title: Evidence for the Formation of alpha-Hydroxydialkylnitrosamines in the pH-Independent Solvolysis of alpha-(Acyloxy)dialkylnitrosamines.
abstract: A kinetic study of the decay of alpha-(acyloxy)dialkylnitrosamines in aqueous solutions, at 25 degrees C, ionic strength 1 M (NaClO(4)), and 4% acetonitrile by volume, is reported. Rate constants for disappearance of the N-NO chromophore or appearance of benzaldehyde product increase with the introduction of electron-withdrawing groups into the acyloxy moiety. For some compounds, in some regions of pH, the kinetics are non-first-order. For these compounds, in other regions of pH, the rate constants are coincident with those previously reported for the decay of the corresponding alpha-hydroxydialkylnitrosamines. These data provide direct evidence that alpha-hydroxydialkylnitrosamines are intermediates in the pH-independent decomposition of the alpha-(acyloxy)dialkylnitrosamines studied.
authors.affiliation: Department of Chemistry, Wake Forest University, Winston-Salem, North Carolina 27109.
authors.forename: Latifa
authors.initials: L
authors.lastname: Chahoua
authors.forename: Milan
authors.initials: M
authors.lastname: Mesic
authors.forename: Cynthia L.
authors.initials: CL
authors.lastname: Revis
authors.forename: Alain
authors.initials: A
authors.lastname: Vigroux
authors.forename: James C.
authors.initials: JC
authors.lastname: Fishbein