131229-60-2Relevant academic research and scientific papers
Solvolysis and mutagenesis of n-acetoxy-n-alkoxybenzamides - Evidence for nitrenium ion formation
Campbell, John J.,Glover, Stephen A.,Rowbottom, Colleen A.
, p. 5377 - 5380 (1990)
Mutagenic N-acetoxy-N-butoxybenzamides undergo acid catalysed solvolysis in acetonitrile/water. Kinetic data and a Hammett σ+ correlation (ρ=-1.4) indicate nitrenium ion formation in the rate determining step. Levels of mutagenicity mirror the rates of solvolysis suggesting nitrenium ion involvement.
Evidence for the Formation of Nitrenium Ions in the Acid-catalysed Solvolysis of Mutagenic N-Acetoxy-N-Alkoxybenzamides
Campbell, John J.,Glover, Stephen A.,Hammond, Gerard P.,Rowbottom, Colleen A.
, p. 2067 - 2080 (2007/10/02)
In aqueous acetonitrile, N-acetoxy-N-alkoxybenzamides undergo acid-catalysed solvolysis by the AAl1 mechanism to give acetic acid and nitrenium ions.This is indicated by an inverse dependence of the acid-independent rate constant, kH, upon the activity of water, a solvent kinetic isotope effect of 0.44 and positive Σ(excit.) values.In addition, relief of steric compression at the nitrogen enhances the rate of solvolysis.Hammett correlations with ?+ substituent constants were found for the rates of solvolysis of para-substituted-N-acetoxy-N-butoxybenzamides and N-acetoxy-N-(para-substituted benzyloxy) benzamides.This fact and the low ρ-values of -1.35 and -1.56, respectively, are indicative of a strong build-up of positive charge in the transition state which has both nitrenium ion and oxonium ion character and is in accordance with computed molecular-orbital properties of N-alkoxynitrenium ions.Greater levels of mutagenicity have been measured for those compounds which are more readily solvolysed to nitrenium ions.
