1,3-bis(phenylmethoxy)propan-2-one

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:1.1000000238418581; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1,3-dibenzyloxy-2-propanol(100.0 g, 367 mmol), acetonitrile (1352 mL) and 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (5.74 g, 36.7 mmol) were placed in a 5,000-mL four-necked flask equipped with a mechanical stirrer and a thermometer under a nitrogen stream, and the mixture was stirred for 5 minutes. Then, 3% aqueous sodium bicarbonate solution (1,028 g, 367 mmol) was added and the mixture was cooled to 1.1° C. using an ice bath. 11.9% aqueous sodium hypochlorite solution (when 10% aqueous sodium hypochlorite solution on the market was titrated, the accurate concentration was 11.9%) (276 g, 441 mmol) was added to the mixture over a period of more than 2 hours while keeping the temperature of the mixture at 5° C. or less (the reaction was a little exothermic), and the mixture was stirred at from 0.5° C. to 2.0° C. for 1 hour. Methyl t-butyl ether (2,700 mL) was added to the reaction mixture, the mixture was stirred for 20 minutes while keeping the temperature at 10° C. or less and allowed to stand for 10 minutes, and the resulting two layers were separated (the water layer weighed 1, 289 g and its pH was 8). The obtained organic layer was washed with 10% aqueous sodium sulfite solution (330 g), 5% saline (200 g) and 20% saline (200 g) in this order. The resulting solution (3,130 g) was analyzed by high performance liquid chromatography and as a result 91.8 g (yield 93%) of the captioned 1,3-dibenzyloxypropanone was obtained. equipped with a mechanical stirrer the accurate concentration was 11.9%) (276 g, 441 mmol) was added to the mixture over a period of more than 2 hours at 5° C. or less was stirred at from 0.5° C. to 2.0° C. for 1 hour the mixture was stirred for 20 minutes at 10° C. or less to stand for 10 minutes the resulting two layers were separated (the water layer The obtained organic layer was washed with 10% aqueous sodium sulfite solution (330 g), 5% saline (200 g) and 20% saline (200 g) in this order

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

実験手順: Tetrabutylammonium fluoride trihydrate (TBAF 3H2O) (2.9 g, 0.5 equivalent) was dissolved in THF (5 ml). This was added cautiously to a stirred and cooled (+15° C.) solution of 1,3-dibenzyloxy-2-propanone in toluene (24.65 g, equivalent to 5 g of the ketone) and (trifluoromethyl)trimethylsilane (7.5 ml). There was an exotherm and a lot of gas evolution on addition of the first 1 ml of TBAF solution. The temperature rose from 18 to 40° C. The TBAF addition was carried out over 3 minutes and then the mixture was stirred at 15-30° C. for a further 2 minutes and then cooled to +10° C. while carrying out an HPLC analysis. The reaction mixture was sequentially washed with 1M aqueous hydrochloric acid (50 ml), 1% aqueous sodium chloride solution (2×25 ml) and a mixture of 1% sodium chloride (25 ml) and saturated sodium bicarbonate (5 ml) solution. The separated organic extract was concentrated in vacuo to give 6.41 g of the desired product as dark brown oil in 101.8% yield. The NMR spectrum showed the presence of residual toluene (8.8%) and starting material (ca 3%). This was added cautiously to rose from 18 to 40° C the mixture was stirred at 15-30° C. for a further 2 minutes cooled to +10° C. The reaction mixture was sequentially washed with 1M aqueous hydrochloric acid (50 ml), 1% aqueous sodium chloride solution (2×25 ml) a mixture of 1% sodium chloride (25 ml) and saturated sodium bicarbonate (5 ml) solution The separated organic extract was concentrated in vacuo

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

実験手順: Tetrabutylammonium fluoride trihydrate (TBAF 3H2O) (2.9 g, 0.5 equivalent) was dissolved in THF (5 ml). This was added cautiously to a stirred and cooled (+15° C.) solution of 1,3-dibenzyloxy-2-propanone in toluene (24.65 g, equivalent to 5 g of the ketone) and (trifluoromethyl)trimethylsilane (7.5 ml). There was an exotherm and a lot of gas evolution on addition of the first 1 ml of TBAF solution. The temperature rose from 18 to 40° C. The TBAF addition was carried out over 3 minutes and then the mixture was stirred at 15-30° C. for a further 2 minutes and then cooled to +10° C. while carrying out an HPLC analysis. The reaction mixture was sequentially washed with 1M aqueous hydrochloric acid (50 ml), 1% aqueous sodium chloride solution (2×25 ml) and a mixture of 1% sodium chloride (25 ml) and saturated sodium bicarbonate (5 ml) solution. The separated organic extract was concentrated in vacuo to give 6.41 g of the desired product as dark brown oil in 101.8% yield. The NMR spectrum showed the presence of residual toluene (8.8%) and starting material (ca 3%). This was added cautiously to rose from 18 to 40° C the mixture was stirred at 15-30° C. for a further 2 minutes cooled to +10° C. The reaction mixture was sequentially washed with 1M aqueous hydrochloric acid (50 ml), 1% aqueous sodium chloride solution (2×25 ml) a mixture of 1% sodium chloride (25 ml) and saturated sodium bicarbonate (5 ml) solution The separated organic extract was concentrated in vacuo

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1,3-dibenzyloxy-2-propanone (2 g) and (trifluoromethyl)trimethylsilane (2.56 ml, 2.3 equivalents) in dichloromethane (20 ml) was stirred and cooled to 0° C. A solution of 1M tetrabutylammonium fluoride in THF (4 ml) was added dropwise over 3 minutes. Initial addition of a few drops gave an exotherm of 10° C. Throughout the addition the batch temperature was maintained below 10° C. After completing the addition the dark brown mixture was stirred at +5° C. for 5 minutes when HPLC analysis indicated the reaction to be complete. The reaction mixture was stirred for an additional 5 minutes and then washed with 1M aqueous hydrochloric acid (15 ml), saturated sodium bicarbonate (15 ml) and 1% w/v aqueous sodium chloride solution (2×15 ml). The organic extract was concentrated in vacuo to give 2.5 g of the desired product as dark oil in 99.3% yield. The NMR spectrum of the product was concordant with a reference sample. Initial addition of a few drops gave an exotherm of 10° C Throughout the addition the batch temperature was maintained below 10° C the addition the dark brown mixture was stirred at +5° C. for 5 minutes when HPLC analysis the reaction The reaction mixture was stirred for an additional 5 minutes washed with 1M aqueous hydrochloric acid (15 ml), saturated sodium bicarbonate (15 ml) and 1% The organic extract was concentrated in vacuo

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1,3-dibenzyloxy-2-propanol (500 g, 1.84 mol, 1.0 eq.), TEMPO (5.5 g, 0.034 mol) in dichloromethane (1.25 L) was placed in a 10 L flange flask fitted with overhead stirrer. A solution of potassium bromide (48 g, 0.40 mol) in water (185 ml) was added and the reaction stirred and cooled to −10° C. A 14% aqueous NaOCl solution was diluted to 1M (2145 g diluted to 4050 ml). The pH of this solution was then adjusted to 9.5 by dissolving NaHCO3 (80 g) immediately before use. This NaOCl solution was added over 1 hour, keeping the temperature of the reaction mixture between 10-15° C. The mixture was the stirred for 60 minutes. The orange coloured organic phase was separated and the aqueous layer was extracted with dichloromethane (5.0 L, 2.0 L). The combined organics were washed with 10% aq. HCl (10.75 L) containing potassium iodide (143 g), 10% aq. Na2S2O5 (5.0 L) and water (5.0 L). The organics were dried over MgSO4 and concentrated under reduced pressure to give the crude title compound (893 g, 90%). This compound was taken through to the next step without further purification. fitted with overhead stirrer between 10-15° C stirred for 60 minutes was separated the aqueous layer was extracted with dichloromethane (5.0 L, 2.0 L) The combined organics were washed with 10% aq. HCl (10.75 L) containing potassium iodide (143 g), 10% aq. Na2S2O5 (5.0 L) and water (5.0 L) The organics were dried over MgSO4 concentrated under reduced pressure

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

実験手順: A mixture of sulfur trioxide/pyridine complex (2.33 g, 4 equivalents) in DMSO (3 ml) and triethylamine (2.05 ml, 4 equivalents) was stirred to give a pale yellow solution. To this was added a solution of 1,3-dibenzyloxy-2-propanol (1 g) in DMSO (1 ml) over 2 minutes. (The reaction mixture was kept in a water bath). The temperature of the reaction mixture reached 30° C. After 10 minutes the water bath was removed and the reaction mixture was stirred at room temperature (ca 20-25° C.) for 3 hours. The reaction mixture was diluted with ethyl acetate (15 ml) and water (15 ml), stirred and the organic extract was separated. The organic extract was washed with 5% w/v sodium chloride (2×10 ml) and water (10 ml). The separated organic extract was concentrated in vacuo to give an oil which solidified to provide 0.75 g of 1,3-dibenzyloxy-2-propanone in 75.8% yield. An NMR spectrum of product was concordant with a reference sample. to give a pale yellow solution (The reaction mixture was kept in a water bath reached 30° C After 10 minutes the water bath was removed the reaction mixture was stirred at room temperature (ca 20-25° C.) for 3 hours The reaction mixture was diluted with ethyl acetate (15 ml) and water (15 ml) stirred the organic extract was separated The organic extract was washed with 5% w/v sodium chloride (2×10 ml) and water (10 ml) The separated organic extract was concentrated in vacuo to give an oil which

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

実験手順: A mixture of sulfur trioxide/pyridine complex (2.33 g, 4 equivalents) in DMSO (3 ml) and triethylamine (2.05 ml, 4 equivalents) was stirred to give a pale yellow solution. To this was added a solution of 1,3-dibenzyloxy-2-propanol (1 g) in DMSO (1 ml) over 2 minutes. (The reaction mixture was kept in a water bath). The temperature of the reaction mixture reached 30° C. After 10 minutes the water bath was removed and the reaction mixture was stirred at room temperature (ca 20-25° C.) for 3 hours. The reaction mixture was diluted with ethyl acetate (15 ml) and water (15 ml), stirred and the organic extract was separated. The organic extract was washed with 5% w/v sodium chloride (2×10 ml) and water (10 ml). The separated organic extract was concentrated in vacuo to give an oil which solidified to provide 0.75 g of 1,3-dibenzyloxy-2-propanone in 75.8% yield. An NMR spectrum of product was concordant with a reference sample. to give a pale yellow solution (The reaction mixture was kept in a water bath reached 30° C After 10 minutes the water bath was removed the reaction mixture was stirred at room temperature (ca 20-25° C.) for 3 hours The reaction mixture was diluted with ethyl acetate (15 ml) and water (15 ml) stirred the organic extract was separated The organic extract was washed with 5% w/v sodium chloride (2×10 ml) and water (10 ml) The separated organic extract was concentrated in vacuo to give an oil which