methyl 2-hydroxy-2,2-diphenylacetate

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:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: ((S)-1-Methyl-pyrrolidin-2-yl)-methanol (2.38 ml, 20 mmol) and hydroxy-diphenyl-acetic acid methyl ester (7.27 g, 30 mmol) are suspended in toluene (20 ml). Molecular sieve 4A (3 g) is added and the suspension is heated under stirring to 80° C. Sodium (0.46 g, 20 mmol) is added and the reaction mixture stirred at 80° C. for 3 hours. The reaction mixture is cooled to room temperature, solid filtered off, and washed with toluene. The filtrate is washed once with saturated aqueous NaHCO3 solution (50 ml) and twice with aqueous HCl 1M (30 ml each). The combined acidic aqueous layers are adjusted to pH 8 with saturated aqueous NaHCO3 solution. The emulsion is extracted with ethyl acetate (50 ml). The combined ethyl acetate layers are dried over sodium sulphate, filtered off and evaporated to dryness to give the product as a yellow oil that crystallises on standing. (M+H)+:326.2 the suspension is heated the reaction mixture stirred at 80° C. for 3 hours The reaction mixture is cooled to room temperature solid filtered off washed with toluene The filtrate is washed once with saturated aqueous NaHCO3 solution (50 ml) and twice with aqueous HCl 1M (30 ml each) The emulsion is extracted with ethyl acetate (50 ml) The combined ethyl acetate layers are dried over sodium sulphate filtered off evaporated to dryness

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of (R)-1-methyl-piperidine-3-ol (4.61 g, 0.040 mol) and hydroxy-diphenyl-acetic acid methyl ester (9.63 g, 0.040 mol) in cyclohexane (50 ml) is added preactivated 4A molecular sieves and the mixture heated to 50° C. Sodium metal (50 mg) is then added and the resulting mixture heated to reflux. After 1 hour further sodium (50 mg) is added and reflux maintained for 5 hours. Concentration, re-dissolution in chloroform and washing with water followed by brine, drying over magnesium sulphate, filtration and evaporation gives a crude product. Purification by vacuum flash silica chromatography (gradient elution: DCM to DCM:methanol 20:1) gives, after evaporation, the title product as a foam. is added the resulting mixture heated to reflux reflux maintained for 5 hours Concentration, re-dissolution in chloroform washing with water drying over magnesium sulphate, filtration and evaporation

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of (R)-1-methyl-piperidine-3-ol (4.61 g, 0.040 mol) and hydroxy-diphenyl-acetic acid methyl ester (9.63 g, 0.040 mol) in cyclohexane (50 ml) is added preactivated 4A molecular sieves and the mixture heated to 50° C. Sodium metal (50 mg) is then added and the resulting mixture heated to reflux. After 1 hour further sodium (50 mg) is added and reflux maintained for 5 hours. Concentration, re-dissolution in chloroform and washing with water followed by brine, drying over magnesium sulphate, filtration and evaporation gives a crude product. Purification by vacuum flash silica chromatography (gradient elution: DCM to DCM:methanol 20:1) gives, after evaporation, the title product as a foam. is added the resulting mixture heated to reflux reflux maintained for 5 hours Concentration, re-dissolution in chloroform washing with water drying over magnesium sulphate, filtration and evaporation

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

実験手順: (1-Methyl-piperidin-4-yl)-methanol (2.58 g, 20 mmol) and hydroxy-diphenyl-acetic acid methyl ester (9.69 g, 40 mmol) are suspended in toluene (65 ml). Molecular sieve 4A (1 g) is added and the mixture is stirred at room temperature for 10 minutes. Sodium (0.08 g) is added and the reaction mixture stirred at 80° C. for 3 hours. Additional sodium (0.1 g) is then added and heating maintained at 80° C. for 18 hours. The reaction mixture is cooled to room temperature, solid filtered off, and washed with ethylacetate. The filtrate is washed once with saturated aqueous NaHCO3 solution (50 ml) and twice with aqueous HCl 1M (25 ml each). The combined acidic aqueous layers are basified with saturated aqueous NaHCO3 solution and solid NaHCO3, the resulting precipitate is removed by filtration, drying under vacuum gives the title product as a white solid (M+H)+:340.09. the reaction mixture stirred at 80° C. for 3 hours heating maintained at 80° C. for 18 hours The reaction mixture is cooled to room temperature solid filtered off washed with ethylacetate The filtrate is washed once with saturated aqueous NaHCO3 solution (50 ml) and twice with aqueous HCl 1M (25 ml each) the resulting precipitate is removed by filtration drying under vacuum

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

実験手順: 30 ml of benzene, 0.4 g (4 mmol) of 3-piperidinol and 1.0 g (4 mmol) of methyl benzilate were put into a 50 ml 3-mouth flask equipped with a stirrer, a reflux condenser, and a molecular sieve 4A (15 g) tube and a soda lime tube for trapping methanol from out of the solvent that drips down through the reflux condensation, and the mixture was refluxed by heating while stirring. After all of the methyl benzilate had dissolved, 20 mg of sodium methoxide (made by Aldrich) was added to the solution and reaction was carried out for 3 hours. After the reaction had been completed, the reaction liquid was cooled to room temperature, and then 50 ml of 1N hydrochloric acid was added, and the organic solvent layer was removed. The aqueous solution layer obtained was washed twice with 50 ml of ether, and was then made basic using a 28% ammonium hydroxide aqueous solution. The aqueous solution was subjected to ether extraction, the ether layer obtained was washed twice with 50 ml of water, and then drying was carried out using anhydrous potassium carbonate. After removing the drying agent, the solvent was evaporated off under reduced pressure, thus obtaining an oily residue, and then this residue was recrystallized from ether-hexane, thus obtaining 0.5 g of (±)3-piperidyl benzilate ((±)3-PB) as crystals (yield 40%). equipped with a stirrer, a reflux condenser down through the reflux condensation the mixture was refluxed by heating the reaction liquid the organic solvent layer was removed The aqueous solution layer obtained was washed twice with 50 ml of ether The aqueous solution was subjected to ether extraction the ether layer obtained was washed twice with 50 ml of water drying After removing the drying agent the solvent was evaporated off under reduced pressure thus obtaining an oily residue this residue was recrystallized from ether-hexane

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

実験手順: 30 ml of benzene, 0.4 g (4 mmol) of 3-piperidinol and 1.0 g (4 mmol) of methyl benzilate were put into a 50 ml 3-mouth flask equipped with a stirrer, a reflux condenser, and a molecular sieve 4A (15 g) tube and a soda lime tube for trapping methanol from out of the solvent that drips down through the reflux condensation, and the mixture was refluxed by heating while stirring. After all of the methyl benzilate had dissolved, 20 mg of sodium methoxide (made by Aldrich) was added to the solution and reaction was carried out for 3 hours. After the reaction had been completed, the reaction liquid was cooled to room temperature, and then 50 ml of 1N hydrochloric acid was added, and the organic solvent layer was removed. The aqueous solution layer obtained was washed twice with 50 ml of ether, and was then made basic using a 28% ammonium hydroxide aqueous solution. The aqueous solution was subjected to ether extraction, the ether layer obtained was washed twice with 50 ml of water, and then drying was carried out using anhydrous potassium carbonate. After removing the drying agent, the solvent was evaporated off under reduced pressure, thus obtaining an oily residue, and then this residue was recrystallized from ether-hexane, thus obtaining 0.5 g of (±)3-piperidyl benzilate ((±)3-PB) as crystals (yield 40%). equipped with a stirrer, a reflux condenser down through the reflux condensation the mixture was refluxed by heating the reaction liquid the organic solvent layer was removed The aqueous solution layer obtained was washed twice with 50 ml of ether The aqueous solution was subjected to ether extraction the ether layer obtained was washed twice with 50 ml of water drying After removing the drying agent the solvent was evaporated off under reduced pressure thus obtaining an oily residue this residue was recrystallized from ether-hexane