Alkaline hydrolysis of tertiary N-(2-pyridyl)carbamates. Contradictory evidence between nucleophilic and general base catalysis

• DOI: 10.1007/s11144-015-0867-7
• Publication Date: 2015-04-15T21:54:39Z
• Authors: Daniel Silva; Fátima Norberto; Susana Santos; Pablo Hervés
• Keywords: Piperidine; Alkaline hydrolysis; Carbamate; Kinetic isotope effect; Base (topology)

The mechanism of the alkaline hydrolysis of phenyl N-methyl-N-(2-pyridyl)carbamate was investigated in order to evaluate the type of catalysis involved. The kinetic solvent isotope effect, the α-effect for the hydrolysis in peroxymonocarbonate ion, the Bronsted plot, and the isolation of the product resulting from trapping the unsaturated intermediate with piperidine, confirmed that the alkaline hydrolysis of phenyl N-methyl-N-(2-pyridyl)carbamate proceeds through a BAC2 mechanism with nucleophilic catalysis rather than a general base catalysis as initially thought.