REACTION MECHANISM OF THE NISTOSATION OF UREAS.

Article abstract of DOI:10.1002/bbpc.19830871226

The nitrosation of methylurea has been studied under catalysis by acetate and mono-, di- and trichloroacetate buffers. The catalysis observed has been found to be due to the organic anions, and Bronsted relation is obeyed with beta equals 0. 24. The experimental results have been interpreted in terms of a reaction mechanism which features the rapid formation of an intermediate, MeNH(NO)CONH//2, when the methylurea is nitrosated. The rate controlling step is the transfer of a proton from this intermediate to the solvent or to a basic catalyst (the nitrite ion or the organic anion). That it is this step that controls the overall rate of reaction is supported by the isotopic effect (k//H/k//D equals 3. 5) observed on carrying out kinetic measurements in D//2O.