tert-butyl 2-amino-4-bromobenzoate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To toluene 15 mL solution of tert-butyl 2-amino-4-bromobenzoate 1.0 g were added 1-fluoro-4-iodobenzene 0.85 mL, cesium carbonate 3.6 g, palladium acetate 8 mg and rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 23 mg at room temperature, and it was heated and refluxed under nitrogen atmosphere for 6 hours. After the reaction mixture was cooled to room temperature, palladium acetate 8 mg and rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl 23 mg were added to it, it was heated and refluxed under nitrogen atmosphere for 8 hours. After the reaction mixture was cooled to room temperature, water was added to it, insoluble matter was filtrated. The organic layer was separated and collected,dried over anhydrous magnesium sulfate after sequential washing with 10% citric acid aqueous solution and saturated sodium chloride aqueous solution, the solvent was removed under reduced pressure. The obtained residue was refined by silica gel column chromatography [eluent; hexane:ethyl acetate=20:1] to give tert-butyl 4-bromo-2-(4-fluoroanilino)benzoate 0.55 g of pale yellow oil. it was heated refluxed under nitrogen atmosphere for 6 hours was heated refluxed under nitrogen atmosphere for 8 hours After the reaction mixture was cooled to room temperature was filtrated The organic layer was separated after sequential washing with 10% citric acid aqueous solution and saturated sodium chloride aqueous solution the solvent was removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Iron powder 3.0 g were added to a mixed solution methanol 28 mL and acetic acid 28 mL of tert-butyl 4-bromo-2-nitrobenzoate 5.5 g, it was heated and refluxed for 1 hour. After the reaction mixture was cooled to room temperature, saturated sodium hydrogen carbonate aqueous solution and ethyl acetate were added to it, and insoluble matter was filtrated. The organic layer was separated and collected,dried over anhydrous magnesium sulfate after sequential washing with saturated sodium hydrogen carbonate aqueous solution and saturated sodium chloride aqueous solution, the solvent was removed under reduced pressure to give tert-butyl 2-amino-4-bromobenzoate 4.3 g of pale yellow oil. was heated refluxed for 1 hour was filtrated The organic layer was separated after sequential washing with saturated sodium hydrogen carbonate aqueous solution and saturated sodium chloride aqueous solution the solvent was removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3.0 g of iron powder was added to a mixed solution of 28 mL of methanol and 28 mL of acetic acid containing 5.5 g of tert-butyl 4-bromo-2-nitrobenzoate, and the resulting mixture was heated to reflux for 1 hour. After one reaction mixture was cooled to room temperature, a saturated sodium hydrogen carbonate aqueous solution and ethyl acetate were added and insoluble were removed by filtration. The organic layer was separated and dried over anhydrous magnesium sulfate after washed with a saturated sodium hydrogen carbonate aqueous solution and a saturated sodium chloride aqueous solution sequentially, and the solvent was evaporated under reduced pressure to obtain 4.3 g of tert-butyl 2-amino-4-bromobenzoate as pale yellow oil. the resulting mixture was heated to reflux for 1 hour After one reaction mixture insoluble were removed by filtration The organic layer was separated dried over anhydrous magnesium sulfate after washed with a saturated sodium hydrogen carbonate aqueous solution a saturated sodium chloride aqueous solution sequentially, and the solvent was evaporated under reduced pressure