4-bromo-2-(trifluoromethyl)phenol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 3.0 g (11.8 mmol) 4-bromo-1-methoxy-2-trifluoromethyl-benzene in 20 mL 1 M HBr in glacial acetic acid is stirred for 60 h at 90° C. The reaction solution is diluted with 300 mL water, adjusted to pH 7 with K2CO3. The aqueous phase is extracted with EtOAc, the combined organic extracts are with washed 40 mL quarter-saturated NaHCO3 solution and dried over MgSO4. The solvent is eliminated i.vac. and the product is further reacted without any more purification. The aqueous phase is extracted with EtOAc with washed 40 mL quarter-saturated NaHCO3 solution dried over MgSO4 and the product is further reacted without any more purification

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 3.0 g (11.8 mmol) 4-bromo-1-methoxy-2-trifluoromethyl-benzene in 20 mL 1 M HBr in glacial acetic acid is stirred for 60 h at 90° C. The reaction solution is diluted with 300 mL water, adjusted to pH 7 with K2CO3. The aqueous phase is extracted with EtOAc, the combined organic extracts are with washed 40 mL quarter-saturated NaHCO3 solution and dried over MgSO4. The solvent is eliminated i.vac. and the product is further reacted without any more purification. The aqueous phase is extracted with EtOAc with washed 40 mL quarter-saturated NaHCO3 solution dried over MgSO4 and the product is further reacted without any more purification

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Then, 8.47 g of 4-bromo-2-trifluoromethylphenol, 5.34 g of potassium carbonate, 4.49 g of benzyl chloride and 100 ml of N,N-dimethylformamide were charged into a reaction vessel, and stirred under ice cooling. After 24 hours, the reaction solution was poured into ice-water and extracted three times with 50 ml of diethyl ether. The ether layers were combined, washed with an aqueous 10 % sodium hydroxide solution, dried over anhydrous magnesium sulfate and then concentrated to give a crude product. This crude product was subjected to silica gel chromatography to give 9.38 g of 4-bromo-2-trifluoromethyl-1-benzyloxybenzene (yield, 81%). extracted three times with 50 ml of diethyl ether washed with an aqueous 10 % sodium hydroxide solution dried over anhydrous magnesium sulfate concentrated to give a crude product

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Then, 8.47 g of 4-bromo-2-trifluoromethylphenol, 5.34 g of potassium carbonate, 4.49 g of benzyl chloride and 100 ml of N,N-dimethylformamide were charged into a reaction vessel, and stirred under ice cooling. After 24 hours, the reaction solution was poured into ice-water and extracted three times with 50 ml of diethyl ether. The ether layers were combined, washed with an aqueous 10 % sodium hydroxide solution, dried over anhydrous magnesium sulfate and then concentrated to give a crude product. This crude product was subjected to silica gel chromatography to give 9.38 g of 4-bromo-2-trifluoromethyl-1-benzyloxybenzene (yield, 81%). extracted three times with 50 ml of diethyl ether washed with an aqueous 10 % sodium hydroxide solution dried over anhydrous magnesium sulfate concentrated to give a crude product

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: First, 41.33 g of 2-trifluoromethylphenol and 1800 ml of chloroform were charged into a reaction vessel, and 129.16 g of tetra-n-butylammonium tribromide was slowly added at room temperature over about one hour with stirring. After stirring at room temperature for 72 hours, the reaction solution was concentrated. Then, 500 ml of 10% hydrochloric acid was added to the resultant residue, and the mixture was extracted four times with 200 ml of diethyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate and then concentrated to give 49.5 g of 4-bromo-2-trifluoromethylphenol as a crude product (yield, 81%). After stirring at room temperature for 72 hours the reaction solution was concentrated Then, 500 ml of 10% hydrochloric acid was added to the resultant residue the mixture was extracted four times with 200 ml of diethyl ether washed with water dried over anhydrous magnesium sulfate concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: First, 41.33 g of 2-trifluoromethylphenol and 1800 ml of chloroform were charged into a reaction vessel, and 129.16 g of tetra-n-butylammonium tribromide was slowly added at room temperature over about one hour with stirring. After stirring at room temperature for 72 hours, the reaction solution was concentrated. Then, 500 ml of 10% hydrochloric acid was added to the resultant residue, and the mixture was extracted four times with 200 ml of diethyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate and then concentrated to give 49.5 g of 4-bromo-2-trifluoromethylphenol as a crude product (yield, 81%). After stirring at room temperature for 72 hours the reaction solution was concentrated Then, 500 ml of 10% hydrochloric acid was added to the resultant residue the mixture was extracted four times with 200 ml of diethyl ether washed with water dried over anhydrous magnesium sulfate concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium hydride (60% w/w dispersion in mineral oil, 0.96 g) was added to a solution of 4-bromo-2-trifluoromethyl-phenol (5.0 g) in dry THF (200 ml) and the mixture was stirred for 30 minutes. 1-Chloromethoxy-2-methoxy-ethane (2.85 ml) was then added and the mixture was stirred for 1 hour at room temperature. The solvent was removed under reduced pressure. The residue was taken into water and tert-butyl methyl ether, the organic layer was washed with brine, dried over sodium sulphate and concentrated under reduced pressure to afford 4-bromo-1-(2-methoxy-ethoxymethoxy)-2-trifluoromethyl-benzene (6.4 g) as an oil. 1H NMR (CDCl3) δ: 7.69 (m, 1H), 7.53 (m, 1H), 7.19 (m, 1H), 5.33 (s, 2H), 3.83 (m, 2H), 3.55 (m, 2H), 3.37 (s, 3H). the mixture was stirred for 1 hour at room temperature The solvent was removed under reduced pressure the organic layer was washed with brine dried over sodium sulphate concentrated under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Bromoethanol (23.3 g) was added to a mixture of 4-bromo-2-(trifluoromethyl)-phenol (30 g) and potassium carbonate (34.4 g) in acetonitrile (200 ml). The above mixture was refluxed for 8 hours then another portion of 2-bromoethanol (8 g) was added and the reflux continued for another 6 hours. After diluting with ethyl acetate (500 ml), the mixture was washed with water (300 ml) then 0.1 M sodium hydroxide (200 ml). Organic layer was dried over magnesium sulphate, solvent removed under reduced pressure, the residue was taken into heptane by heat, 2-(4-bromo-2-(trifluoromethyl)-phenoxy)-ethanol crystalised and collected by filtration (17 g). The above mixture was refluxed for 8 hours the mixture was washed with water (300 ml) Organic layer was dried over magnesium sulphate, solvent removed under reduced pressure by heat 2-(4-bromo-2-(trifluoromethyl)-phenoxy)-ethanol crystalised collected by filtration (17 g)