216434-79-6Relevant articles and documents
The acid-catalysed decomposition of N-nitrotolazoline
Iley, Jim,Norberto, Fatima,Sardinha, Paula
, p. 2207 - 2209 (2007/10/03)
Reaction of tolazoline with N2O4 yields N-nitrotolazoline, the prototypical nitroamidine. N-Nitrotolazoline undergoes acid-catalysed hydrolysis of the nitroamidine function to form N-(2hydroxyethyl)phenylacetamide. The observed pseudo-first-order rate constants, k0, have a non-linear dependence upon acidity, displaying saturation at higher acide concentrations consistent with a mechanism involving equilibrium protonation of N-nitrotolazoline prior to subsequent decomposition of the protonated intermediate. Reactions are subject neither to general acid-or base-catalysis nor to catalyss by thiocyanate ion. The solvent deuterium isotope effect for protonation was found to be 0.3, and for decomposition of the protonated intermediate, 1.7. A value of (-100 ± 5) J K-1 mol-1 was determined for ΔS? for the decomposition step. Thus, hydrolysis of the protonated intermediate involves rapid attack of a molecule of water at the amidine carbon atom followed by a slow, intramolecular rearrangement involving proton transfer.
