1-(3-bromo-4-hydroxyphenyl)ethanone

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

Procedure: To a stirred solution of (4-chloro-2-pyridinyl)methanol (Commercial eg Aldrich) (0.2 g) in THF (5 ml) were added 1-(3-bromo-4-hydroxyphenyl)ethanone (0.3 g) and triphenylphosphine (0.547 g). This was stirred for 10 min before cooling and adding slowly DEAD (0.363 g). This was stirred for 16 h. The reaction mixture was partitioned between water and ethyl acetate. The aqueous was reextracted with ethyl acetate and the combined organics were washed with brine, dried over sodium sulfate and concentrated in vacuo. This was purified through silica eluting with 0-35% ethyl acetate in hexane to give the title compound, 0.30 g before cooling This was stirred for 16 h The reaction mixture was partitioned between water and ethyl acetate the combined organics were washed with brine dried over sodium sulfate concentrated in vacuo This was purified through silica eluting with 0-35% ethyl acetate in hexane

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

Procedure: To a stirred solution of (4-chloro-2-pyridinyl)methanol (Commercial eg Aldrich) (0.2 g) in THF (5 ml) were added 1-(3-bromo-4-hydroxyphenyl)ethanone (0.3 g) and triphenylphosphine (0.547 g). This was stirred for 10 min before cooling and adding slowly DEAD (0.363 g). This was stirred for 16 h. The reaction mixture was partitioned between water and ethyl acetate. The aqueous was reextracted with ethyl acetate and the combined organics were washed with brine, dried over sodium sulfate and concentrated in vacuo. This was purified through silica eluting with 0-35% ethyl acetate in hexane to give the title compound, 0.30 g before cooling This was stirred for 16 h The reaction mixture was partitioned between water and ethyl acetate the combined organics were washed with brine dried over sodium sulfate concentrated in vacuo This was purified through silica eluting with 0-35% ethyl acetate in hexane

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

Procedure: To a stirred solution of (4-chloro-2-pyridinyl)methanol (Commercial eg Aldrich) (0.2 g) in THF (5 ml) were added 1-(3-bromo-4-hydroxyphenyl)ethanone (0.3 g) and triphenylphosphine (0.547 g). This was stirred for 10 min before cooling and adding slowly DEAD (0.363 g). This was stirred for 16 h. The reaction mixture was partitioned between water and ethyl acetate. The aqueous was reextracted with ethyl acetate and the combined organics were washed with brine, dried over sodium sulfate and concentrated in vacuo. This was purified through silica eluting with 0-35% ethyl acetate in hexane to give the title compound, 0.30 g before cooling This was stirred for 16 h The reaction mixture was partitioned between water and ethyl acetate the combined organics were washed with brine dried over sodium sulfate concentrated in vacuo This was purified through silica eluting with 0-35% ethyl acetate in hexane

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

Procedure: To a stirred solution of (4-chloro-2-pyridinyl)methanol (Commercial eg Aldrich) (0.2 g) in THF (5 ml) were added 1-(3-bromo-4-hydroxyphenyl)ethanone (0.3 g) and triphenylphosphine (0.547 g). This was stirred for 10 min before cooling and adding slowly DEAD (0.363 g). This was stirred for 16 h. The reaction mixture was partitioned between water and ethyl acetate. The aqueous was reextracted with ethyl acetate and the combined organics were washed with brine, dried over sodium sulfate and concentrated in vacuo. This was purified through silica eluting with 0-35% ethyl acetate in hexane to give the title compound, 0.30 g before cooling This was stirred for 16 h The reaction mixture was partitioned between water and ethyl acetate the combined organics were washed with brine dried over sodium sulfate concentrated in vacuo This was purified through silica eluting with 0-35% ethyl acetate in hexane

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

Procedure: Starting from 1-(3-bromo-4-hydroxy-phenyl)-ethanone (example B.a4) and commercially available bromomethyl-cyclopropane the title compound is obtained as colorless solid.

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

Procedure: Starting from 1-(3-bromo-4-hydroxy-phenyl)-ethanone prepared according to literature (Heravi et al, Tetrahedron Letters 2005, 46, 8959) and bromomethyl-cyclopropane the title compound is obtained as colorless solid. prepared

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

Procedure: To a solution of 1-(3-bromo-4-hydroxyphenyl)ethanone (15) (963 mg, 4.48 mmol, 1 eq, Aldrich, Milwaukee, Wis., USA) in DMF (15 mL), was added methyl 2-bromoacetate (1.02 g, 6.72 mmol, 1.5 eq) and potassium carbonate (1.86 g, 13.5 mmol; 3 eq). The reaction mixture was stirred at room temperature for 18 h. Solvent was removed in vacuo, and the residue was dissolved in EtOAc, washed by water and brine, dried (Na2SO4), filtered, and concentrated in vacuo to give 1.05 g, (81%) of methyl 2-(4-acetyl-2-bromophenoxy)acetate (16) as a brown solid. Solvent was removed in vacuo the residue was dissolved in EtOAc washed by water and brine dried (Na2SO4) filtered concentrated in vacuo

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

Procedure: To a solution of 4-hydroxyacetophenone (6.8 g, 0.05 mol, 1 eq) in 60% acetic acid (50 mL), was added a solution of bromine (2.6 mL, 0.05 mol, 1 eq) in 80% acetic acid (20 mL). After stirring at room temperature for 30 min, the reaction mixture was poured into 100 mL of cold water. The solid was filtered and the filtrate was further diluted with 500 mL of cold water. The white precipitate was collected by filtration, washed with water and dried under vacuum to afford 4.2 g (39%) of 1-(3-bromo-4-hydroxyphenyl)ethanone (15) as white solid. 1HNMR (CDCl3, 400 MHz): δ 8.15 (s, 1H), 7.86 (d, 1H), 7.18 (d, 1H), 5.96 (s, 1H), 2.56 (s, 3H). MS (ES-API): M+1=216.9. HPLC (Method B) tR=2.48 min. The solid was filtered the filtrate was further diluted with 500 mL of cold water The white precipitate was collected by filtration washed with water dried under vacuum

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

Procedure: Starting from 1-(3-bromo-4-hydroxy-phenyl)-ethanone (example B.a4) and commercially available bromomethyl-cyclopropane the title compound is obtained as colorless solid.

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

Procedure: To a stirred solution of (4-chloro-2-pyridinyl)methanol (Commercial eg Aldrich) (0.2 g) in THF (5 ml) were added 1-(3-bromo-4-hydroxyphenyl)ethanone (0.3 g) and triphenylphosphine (0.547 g). This was stirred for 10 min before cooling and adding slowly DEAD (0.363 g). This was stirred for 16 h. The reaction mixture was partitioned between water and ethyl acetate. The aqueous was reextracted with ethyl acetate and the combined organics were washed with brine, dried over sodium sulfate and concentrated in vacuo. This was purified through silica eluting with 0-35% ethyl acetate in hexane to give the title compound, 0.30 g before cooling This was stirred for 16 h The reaction mixture was partitioned between water and ethyl acetate the combined organics were washed with brine dried over sodium sulfate concentrated in vacuo This was purified through silica eluting with 0-35% ethyl acetate in hexane

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

Procedure: To a stirred solution of (4-chloro-2-pyridinyl)methanol (Commercial eg Aldrich) (0.2 g) in THF (5 ml) were added 1-(3-bromo-4-hydroxyphenyl)ethanone (0.3 g) and triphenylphosphine (0.547 g). This was stirred for 10 min before cooling and adding slowly DEAD (0.363 g). This was stirred for 16 h. The reaction mixture was partitioned between water and ethyl acetate. The aqueous was reextracted with ethyl acetate and the combined organics were washed with brine, dried over sodium sulfate and concentrated in vacuo. This was purified through silica eluting with 0-35% ethyl acetate in hexane to give the title compound, 0.30 g before cooling This was stirred for 16 h The reaction mixture was partitioned between water and ethyl acetate the combined organics were washed with brine dried over sodium sulfate concentrated in vacuo This was purified through silica eluting with 0-35% ethyl acetate in hexane