A green synthesis strategy of 2‐arylquinoxalines and 3‐arylquinoxalin‐2(1H)‐ones via ball milling, which could avoid copious solvent waste, was accomplished in this work. Aryl radicals were produced from aryldiazonium salts by using a solvent‐free or catalyst‐free single electron transfer process induced by mechanical force, affording a series of 2‐arylquinoxalines and 3‐arylquinoxalin‐2(1H)‐ones with 28%–85 yield.
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