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The ability of the oxidative arylamination process to derivatize electron‐deficient 1,3,7‐triazapyrenes has been investigated. These triazapyrenes react with a wide range of sodium aryl(hetaryl) amides to give access to the corresponding 6‐aryl(hetaryl)amino‐1,3,7‐triazapyrenes in moderate to good yields. The reaction of 6,8‐dialkoxy‐1,3,7‐triazapyrene with sodium arylamides gives rise to 6,8‐bis(arylamino)‐1,3,7‐triazapyrenes or 6‐methoxy‐8‐arylamino‐1,3,7‐triazapyrenes, depending on the reaction conditions.

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Arylamination of 3-nitropyridine via the nucleophilic substitution of hydrogen leads to a mixture of 2-arylamino-5-nitropyridines and novel 2-arylamino-5-nitrosopyridines, with the latter as the major product. The proposed mechanism includes the formation of σH-adducts and their further aromatization proceeding either through an oxidative pathway or intramolecular Red/Ox pathway of the SN H reaction. Moreover, we have shown that nitroso compounds can be selectively oxidized with m-chloroperbenzoic acid to give the corresponding nitro derivatives or their N-oxides, depending on the reaction temperature and the amount of oxidant.

The ability of urea anions to react as nucleophiles with alkoxy derivatives of 1,3,7‐triazapyrenes has been investigated. It was found that against all expectations, the products of the substitution of an alkoxy groups (SNipso) by amino group were isolated in good yields. The reactions proceed in anhydrous dimethyl sulfoxide solution at room temperature. But when anions of the mono‐substituted ureas containing bulky substituents were used, the first products of the earlier unknown SNAr reactions of alkyl carbamoyl amination were obtained.