The invention of new radical chain reactions. Part VIII. Radical chemistry of thiohydroxamic esters; A new method for the generation of carbon radicals from carboxylic acids

The aliphatic and alicyclic esters of N-hydroxypyridine-2-thione are readily reduced by tributylstannane in a radical chain reaction to furnish nor-alkanes.¹ In the absence of the stannane a smooth decarboxylatlive rearrangement occurs to give 2-substituted thiopyridines.¹ The radicals present in this reaction provoke with $\text{t}$-butylthiol an efficient radical reaction with formation of nor-alkane and 2-pyridyl-$\text{t}$-butyl disulphide.¹Similarly these carbon radicals can be captured by halogen atom transfer to give noralkyl chlorides, bromides and iodides. 2 With oxygen in the presence of t-butylthiol the corresponding noralkyl hydroperoxides are formed in another radical chain reaction.³