2-amino-4-bromo-5-fluorobenzaldehyde

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of pyridine (310.6 mg, 3.927 mmol) in EtOH (8.0 mL), a solution of ethyl bromopyruvate (752.1 mg, 3.857 mmol) in EtOH (8.0 mL) was added dropwise over a period of 20 min. The mixture was heated to 65° C. for 1 h, and then cooled to room temperature. 2-Amino-4-bromo-5-fluorobenzaldehyde (796.1 mg, 3.651 mmol) was added, followed by pyridine (690.6 mg, 8.731 mmol). The mixture was heated at 85° C. for 5 h. Pyrrolidine (640.1 mg, 9.000 mmol) was then added. After heating for an additional 3 h, the reaction mixture was allowed to cool and was then concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (0-100% EtOAc in hexanes) to give the sub-title compound as a yellow solid (882.5 mg, 77%). LCMS calc. for C12H11BrFN2O2(M+H)+: m/z=313.0. found 313.0. cooled to room temperature The mixture was heated at 85° C. for 5 h After heating for an additional 3 h to cool was then concentrated under reduced pressure The residue was purified by flash chromatography on silica gel (0-100% EtOAc in hexanes)

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of pyridine (310.6 mg, 3.927 mmol) in EtOH (8.0 mL), a solution of ethyl bromopyruvate (752.1 mg, 3.857 mmol) in EtOH (8.0 mL) was added dropwise over a period of 20 min. The mixture was heated to 65° C. for 1 h, and then cooled to room temperature. 2-Amino-4-bromo-5-fluorobenzaldehyde (796.1 mg, 3.651 mmol) was added, followed by pyridine (690.6 mg, 8.731 mmol). The mixture was heated at 85° C. for 5 h. Pyrrolidine (640.1 mg, 9.000 mmol) was then added. After heating for an additional 3 h, the reaction mixture was allowed to cool and was then concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (0-100% EtOAc in hexanes) to give the sub-title compound as a yellow solid (882.5 mg, 77%). LCMS calc. for C12H11BrFN2O2(M+H)+: m/z=313.0. found 313.0. cooled to room temperature The mixture was heated at 85° C. for 5 h After heating for an additional 3 h to cool was then concentrated under reduced pressure The residue was purified by flash chromatography on silica gel (0-100% EtOAc in hexanes)

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

Procedure: To a mixture of 4-bromo-5-fluoro-2-nitrobenzaldehyde (2.219 g, 8.947 mmol) and iron powder (2.535 g, 45.39 mmol), EtOH (30.0 mL) was added, followed by AcOH (10.0 mL) and water (5.0 mL). The reaction mixture was stirred at room temperature for 2 h, then concentrated under reduced pressure. EtOAc (150 mL) was added to the resulting residue. The mixture formed was filtered through a pad of diatomaceous earth. The diatomaceous earth pad was washed with 10 wt % aq. K3PO4 (150 mL) and EtOAc (100 mL). The organic layer was separated and then was washed with brine (150 mL), dried over Na2SO4 and concentrated under reduced pressure. The resulting residue was purified by flash chromatography on silica gel (0-30% EtOAc in hexanes) to give the sub-title compound as a yellow solid (1.518 g, 78%). LCMS calc. for C7H6BrFNO (M+H)+: m/z=218.0. found 217.9. was added concentrated under reduced pressure EtOAc (150 mL) was added to the resulting residue The mixture formed was filtered through a pad of diatomaceous earth The diatomaceous earth pad was washed with 10 wt % aq. K3PO4 (150 mL) and EtOAc (100 mL) The organic layer was separated was washed with brine (150 mL) dried over Na2SO4 concentrated under reduced pressure The resulting residue was purified by flash chromatography on silica gel (0-30% EtOAc in hexanes)

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of pyridine (310.6 mg, 3.927 mmol) in EtOH (8.0 mL), a solution of ethyl bromopyruvate (752.1 mg, 3.857 mmol) in EtOH (8.0 mL) was added dropwise over a period of 20 min. The mixture was heated to 65° C. for 1 h, and then cooled to room temperature. 2-Amino-4-bromo-5-fluorobenzaldehyde (796.1 mg, 3.651 mmol) was added, followed by pyridine (690.6 mg, 8.731 mmol). The mixture was heated at 85° C. for 5 h. Pyrrolidine (640.1 mg, 9.000 mmol) was then added. After heating for an additional 3 h, the reaction mixture was allowed to cool and was then concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (0-100% EtOAc in hexanes) to give the sub-title compound as a yellow solid (882.5 mg, 77%). LCMS calc. for C12H11BrFN2O2(M+H)+: m/z=313.0. found 313.0. cooled to room temperature The mixture was heated at 85° C. for 5 h After heating for an additional 3 h to cool was then concentrated under reduced pressure The residue was purified by flash chromatography on silica gel (0-100% EtOAc in hexanes)

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

Procedure: To a mixture of 4-bromo-5-fluoro-2-nitrobenzaldehyde (2.219 g, 8.947 mmol) and iron powder (2.535 g, 45.39 mmol), EtOH (30.0 mL) was added, followed by AcOH (10.0 mL) and water (5.0 mL). The reaction mixture was stirred at room temperature for 2 h, then concentrated under reduced pressure. EtOAc (150 mL) was added to the resulting residue. The mixture formed was filtered through a pad of diatomaceous earth. The diatomaceous earth pad was washed with 10 wt % aq. K3PO4 (150 mL) and EtOAc (100 mL). The organic layer was separated and then was washed with brine (150 mL), dried over Na2SO4 and concentrated under reduced pressure. The resulting residue was purified by flash chromatography on silica gel (0-30% EtOAc in hexanes) to give the sub-title compound as a yellow solid (1.518 g, 78%). LCMS calc. for C7H6BrFNO (M+H)+: m/z=218.0. found 217.9. was added concentrated under reduced pressure EtOAc (150 mL) was added to the resulting residue The mixture formed was filtered through a pad of diatomaceous earth The diatomaceous earth pad was washed with 10 wt % aq. K3PO4 (150 mL) and EtOAc (100 mL) The organic layer was separated was washed with brine (150 mL) dried over Na2SO4 concentrated under reduced pressure The resulting residue was purified by flash chromatography on silica gel (0-30% EtOAc in hexanes)