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

作者：Silva Daniel^*; Norberto Fatima; Santos Susana; Herves Pablo

来源：Reaction Kinetics, Mechanisms and Catalysis, 2015, 115(2): 421-430.

DOI：10.1007/s11144-015-0867-7

• Carbamates
• Heterocycles
• Pyridyl group
• Kinetics
• Mechanism

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 alpha-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 B(AC)2 mechanism with nucleophilic catalysis rather than a general base catalysis as initially thought.

• 出版日期2015-8