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We have successfully developed a new method for synthesis of o-chloroaniline derivatives by three-component reactions of tertiary amines,arynes and carbon tetrachloride.With 2-(trimethylsilyl)aryl triflates as aryne precursors,a range of tertiary amines smoothly reacted with arynes and carbon tetrachloride to afford structurally diverse tertiary o-chloroaniline in moderate to excellent yields with mild conditions and without transition metals.