The e.s.r. signal observed during the reaction of aniline and pentyl nitrite in benzene is shown to be due not to phenyldiazoxyl (Ph-N=N-O.), as previously reported, but to a mixtnre of pentyloxyphenylnitmxyl and diphenylnihxyl radicais, this assignment being made with the aid of denterium labelling and on the basis of their observed hyperhe coupling constants and g values.
Summary4,2-Chloronitrobenzenediazonium ions in aqueous buffer solutions between pH 2.9 and 7.9 do not hydrolyze by dediazoniation as previous authors have assumed, but by denitration. The isomeric 2,4-compound reacts by denitration (ca. 70%) and dechlorination (ca. 30%). The reactions are general base catalyzed. The products and kinetics are consistent with an S,Ar-mechanism in which the general base-catalyzed addition of a hydroxyl group at the reacting C-atom is rate-limiting. The rate maxima at or near the pH-values corresponding to (pK, + pK2)/2 of the diazonium cis-diazotate equilibria can be rationalized on the assumption that the diazonium ion is the only equilibrium form of the diazo compound which enters the substitution proper, and the superposition of rate term ;,k, [B] of all nucleophiles involved (HzO, OH-and buffer bases).
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.