(4-bromophenyl) propanoate

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

Procedure: 4-Bromophenyl propionate (34 g, 0.15 mmol) and aluminum chloride (44 g, 0.3 mmol) were heated together at 100° C. for 30 mins. The solution became dark and hydrogen chloride gas was evolved. After cooling, the reaction mixture was carefully poured into ice water, and the resulting mixture was extracted with dichloromethane. The organic layer was washed with brine, dried and concentrated to give the residue, which was purified by column chromatography to give 1-(5-bromo-2-hydroxyphenyl)propan-1-one. (20 g, 59%) 1H NMR (CDCl3, 400 MHz): 1.24 (t, 3H), 2.98-3.04 (m, 2H), 6.88 (d, 1H), 7.52 (t, 1H), 7.76 (s, 1H). After cooling the resulting mixture was extracted with dichloromethane The organic layer was washed with brine dried concentrated to give the residue, which was purified by column chromatography

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

Procedure: 4-Bromophenol (28.4 g, 0.165 mol) and DMAP (0.17 g, 1.4 mmol) were dissolved in dichloromethane (110 mL). The solution was cooled in an ice-bath and triethylamine (24 mL) was added portionwise. Propionyl chloride (16 g, 0.17 mmol) was then added dropwise and the resulting mixture was stirred at room temperature for 2 hrs. The mixture was washed with water, followed by brine, dried and concentrated to give 4-bromophenyl propionate, which was used in the next step without further purification (34 g, 92%). 1H NMR (MeOD, 400 MHz): 1.12-1.24 (m, 3H), 2.57-2.63 (m, 2H), 7.02-7.06 (m, 2H), 7.51-7.55 (m, 2H). The solution was cooled in an ice-bath The mixture was washed with water dried concentrated

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

Procedure: Triethylamine (219 ml) was added to a solution of 4-bromophenol (259 g) and 4-dimethylaminopyridine (1.5 g) in dichloromethane (1000 ml) at 0° C. at such a rate that the temperature did not rise above 20° C. When the addition was complete propionyl chloride (137 ml) was added in portions over 1 hour such that the temperature did not rise above 20° C. Finally, the mixture was stirred at room temperature for 2 hours. Water (700 ml) was added and the layers were separated. The dichloromethane solution was washed with brine (500 ml), dried (MgSO4) and concentrated in vacuo to give the title compound as an oil, 344 g. did not rise above 20° C When the addition was added in portions over 1 hour such that the temperature did not rise above 20° C the layers were separated The dichloromethane solution was washed with brine (500 ml) dried (MgSO4) concentrated in vacuo

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

Procedure: 4-Bromophenyl propionate (115 g) (see Preparation 1) and aluminium chloride (150 g) were heated together at approximately 90° C. for 15 minutes. The solution became dark and hydrogen chloride gas was evolved. After cooling the black mass was carefully added to ice and a brown solid formed. The mixture was extracted with dichloromethane. The organic extract was separated, washed with brine, dried (anhydrous magnesium sulphate) and the solvent removed under reduced pressure to yield 1-(5-bromo-2-hydroxyphenyl)propane-1-one (110 g) as a yellow solid. After cooling the black mass was carefully added to ice a brown solid formed The mixture was extracted with dichloromethane The organic extract was separated washed with brine dried (anhydrous magnesium sulphate) the solvent removed under reduced pressure

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

Procedure: 4-Bromophenol (259 g) and 4-dimethylaminopyridine (1.5 g) were dissolved in dichloromethane (1000 ml), the solution was cooled in an ice bath and triethylamine (219 ml) was added portionwise such that the reaction temperature was kept below 20° C. Propionyl chloride (137 ml) was then added over 1 hour and the resulting mixture was stirred at room temperature for 2 hours. The mixture was washed with water followed by brine, then dried (anhydrous magnesium sulphate) and the solvent removed under reduced pressure to yield 4-bromophenyl propionate (344 g) as a green oil. the solution was cooled in an ice bath was kept below 20° C The mixture was washed with water dried (anhydrous magnesium sulphate) the solvent removed under reduced pressure

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

Procedure: 4-Bromophenyl propionate (115 g) (see Preparation 1) and aluminium chloride (150 g) were heated together at approximately 90° C. for 15 minutes. The solution became dark and hydrogen chloride gas was evolved. After cooling the black mass was carefully added to ice and a brown solid formed. The mixture was extracted with dichloromethane. The organic extract was separated, washed with brine, dried (anhydrous magnesium sulphate) and the solvent removed under reduced pressure to yield 1-(5-bromo-2-hydroxyphenyl)propan-1-one (110 g) as a yellow solid. After cooling the black mass was carefully added to ice a brown solid formed The mixture was extracted with dichloromethane The organic extract was separated washed with brine dried (anhydrous magnesium sulphate) the solvent removed under reduced pressure

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

Procedure: 4-Bromophenol (259 g) and 4-dimethylaminopyridine (1.5 g) were dissolved in dichloromethane (1000 ml), the solution was cooled in an ice bath and triethylamine (219 ml) was added portionwise such that the reaction temperature was kept below 20° C. Propionyl chloride (137 ml) was then added over 1 hour and the resulting mixture was stirred at room temperature for 2 hours. The mixture was washed with water followed by brine, then dried (anhydrous magnesium sulphate) and the solvent removed under reduced pressure to yield 4-bromophenyl propionate (344 g) as a green oil. the solution was cooled in an ice bath was kept below 20° C The mixture was washed with water dried (anhydrous magnesium sulphate) the solvent removed under reduced pressure

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

Procedure: 4-Bromophenyl propionate (34 g, 0.15 mmol) and aluminum chloride (44 g, 0.3 mmol) were heated together at 100° C. for 30 mins. The solution became dark and hydrogen chloride gas was evolved. After cooling, the reaction mixture was carefully poured into ice water, and the resulting mixture was extracted with dichloromethane. The organic layer was washed with brine, dried and concentrated to give the residue, which was purified by column chromatography to give 1-(5-bromo-2-hydroxyphenyl)propan-1-one. (20 g, 59%) 1H NMR (CDCl3, 400 MHz): 1.24 (t, 3H), 2.98-3.04 (m, 2H), 6.88 (d, 1H), 7.52 (t, 1H), 7.76 (s, 1H). After cooling the resulting mixture was extracted with dichloromethane The organic layer was washed with brine dried concentrated to give the residue, which was purified by column chromatography

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

Procedure: 4-Bromophenol (28.4 g, 0.165 mol) and DMAP (0.17 g, 1.4 mmol) were dissolved in dichloromethane (110 mL). The solution was cooled in an ice-bath and triethylamine (24 mL) was added portionwise. Propionyl chloride (16 g, 0.17 mmol) was then added dropwise and the resulting mixture was stirred at room temperature for 2 hrs. The mixture was washed with water, followed by brine, dried and concentrated to give 4-bromophenyl propionate, which was used in the next step without further purification (34 g, 92%). 1H NMR (MeOD, 400 MHz): 1.12-1.24 (m, 3H), 2.57-2.63 (m, 2H), 7.02-7.06 (m, 2H), 7.51-7.55 (m, 2H). The solution was cooled in an ice-bath The mixture was washed with water dried concentrated