2-Bromoaniline → Ethyl 4-(2-bromoanilino)benzoate

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2-Bromoaniline (1.851 mL, 16.35 mmol) and ethyl 4-iodobenzoate (2.60 mL, 15.58 mmol) were dissolved in toluene (argon bubbled through for 10 min) (80 mL). To the stirred mixture were palladium acetate (0.175 g, 0.78 mmol), rac-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (0.776 g, 1.25 mmol) and cesium carbonate (7.10 g, 21.81 mmol) added, argon bubbled through the reaction for 2 min and heated then at 100 °C for 3 h. The reaction was not complete (the reaction was checked on a worked-up portion on GCMS and the product was 20% on GCMS). The following were added to the cooled reaction mixture: rac-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (400 mg) and palladium acetate (100 mg) and then argon bubbled through the reaction for 1 min and heated then at 100 °C overnight. The reaction was checked on a worked- up portion on GCMS => 85% product. The following were added to the cooled reaction mixture: rac-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (200 mg) and palladium acetate (50 mg) and then argon bubbled through the reaction for 1 min and heated then at 100 °C for 3 h => done. The reaction was poured on a filter-funnel (silica, packed in toluene, eluted with toluene, Rf 0.32). The product came out in fractions 5-8 (Note 1) and they were pooled and the solvent was removed on the rotovap to give ethyl 4-(2-bromophenylamino)benzoate (3.00 g, 60.2 %) as a light brown oil.

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