Mechanisms of hydrolysis and nitrosation reactions of alkyl nitrites in various media

We review some of the work that we have been doing in the field of chemical kinetics on the reactivity of alkyl nitrites in microorganized media. For comparative purposes, the reactivity of alkyl nitrites in water, organic solvents, aqueous beta-cyclodextrin solutions and aqueous micellar solutions is reviewed. After a brief description of common properties of alkyl nitrites and of microorganized media, we report kinetic studies on the reactivity of alkyl nitrites. The emphasis is on three important reactions undergone by these reagents in solution, namely acid-catalysed hydrolysis, base-catalysed hydrolysis and NO-transfer reactions, mainly to amines to produce nitroso compounds. The principal features observed through the experimental study of these reactions allow reaction mechanisms in each reaction medium to be prepared; these give information on the constitution of the transition state and its energy characteristics, the presence of possible intermediates, the effects of structural variation on rate and the role of the solvent.