title: Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism.
abstract: Conventional kinetic analysis of the reactions of nitromethane (NM), nitroethane (NE) and 2-nitropropane (2-NP) with hydroxide ion in water revealed that the reactions are complex and involve kinetically significant intermediates. Kinetic experiments at the isosbestic points where changes in reactant and product absorbance cancel indicate the evolution and decay of absorbance characteristic of the formation of reactive intermediates. The deviations from 1st-order kinetics were observed to increase with increasing extent of reaction and in the reactant order: NM < NE < 2-NP. The apparent deuterium kinetic isotope effects for proton/deuteron transfer approach unity near zero time and increased with time toward plateau values as the reaction kinetics reach steady state. It is proposed that the initially formed preassociation complexes are transformed to more intimate reactant complexes which can give products by two possible pathways.
authors.affiliation: Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322, USA.
authors.forename: Zhao
authors.initials: Z
authors.lastname: Li
authors.forename: Jin-Pei
authors.initials: JP
authors.lastname: Cheng
authors.forename: Vernon D
authors.initials: VD
authors.lastname: Parker