Rapid amidic hydrolysis: a competitive reaction pathway under basic conditions for N-(hydroxymethyl)benzamide derivatives bearing electron-donating groups
Studies of N-(hydroxymethyl)benzamide derivatives have concluded that the hydroxide-dependent reaction occurs via a specific-base catalyzed deprotonation of the hydroxyl group followed by rate-determining loss of the benzamidate and generation of the aldehyde. The 3-methyl, 4-methyl, and 4-methoxy-N-(hydroxymethyl)benzamide reaction mechanism deviates at higher [HO-] with amidic hydrolysis becoming competitive and having reaction half-lives of ~17 s, in 1 M KOH, I = 1.0 M (KCl), 25 °C. An intramolecular general-base catalyzed mechanism has been suggested for the amidic hydrolysis reaction.
Murphy, John L.,Tenn III, William J.,Labuda, Joseph J.,Nagorski, Richard W.
A convenient and clean synthesis of methylenebisamides and carbinolamides over zeolites in aqueous media
A simple, efficient and environmentally benign protocol for the synthesis of methylenebisamides and carbinolamides in high yields from aromatic amides and formaldehyde in the presence of heterogeneous catalysts (Hβ and NaY zeolites) using water as a solvent is demonstrated. Moreover, the catalyst is recyclable and can be reused without significant loss in its catalytic activity.