The base catalyzed hydrolysis of N-methylacetamide is elucidated by means of Car-Parrinello simulation. The process is investigated in aqueous solution, including a quantum treatment of all electronic degrees of freedom. The rate-determining step is the attack of a hydroxide ion on the amide carbon atom. This is followed by protonation of the nitrogen atom. The final dissociation may occur via two different pathways: (i) dissociation into an amine and a carboxylic acid and (ii) oxygen deprotonation and dissociation into an amine and a carboxyl anion. The later pathway was found to be strongly favored. (C) 2003 Elsevier B.V. All rights reserved.