Acid-catalysed N-alkyl heterolysis of tertiary pyridinecarboxamides and benzamides under mild conditions

Tertiary pyridinecarboxamides 1-9 and related benzamides 10-18 bearing a te rt-butyl substituent were found to undergo alkyl-nitrogen heterolysis under unusually mild conditions. Accordingly, the corresponding secondary amides 19-33 have been isolated in high yields as the sole reaction product. Thro ugh a kinetic study based on pH-rate profiles and activation parameters, we have shown that the alkyl-nitrogen fission involved an initial protonation of the amide group that would concern the oxygen atom.