds.

alpha -Nitrothiocyanates R2C(SCN)NO2 have been prepared by oxidative additi on of thiocyanate anion to nitronate anions and undergo S(RN)1 substitution reactions by loss of thiocyanate with nitronate anions, phenylsulfinate, a zide and p-nitro- and p-chloro-benzenethiolates in dipolar aprotic solvents . 2-Nitro-2-thiocyanatopropane and other 2-substituted-2-nitropropanes [Me2 C(X)NO2 with X = I, Br, Cl, NO2, PhSO2] react with thiolates by S(RN)1 reac tions. and/or redox reactions to give disulfides by a polar abstraction or chain SET (S(ET)2) mechanisms. The products are dependent on the nucleophil icity of the thiolates, the polarisability of the alpha -substituent, the s olvent and the presence of light catalysis, radical traps or strong electro n acceptors. 2-Substituted-2-nitropropanes [Me2C(X)NO2 with X = N-3, NO2, C N, p-NO2-C6H4 N=N] undergo S(RN)1 substitutions with thiolates by loss of n itrite.. 2-Substituted-2-nitropropanes Me2C(X)NO2 and thiolates only yield disulfides in methanol due to solvation of the nitro groups.