1-(2-hydroxyphenyl)propan-1-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:; See reaction.notes.procedure_details.

実験手順: 2'-Hydroxypropiophenone (15.02 g) and diethyl oxalate (17.54 g) were added to a solution of sodium ethoxide in ethanol (prepared from 6.90 g of sodium and 200 ml of ethanol), and the mixture was heated for 2.5 hours while refluxing. The mixture was cooled, poured over 2N HCl (320 ml) and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried (MgSO4), after which the solvent was distilled off. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1:3, v/v) to yield an oily substance (4.26 g). This oily substance was dissolved in acetic acid-concentrated hydrochloric acid (1:1, 30 ml) and heated for 1 hour while refluxing. After cooling, the reaction mixture was poured over water (150 ml) and stirred at room temperature for 10 minutes. The separated crystals were collected by filtration to yield 3-methyl-4-oxo-4H-1-benzopyran-2-carboxylic acid (2.62 g, 13%), which was then recrystallized from ethanol to yield colorless prisms having a melting point of 192° to 193° C. the mixture was heated for 2.5 hours while refluxing The mixture was cooled extracted with ethyl acetate The ethyl acetate layer was washed with water dried (MgSO4) after which the solvent was distilled off eluted with ethyl acetate-hexane (1:3 v/v) to yield an oily substance (4.26 g) heated for 1 hour while refluxing After cooling The separated crystals were collected by filtration

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: A mixture of 2'-hydroxypropiophenone (25.8 g), benzyl chloride (21.8 g), sodium iodide (2.6 g), potassium carbonate (23.8 g) and dry dimethylformamide (260 ml) was heated with stirring at 80° C. for 23 hours. The mixture was cooled and filtered and the filtrate was concentrated under reduced pressure. The residue was extracted with ether and the extract was washed with water, 1N aqueous sodium hydroxide, water, 10% hydrochloric acid, aqueous sodium hydrogen carbonate and aqueous sodium chloride in that order, dried, and concentrated to dryness to give 2'-benzyloxypropiophenone (37.9 g) as an oil. was heated The mixture was cooled filtered the filtrate was concentrated under reduced pressure The residue was extracted with ether the extract was washed with water, 1N aqueous sodium hydroxide, water, 10% hydrochloric acid, aqueous sodium hydrogen carbonate and aqueous sodium chloride in that order dried concentrated to dryness

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

実験手順: A mixture of 2'-hydroxypropiophenone (25.8 g), benzyl chloride (21.8 g), sodium iodide (2.6 g), potassium carbonate (23.8 g) and dry dimethylformamide (260 ml) was heated with stirring at 80° C. for 23 hours. The mixture was cooled and filtered and the filtrate was concentrated under reduced pressure. The residue was extracted with ether and the extract was washed with water, 1N aqueous sodium hydroxide, water, 10% hydrochloric acid, aqueous sodium hydrogen carbonate and aqueous sodium chloride in that order, dried, and concentrated to dryness to give 2'-benzyloxypropiophenone (37.9 g) as an oil. was heated The mixture was cooled filtered the filtrate was concentrated under reduced pressure The residue was extracted with ether the extract was washed with water, 1N aqueous sodium hydroxide, water, 10% hydrochloric acid, aqueous sodium hydrogen carbonate and aqueous sodium chloride in that order dried concentrated to dryness

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

実験手順: To a mixture of 1-(2-hydroxyphenyl)propan-1-one (10.0 g), methyl bromoacetate (5.11 mL) and acetone (100 mL) was added potassium carbonate (18.4 g), and the mixture was stirred overnight at room temperature. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:4, volume ratio) to give a colorless oil. To a solution (150 mL) of the obtained oil in N,N-dimethylformamide was added 1,8-diazabicyclo[5.4.0]undec-7-ene (8.12 mL), and the mixture was stirred at 120° C. for 2 hr. 1N Hydrochloric acid was added to quench the reaction, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. Ethyl acetate was added to the residue, the insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:9, volume ratio) to give the title object compound (7.14 g, 52%) as a white solid. The insoluble material was filtered off the filtrate was concentrated under reduced pressure The residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:4, volume ratio) to give a colorless oil the mixture was stirred at 120° C. for 2 hr to quench the reaction the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over magnesium sulfate concentrated under reduced pressure Ethyl acetate was added to the residue the insoluble material was filtered off the filtrate was concentrated under reduced pressure The residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:9, volume ratio)

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

実験手順: 15 g of 1-(2-hydroxyphenyl)-1-propanone are added dropwise to 170 ml of a 40% aqueous solution of potassium hydroxide. To this emulsion are then added, in increments, 31.2 g of hydroxylamine hydrochloride and the mixture is stirred for 4 h at 0°-5° C. The reaction mixture is then acidified with 150 ml of concentrated hydrochloric acid, the precipitated product is isolated by filtration, washed with water and dried, giving 1-(2-hydroxyphenyl)-1-propanone oxime having a melting point of 88°-90° C. the precipitated product is isolated by filtration washed with water dried

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

実験手順: 2-Isoquinolin-3-yl-3-methyl-chromen-4-one was prepared in 76% yield using method A, starting from 2′-hydroxy-propiophenone and methyl isoquinoline-3-carboxylate.

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

実験手順: 2'-Hydroxypropiophenone (15.02 g) and diethyl oxalate (17.54 g) were added to a solution of sodium ethoxide in ethanol (prepared from 6.90 g of sodium and 200 ml of ethanol), and the mixture was heated for 2.5 hours while refluxing. The mixture was cooled, poured over 2N HCl (320 ml) and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried (MgSO4), after which the solvent was distilled off. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1:3, v/v) to yield an oily substance (4.26 g). This oily substance was dissolved in acetic acid-concentrated hydrochloric acid (1:1, 30 ml) and heated for 1 hour while refluxing. After cooling, the reaction mixture was poured over water (150 ml) and stirred at room temperature for 10 minutes. The separated crystals were collected by filtration to yield 3-methyl-4-oxo-4H-1-benzopyran-2-carboxylic acid (2.62 g, 13%), which was then recrystallized from ethanol to yield colorless prisms having a melting point of 192° to 193° C. the mixture was heated for 2.5 hours while refluxing The mixture was cooled extracted with ethyl acetate The ethyl acetate layer was washed with water dried (MgSO4) after which the solvent was distilled off eluted with ethyl acetate-hexane (1:3 v/v) to yield an oily substance (4.26 g) heated for 1 hour while refluxing After cooling The separated crystals were collected by filtration

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

実験手順: 2'-Hydroxypropiophenone (15.02 g) and diethyl oxalate (17.54 g) were added to a solution of sodium ethoxide in ethanol (prepared from 6.90 g of sodium and 200 ml of ethanol), and the mixture was heated for 2.5 hours while refluxing. The mixture was cooled, poured over 2N HCl (320 ml) and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried (MgSO4), after which the solvent was distilled off. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1:3, v/v) to yield an oily substance (4.26 g). This oily substance was dissolved in acetic acid-concentrated hydrochloric acid (1:1, 30 ml) and heated for 1 hour while refluxing. After cooling, the reaction mixture was poured over water (150 ml) and stirred at room temperature for 10 minutes. The separated crystals were collected by filtration to yield 3-methyl-4-oxo-4H-1-benzopyran-2-carboxylic acid (2.62 g, 13%), which was then recrystallized from ethanol to yield colorless prisms having a melting point of 192° to 193° C. the mixture was heated for 2.5 hours while refluxing The mixture was cooled extracted with ethyl acetate The ethyl acetate layer was washed with water dried (MgSO4) after which the solvent was distilled off eluted with ethyl acetate-hexane (1:3 v/v) to yield an oily substance (4.26 g) heated for 1 hour while refluxing After cooling The separated crystals were collected by filtration