Electrochemical C–H Nitration of N ‐Substituted Anilines With Sodium Nitrite

An environmentally friendly electrochemical nitration of N ‐substituted anilines using NaNO 2 as the nitro source is reported. The method operates under constant current conditions in a CH 3 CN/H 2 O solvent mixture without the need for external oxidants, metal catalysts, or additional electrolytes. A wide range of aniline derivatives bearing both electron‐donating and electron‐withdrawing groups undergo smooth nitration to afford the corresponding nitroanilines in moderate to excellent yields. Cyclic voltammetry studies reveal that the presence of nitrite facilitates the oxidation of the aniline substrate, while radical trapping experiments support an ionic reaction pathway. The scalability of the protocol is demonstrated by gram‐scale synthesis. This work provides a sustainable and operationally simple approach to the construction of valuable nitroaniline scaffolds.