1-(5-bromo-2-hydroxyphenyl)-2-methylpropan-1-one

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

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

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-(5-Bromo-2-hydroxyphenyl)-2-methylpropan-1-one (0.82 g, 3.37 mmol) was dissolved in EtOH (10 mL) then hydroxylamine (50% solution in water, 0.267 g, 4.05 mmol) was added followed by HOAc (1 drop). The mixture was heated to about 80° C. for about 2 h. The mixture was cooled then evaporated under reduced pressure to give an oil. Acetic anhydride (2 mL, 20 mmol) was added and the mixture was stirred for about 45 min at ambient temperature. The mixture was concentrated under reduced pressure then pyridine (7 mL) was added and then the mixture was heated to about 145° C. for about 3 h. The mixture was cooled, treated with 1 N HCl, and extracted with EtOAc. The organic extract was dried over MgSO4, filtered and evaporated to a residue that was then dissolved in DME (4 mL). Cesium carbonate (1.09 g, 3.35 mmol) was added and the mixture was heated at about 150° C. for about 30 min in the microwave. The mixture was evaporated and then purified by flash chromatography with 9:1 heptane/EtOAc to give the title compound (0.12 g, 15%): LC/MS (Table 1, Method a) Rt=3.33 min; MS m/z: 340.1 (M+H)+. The mixture was cooled then evaporated under reduced pressure to give an oil The mixture was concentrated under reduced pressure pyridine (7 mL) was added the mixture was heated to about 145° C. for about 3 h The mixture was cooled treated with 1 N HCl extracted with EtOAc The organic extract was dried over MgSO4 filtered evaporated to a residue that was then dissolved in DME (4 mL) the mixture was heated at about 150° C. for about 30 min in the microwave The mixture was evaporated purified by flash chromatography with 9:1 heptane/EtOAc

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Bromo-2-(1-hydroxy-2-methylpropyl)phenol (4.88 g, 19.9 mmol) was dissolved in DCM (50 mL) then manganese dioxide (2.44 g, 23.8 mmol) was added. After stirring for about 2 h at ambient temperature another portion of manganese dioxide (2.44 g, 23.8 mmol) was added then the mixture was heated to about 40° C. After about 2 d the mixture was filtered then evaporated and the residue purified by flash chromatography on silica gel with 9:1 Heptane/EtOAc as an eluent to give the title compound (0.82 g, 17%): LC/MS (Table 1, Method a) Rt, =3.38 min; MS m/z: 241.1 (M−H)−. was added After about 2 d the mixture was filtered then evaporated the residue purified by flash chromatography on silica gel with 9:1 Heptane/EtOAc as an eluent