Halide ion trapping of nitrenium ions formed in the Bamberger rearrangement of <i>N</i>-arylhydroxylamines. Lifetime of the parent phenylnitrenium ion in water

Abstract

The acid reactions of five arylhydroxylamines (Ar = 2,6-Me 2 C 6 H 3 , 2,5-Me 2 C 6 H 3 , 2-MeC 6 H 4 , 2-ClC 6 H 4 , and C 6 H 5 ) have been studied at constant ionic strength (NaClO 4 ) in the presence of varying amounts of NaBr and NaCl. Each system resulted in the corresponding p-aminophenol, the product of Bamberger rearrangement, as the only detectable product in the absence of halide. The addition of halide ion reduced the yield of this product, with the appearance of the corresponding p-haloaniline, o-haloaniline (where appropriate), and the parent aniline (predominantly with bromide). Rate constants for the reaction were measured in the case of the parent and 2,6-dimethyl systems and showed small decreases (chloride) or increases (bromide) with increasing halide concentration. These changes did not correlate with the change in products, implying that the rate variations were caused by specific salt effects. Product data were analyzed by a mechanism involving rate-limiting formation of the appropriate arylnitrenium ion followed by product-determining steps involving trapping by the solvent or by the added halide. The possibility that a portion of the halide-trapped products were derived from a pre-association mechanism was also included. Kinetic analyses then produced k Br :k w and k Cl :k w ratios for two limiting cases, one involving pre-association with an equilibrium constant k as = 0.3, and one ignoring pre-association. From an azide:water ratio (k Az :k w ) previously determined for the 2,6-dimethylphenylnitrenium, k Br was concluded to lie in the range (4–5) × 10 9 M −1 s −1 for all of the nitrenium ions of this study. This range for k Br then led to k w values of (1–2) × 10 9 s −1 (2,5-Me 2 ), (2–3) × 10 9 s −1 (2-Me), and (4–8) × 10 9 s −1 (parent and 2-Cl), where the ranges reflect uncertainties in the exact value of k Br and in the contribution from pre-association. The lifetime of the parent phenylnitrenium ion in water at one molar ionic strength is concluded to lie in the range 125–250 ps. Key words: nitrenium ion lifetime, phenylhydroxylamine, phenylnitrenium ion, Bamberger rearrangement.