The hydrolysis reactions of the title compounds N-sulfonatooxy-N-acetyl-1-aminonaphthalene, 2d, and N-sulfonatooxy-N-acetyl-2-aminonaphthalene, 2e, in 5% CH 3 CN-H 2 O (20 °C, pH 5.7-7.5, µ ) 0.5) appear to involve nitrenium ion intermediates that exhibit very small azide/solvent trapping efficiencies. The azide/solvent selectivities, S, were estimated from fitting azide-and solvent-derived product yields as a function of [N 3 -]. The derived values of S for the N-acetyl-N-(1-naphthyl)nitrenium ion (3d) of 0.7 ( 0.1 M -1 and the N-acetyl-N-(2-naphthyl)nitrenium ion (3e) of 1.5 ( 0.2 M -1 show that these ions have short lifetimes (ca. 10 -10 s) in aqueous solution. In turn, these results suggest that the hydrolysis reactions of 2d and 2e should proceed, in part, through ion-pair and/or preassociation pathways. The decrease in the yield of the rearrangement products N-acetyl-1-amino-2-sulfonatooxynaphthalene, 6, and N-acetyl-2-amino-1-sulfonatooxynaphthalene, 11, with increasing [N 3 -] indicates that this is the case. Plots of log(mutagenicity) toward Salmonella typhimurium TA 98 and TA 100 for a series of polycyclic and monocyclic aromatic amines vs log(S) for ArNAc + show that there is no general correlation of mutagenicity with nitrenium ion selectivity, but there does appear to be a limited correlation of these two quantities for five polycyclic amines for which there are reliable mutagenicity and nitrenium ion selectivity data. These results suggest that nitrenium ion selectivity is one of several factors that determines the mutagenicity of aromatic amines.

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