Bornylacetate

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 1-p-tolyl-ethanone (0.5 g, 4.16 mmol) in dichloromethane-methanol (50 ml-20 mL) was added tetrabutylammonium tribromide (2.2 g, 4.58 mmol) at room temperature. The mixture was stirred until the orange color faded. The solvent was then distilled under reduced pressure and the resulting precipitate was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and evaporated in vacuo to give a residue which was purified by flash column chromatography to yield the desired product 2-bromo-1-p-tolyl-1-ethanone (0.74 g, 84%). 1H NMR (300 MHz, DMSO-d6) δ 2.39 (s, 3H), 4.89 (s, 2H), 7.37 (d, 2H), 7.89 (d, 2H); ESI-MS (MK): 213 and 215. The solvent was then distilled under reduced pressure the resulting precipitate was extracted with ethyl acetate The organic layer was dried over sodium sulfate evaporated in vacuo to give a residue which was purified by flash column chromatography

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 3,5-diethylphenol (9.30 g, 61.9 mmol) in methanol (100 mL) was added tetrabutylammonium tribromide (29.8 g, 61.9 mmol), and the mixture was stirred at room temperature for 15 hr. The solvent was evaporated under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=0:100-25:75), and the obtained crystals were recrystallized from heptane to give the title compound (1.85 g) as colorless crystals. The mother liquor was concentrated under reduced pressure to give the title compound (8.68 g) as dark-brown crystals (total 10.5 g, total yield 74%). The solvent was evaporated under reduced pressure, water was added to the residue the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was purified by silica gel column chromatography (ethyl acetate:hexane=0:100-25:75) the obtained crystals were recrystallized from heptane

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Benzyl-[2-(4-acetyl-phenoxy)-ethyl]-carbamate (10.2 g, 32.5 mmol) was dissolved in methylene chloride (100 ml) and methanol (50 ml), and tetrabutylamonium tribromide (15.7 g, 32.5 mmol) was added in one portion. The reaction mixture was stirred for about sixteen hours, and then quenched with water. The aqueous phase was extracted with ethyl acetate and then washed with saturated aqeous sodium bicarbonate, and saturated Na2S2O3. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated in vacuo, and the resulting crude material was purified by column chromatography (silica gel; hexanes to 2:1 hexanes/ethyl acetate) to afford a colorless oil which solidified upon standing. (11.5 g, 90% yield). quenched with water The aqueous phase was extracted with ethyl acetate washed with saturated aqeous sodium bicarbonate, and saturated Na2S2O3 The combined organic extracts were dried over magnesium sulfate filtered concentrated in vacuo the resulting crude material was purified by column chromatography (silica gel; hexanes to 2:1 hexanes/ethyl acetate) to afford a colorless oil which

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a round-bottomed flask, N-(1,1-dimethyl-2-phenyl-ethyl)-2,2,2-trifluoroacetamide (6.90 g, 21.0 mmol) was dissolved in methylene chloride (66 ml) and methanol (33 ml). Tetrabutylammonium tribromide (10.6 g, 22.0 mmol) was added to this solution in one portion, and the mixture was allowed to stir at room temperature overnight. The volatiles were then removed in vacuo to an oil, which was then resuspended in 100 ml of methylene chloride and extracted with 125 ml of saturated aqueous sodium bicarbonate. The aqueous extracts were reextracted with methylene chloride (3×10 ml), and the combined organic extracts were then washed with water and dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude oil was purified by column chromatography (silica gel; 60% methylene chloride/hexanes to 10% ethyl acetate/methylene chloride), and the resulting material (5.18 g) was recrystallized from hexanes to afford 3.14 g (41% yield) of pure product as a fluffy white solid. The volatiles were then removed in vacuo to an oil, which extracted with 125 ml of saturated aqueous sodium bicarbonate the combined organic extracts were then washed with water dried over magnesium sulfate filtered concentrated in vacuo The crude oil was purified by column chromatography (silica gel; 60% methylene chloride/hexanes to 10% ethyl acetate/methylene chloride) the resulting material (5.18 g) was recrystallized from hexanes

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a round-bottomed flask, N-[2-(4-acetyl-phenyl)-ethyl]-acetamide (7.23 g, 35.2 mmol) was dissolved in methylene chloride (120 ml), and methanol (60 ml). Tetrabutylammonium tribromide (17.0 g, 35.2 mmol) was added to this solution in one portion, and the mixture was allowed to stir overnight at room temperature. The volatiles were then removed in vacuo to afford an oil, which was then resuspended in 100 ml of methylene chloride and extracted with 125 ml of saturated aqueous sodium bicarbonate. The aqueous extracts were reextracted with methylene chloride (3×100 ml), and the combined organic extracts were then washed with water, dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude oil was purified by column chromatography (silica gel; methylene chloride to 7% methanol/methylene chloride), and the resulting material was washed with 110 ml of water to afford 8.27 g (83% yield) of pure product as a white solid. LRMS ([M−1 ]−)=283.0, 284.9. The volatiles were then removed in vacuo to afford an oil, which extracted with 125 ml of saturated aqueous sodium bicarbonate the combined organic extracts were then washed with water dried over magnesium sulfate filtered concentrated in vacuo The crude oil was purified by column chromatography (silica gel; methylene chloride to 7% methanol/methylene chloride) the resulting material was washed with 110 ml of water

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-Fluoro-5-methylphenol (5.0 g, 40 mmol) was dissolved in chloroform (200 mL). Tetrabutylammonium tribromide (19 g, 40 mmol) was added and the reaction stirred at ambient temperature for 30 minutes. The reaction was concentrated and purified over silica gel (20% EtOAc in hexanes) to afford 4-bromo-2-fluoro-5-methylphenol (7.8 g, 38 mmol, 96% yield) as an amber oil. The reaction was concentrated purified over silica gel (20% EtOAc in hexanes)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of tetrabutylammonium tribromide (11.8 g, 24.4 mmol) in dichloromethane (80 ml) was added dropwise to a solution of the product from Step C (5.0 g, 22.2 mmol) in dichloromethane (20 ml) and methanol (20 ml) at room temperature over 1 hour. At completion of the addition, the mixture was stirred at room temperature for 15 hours and was then concentrated. The residue was taken into dichloromethane and was washed with saturated sodium bicarbonate three times. The organic layer was concentrated and the residue was dissolved in dimethylformamide (100 ml). Lithium carbonate (5.3 g, 71.1 mmol) and lithium bromide (4.1 g, 46.6 mmol) were added and the resulting mixture was stirred at 140° C. for 1.5 hours. After cooling to room temperature, the solids were filtered and rinsed with ethyl acetate. The filtrate was washed with water four times and dried over sodium sulfate to give 7-bromonaphthalen-1-ol (2.7 g, 56%): 1H NMR (300 MHz, CDCl3) δ 8.41 (d, J=1.8 Hz, 1H), 7.68 (d, J=8.7 Hz, 1H), 7.57 (dd, J=8.7, 1.8 Hz, 1H), 7.41 (d, J=8.4 Hz, 1H), 7.28-7.35 (m, 1H), 6.62 (d, J=7.2 Hz, 1H), 5.80 (br s, 1H). At completion of the addition was then concentrated was washed with saturated sodium bicarbonate three times The organic layer was concentrated the residue was dissolved in dimethylformamide (100 ml) the resulting mixture was stirred at 140° C. for 1.5 hours After cooling to room temperature the solids were filtered rinsed with ethyl acetate The filtrate was washed with water four times dried over sodium sulfate

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 17.4 g of tetra-butylammonium tribromide are added, at room temperature, to 7 g of 1-(2,4-dichlorophenyl)-1-propanone dissolved in a mixture of 420 ml of methylene chloride and 140 ml of methanol. After 24 hours, the reaction medium is evaporated to dryness under vacuum. The residue is taken up in water and extracted with ethyl acetate, and the organic phase is dried over sodium sulphate. The solvent is evaporated off under vacuum and the product is then purified on a column of silica, using a mixture of cyclohexane and ethyl acetate (20:1 v/v) as eluent. the reaction medium is evaporated to dryness under vacuum extracted with ethyl acetate the organic phase is dried over sodium sulphate The solvent is evaporated off under vacuum the product is then purified on a column of silica a mixture of cyclohexane and ethyl acetate (20:1 v/v) as eluent

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 30 g (170 mmol) of 2-(4,5-dihydroisoxazol-3-yl)-3-methylaniline are dissolved in 400 ml of acetonitrile, and 94 g (0.68 mol) of potassium carbonate are added. At temperatures <30° C., 84 g (174 mmol) of tetrabutylammonium tribromide are then added a little at a time, with vigorous stirring. For work-up, the solid is filtered off with suction and the solution is diluted with methylene chloride and extracted with water. The solvent is stripped off and the residue is then taken up again in methyl tert-butyl ether and washed twice with water. The organic phase is dried and concentrated. For work-up, the solid is filtered off with suction the solution is diluted with methylene chloride extracted with water washed twice with water The organic phase is dried concentrated

反应条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of quinolin-6-ylamine (503 mg, 3.49 mmol) in dichloromethane (17 mL) and methanol (8.6 mL) was added tetra-n-butylammonium tribromide (1.68 g, 3.49 mmol). The mixture was stirred at 25° C. for 90 minutes, and then 10 5 mL of aqueous sodium thiosulfate was added. The mixture was extracted with dichloromethane, and the combined extracts were washed with water, dried (Na2SO4), filtered and concentrated to dryness under reduced pressure. Purification by flash column (hexanes/ethylacetate gradient) gave 5-bromo-quinolin-6-ylamine (246 mg, 32%). The mixture was extracted with dichloromethane the combined extracts were washed with water dried (Na2SO4) filtered concentrated to dryness under reduced pressure Purification by flash column (hexanes/ethylacetate gradient)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 5-acetylindan (500 mg, 3.1 mmol) in dichloromethane-methanol (2:1, 15 ml) was added tetrabutylammonium tribromide (1.64 g, 3.4 mmol) was added at room temperature. After 23 h, the mixture was concentrated and the residue was partitioned between diethyl ether (50 ml) and water (50 ml). The organic layer was separated and washed with water (50 ml), brine (50 ml), and dried (MgSO4). Removal of solvent gave 698 mg (56%) of the title compound as white solids. was added at room temperature the mixture was concentrated the residue was partitioned between diethyl ether (50 ml) and water (50 ml) The organic layer was separated washed with water (50 ml), brine (50 ml) dried (MgSO4) Removal of solvent

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Then, 16 g of 2-ethyl-6-methylphenol was dissolved in 200 ml of chloroform, which was stirred at 0° C., and 56.6 g of tetrabutylammonium tribromide was added in small portions to this solution. After stirring at room temperature for 1 hour, the solvent was distilled out under reduced pressure. The residue was dissolved in 300 ml of diethyl ether, successively washed with 10% hydrochloric acid and water, dried over anhydrous magnesium sulfate, and then concentrated to give a crude product. The crude product was subjected to silica gel chromatography, which afforded 23 g of 4-bromo-2-ethyl-6-methylphenol (92% yield). After stirring at room temperature for 1 hour the solvent was distilled out under reduced pressure The residue was dissolved in 300 ml of diethyl ether successively washed with 10% hydrochloric acid and water dried over anhydrous magnesium sulfate concentrated to give a crude product