(2-amino-5-bromo-3-methoxyphenyl)methanol

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

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-amino-5-bromo-3-methoxybenzoic acid (20.0 g, 81.30 mmol) is suspended in 250 mL THF, cooled to 0° C. and combined with borane-THF complex (315 mL, 0.315 mol). The reaction mixture is stirred for 5 d at 20° C. and then combined with 10 mL EtOH, stirred for 15 min and then stirred into 250 mL water. The mixture is extracted 3× with DCM, the combined organic phases are dried and the solvent is eliminated in vacuo. The crude product is suspended in DCM and extracted 2× with 400 mL 1 N hydrochloric acid. The combined aqueous phases are adjusted to pH 5-6 with potassium carbonate, the precipitate formed is filtered off and (2-amino-5-bromo-3-methoxy-phenyl)-methanol (HPLC-MS: tRet.=1.41 min, MS(M+H)+=232/234; method FEC3) is obtained. stirred for 15 min The mixture is extracted 3× with DCM the combined organic phases are dried extracted 2× with 400 mL 1 N hydrochloric acid the precipitate formed is filtered off

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

Procedure: To a 0.15 M chloroform solution of (2-amino-5-bromo-3-methoxyphenyl)methanol (10.16 g, 43.96 mmol) was added manganese dioxide (19.9 g, 280.5 mmol). The mixture was stirred under argon at room temperature for 16 hours. The resulting mixture was filtered through celite and washed with dichloromethane. The filtrate was concentrated to dryness and used in next step. ES/MS m/z 228/230 (MH+). The resulting mixture was filtered through celite washed with dichloromethane The filtrate was concentrated to dryness

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-amino-5-bromo-3-methoxybenzoic acid (20.0 g, 81.30 mmol) is suspended in 250 mL THF, cooled to 0° C. and combined with borane-THF complex (315 mL, 0.315 mol). The reaction mixture is stirred for 5 d at 20° C. and then combined with 10 mL EtOH, stirred for 15 min and then stirred into 250 mL water. The mixture is extracted 3× with DCM, the combined organic phases are dried and the solvent is eliminated in vacuo. The crude product is suspended in DCM and extracted 2× with 400 mL 1 N hydrochloric acid. The combined aqueous phases are adjusted to pH 5-6 with potassium carbonate, the precipitate formed is filtered off and (2-amino-5-bromo-3-methoxy-phenyl)-methanol (HPLC-MS: tRet.=1.41 min, MS(M+H)+=232/234; method FEC3) is obtained. stirred for 15 min The mixture is extracted 3× with DCM the combined organic phases are dried extracted 2× with 400 mL 1 N hydrochloric acid the precipitate formed is filtered off