If k az for these ions is diffusion limited at ca. The N 3 -/solvent selectivities of these ions (5.1 × 10 6 M - 1 for 2a, 2.3 × 10 6 M - 1 for 2b, 1.2 × 10 5 M - 1 for 2c, and 5.2 × 10 4 M - 1 for 2d) are comparable to those of highly selective carbocyclic nitrenium ions.

Similar reactions have previously only been reported for heterocyclic 1-alkyl-2-imidazolium ions. The reactions with N 3 - and d-G generally follow patterns previously established for carbocyclic nitrenium ions, but the reactions with AcO - and HPO 4 2 - are unusual. The reactions of the nitrenium ions with AcO -, HPO 4 2 -, N 3 -, and 2‘-deoxyguanosine (d-G) were characterized in aqueous solution by using a combination of competitive trapping methods and product isolation and identification. The less reactive esters 1a and 1b also undergo acid-catalyzed ester hydrolysis to generate the corresponding hydroxamic acids at pH <2, while the more reactive 2c and 2d are prone to rearrangement in nonaqueous solvents.

The model ultimate carcinogens 1a− d, related to the metabolites of the food-derived carcinogenic heterocyclic amines Glu-P-1, Glu-P-2, MeIQx, and IQx, spontaneously decompose in neutral aqueous solution to generate the heterocyclic nitrenium ions, 2a− d.

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