REACTION OF SOME SATURATED HETEROCYCLES AND RELATED AMINES WITH 49-PERCENT FORMIC-ACID AT 350-DEGREES-C - PART 27 - AQUATHERMOLYSIS

Two primary amines (benzylamine and aniline:, two secondary amines (di phenylamine and morpholine) and four tertiary amines (quinuclidine, tr ibenzylamine, N-butylpyrrolidine and N,N-phenylpyrrole) were each heat ed at 350 degrees C with 49 % aqueous formic acid for varying periods of time. Aniline underwent N-formylation with subsequent reduction to give N-methylaniline and N,N-dimethylaniline. Benzylamine was hydrolyz ed to benzyl alcohol and reduced to toluene. Tertiary amines underwent reductive cleavage to secondary and primary amines, which subsequentl y followed the reaction sequences observed for the primary amines. Dip henylamine yielded minor amounts of N-methyldiphenylamine. Morpholine underwent N-formylation with subsequent reduction to give N-alkylmorph olines and it also formed a denitrogenated cyclic product in small amo unts. N-Phenylpyrrole gave rise to N-phenylpyrrolidine, while N-butylp yrrolidine underwent partial oxidation to form N-bulylpyrrole.