Unexpected formation of N,N-disubstituted formamidines from aromatic amines, formamides and trifluoroacetic anhydride

An intriguing selectivity towards the formation of the formamidine was observed upon the reaction of an amine with sodium hydride and trifluoroacetic anhydride in dimethyl formamide. Various aromatic amines were reacted with a series of N,N-disubstituted formamides as a solvent under the influence of trifluoroacetic anhydride to thoroughly probe this behaviour. A trend in selectivity is discussed and a proposed mechanism for the reaction is also presented.