bis(2-methoxyphenyl)methanone

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: 2,2'-Dimethoxybenzophenone (24.2 g, 0.14 mole) and 400 ml of ether were placed in a 1 1 flask and stirred at ambient temperature and methyl magnesium bromide (40 ml of 3.0 M solution in ether) was added dropwise. The resulting mixture was stirred overnight and then a few ml of water were added to quench the Grignard reagent. About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added and the mixture was shaken. The organic layer was next recovered, extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain 25.6 g (98 percent of theory) of the title compound as a white solid melting at 122°-123° C. The proton NMR spectrum was consistent with the assigned structure. The resulting mixture was stirred overnight to quench the Grignard reagent About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added the mixture was shaken extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure

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

実験手順: Sodium hydride (4.4 g of 60 percent oil dispersion) was placed in a flask with 140 ml of dimethoxyethane. This mixture was cooled with an ice bath and 22.3 g of triethyl phosphonoacetate was added dropwise with stirring over a 30 min period. A murky yellow solution was obtained. 2,2'-Dimethoxybenzophenone (20.2 g) was added and the resulting mixture was heated at reflux with stirring for 20 hours. It was then allowed to cool to ambient temperature and was diluted with 500 ml of ether. The resulting mixture was washed with 3-200 ml portions of 1 N hydrochloric acid and with saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain a turbid, viscous yellow oil. This material was found by gas chromatagraphy to be about 79 percent one compound. It was dissolved in 100 ml of tetrahydrofuran and the solution added dropwise with stirring to a slurry of 4.70 g of lithium aluminum hydride in 100 ml of tetrahydrofuran over a 40 min period. An exothermic reaction ensued. The mixture was heated at reflux for 3 hours and allowed to stand at ambient temperature overnight. About 100 ml of 10 percent sulfuric acid was added carefully with stirring to quench the excess lithium aluminum hydride. About 700 ml of ether was then added and the layers were separated. The ether layer was extracted with water, 10 percent hydrochloric acid, 10 percent potassium hydroxide, and brine. It was then dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure. The residue was purified by filtration chromatography on silica eluting with a 10:90 mixture of ether and hexane. The solvents were removed by evaporation under reduced pressure to obtain 5.6 g (26 percent of theory) of the title compound as pale yellow crystals melting at 146°-149° C. The carbon-13 and proton nmr spectra were in agreement with the assigned structure. This mixture was cooled with an ice bath A murky yellow solution was obtained the resulting mixture was heated at reflux with stirring for 20 hours The resulting mixture was washed with 3-200 ml portions of 1 N hydrochloric acid and with saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure to obtain a turbid, viscous yellow oil the solution added dropwise An exothermic reaction The mixture was heated at reflux for 3 hours to stand at ambient temperature overnight with stirring to quench the excess lithium aluminum hydride About 700 ml of ether was then added the layers were separated The ether layer was extracted with water, 10 percent hydrochloric acid, 10 percent potassium hydroxide, and brine It was then dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure The residue was purified by filtration chromatography on silica eluting with a 10:90 mixture of ether and hexane The solvents were removed by evaporation under reduced pressure

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

実験手順: 2,2'-Dimethoxybenzophenone (24.2 g, 0.14 mole) and 400 ml of ether were placed in a 1 l flask and stirred at ambient temperature and methyl magnesium bromide (40 ml of 3.0M solution in ether) was added dropwise. The resulting mixture was stirred overnight and then a few ml of water were added to quench the Grignard reagent. About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added and the mixture was shaken. The organic layer was next recovered, extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain 25.6 g (98 percent of theory) of the title compound as a white solid melting at 122°-123° C. The proton NMR spectrum was consistent with the assigned structure. The resulting mixture was stirred overnight to quench the Grignard reagent About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added the mixture was shaken extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure

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

実験手順: 2,2'-Dimethoxybenzophenone (24.2 g, 0.14 mole) and 400 ml of ether were placed in a 1 l flask and stirred at ambient temperature and methyl magnesium bromide (40 ml of 3.0M solution in ether) was added dropwise. The resulting mixture was stirred overnight and then a few ml of water were added to quench the Grignard reagent. About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added and the mixture was shaken. The organic layer was next recovered, extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain 25.6 g (98 percent of theory) of the title compound as a white solid melting at 122°-123° C. The proton NMR spectrum was consistent with the assigned structure. The resulting mixture was stirred overnight to quench the Grignard reagent About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added the mixture was shaken extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure

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

実験手順: Sodium hydride (4.4 g of 60 percent oil dispersion) was placed in a flask with 140 ml of dimethoxyethane. This mixture was cooled with an ice bath and 22.3 g of triethyl phosphonoacetate was added dropwise with stirring over a 30 min period. A murky yellow solution was obtained. 2,2'-Dimethoxybenzophenone (20.2 g) was added and the resulting mixture was heated at reflux with stirring for 20 hours. It was then allowed to cool to ambient temperature and was diluted with 500 ml of ether. The resulting mixture was washed with 3-200 ml portions of 1N hydrochloric acid and with saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain a turbid, viscous yellow oil. This material was found by gas chromatagraphy to be about 79 percent one compound. It was dissolved in 100 ml of tetrahydrofuran and the solution added dropwise with stirring to a slurry of 4.70 g of lithium aluminum hydride in 100 ml of tetrahydrofuran over a 40 min period. An exothermic reaction ensued. The mixture was heated at reflux for 3 hours and allowed to stand at ambient temperature overnight. About 100 ml of 10 percent sulfuric acid was added carefully with stirring to quench the excess lithium aluminum hydride. About 700 ml of ether was then added and the layers were separated. The ether layer was extracted with water, 10 percent hydrochloric acid, 10 percent potassium hydroxide, and brine. It was then dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure. The residue was purified by filtration chromatography on silica eluting with a 10:90 mixture of ether and hexane. The solvents were removed by evaporation under reduced pressure to obtain 5.6 g (26 percent of theory) of the title compound as pale yellow crystals melting at 146°-149° C. The carbon-13 and proton nmr spectra were in agreement with the assigned structure. This mixture was cooled with an ice bath A murky yellow solution was obtained the resulting mixture was heated at reflux with stirring for 20 hours The resulting mixture was washed with 3-200 ml portions of 1N hydrochloric acid and with saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure to obtain a turbid, viscous yellow oil the solution added dropwise An exothermic reaction The mixture was heated at reflux for 3 hours to stand at ambient temperature overnight with stirring to quench the excess lithium aluminum hydride About 700 ml of ether was then added the layers were separated The ether layer was extracted with water, 10 percent hydrochloric acid, 10 percent potassium hydroxide, and brine It was then dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure The residue was purified by filtration chromatography on silica eluting with a 10:90 mixture of ether and hexane The solvents were removed by evaporation under reduced pressure

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

実験手順: This procedure is based on that reported in Tetrahedron Lett., 1966, 4153. To a solution of 2,2′-dimethoxybenzophenone (11) (6.7 g, 0.0277 mol) in anhydrous dichloromethane (95 mL) cooled to −65° C. under nitrogen was added 52 mL of a 1.0 M solution of boron trichloride in heptane (0.052 mol). The mixture was allowed to warm to room temperature and stirred for 75 minutes. The reaction mixture was slowly poured into a cold (0° C.) solution of saturated aqueous sodium bicarbonate, which was then extracted with dichloromethane. The organic extracts were washed with water and saturated with NaCl, followed by drying over anhydrous sodium sulfate. Analytically pure product was obtained after removal of the solvent in quantitative yield. was then extracted with dichloromethane The organic extracts were washed with water and saturated with NaCl by drying over anhydrous sodium sulfate Analytically pure product was obtained after removal of the solvent in quantitative yield

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

実験手順: This procedure is based on that reported in Tetrahedron Lett., 1966, 4153. To a solution of 2,2′-dimethoxybenzophenone (11) (6.7 g, 0.0277 mol) in anhydrous dichloromethane (95 mL) cooled to −65° C. under nitrogen was added 52 mL of a 1.0 M solution of boron trichloride in heptane (0.052 mol). The mixture was allowed to warm to room temperature and stirred for 75 minutes. The reaction mixture was slowly poured into a cold (0° C.) solution of saturated aqueous sodium bicarbonate, which was then extracted with dichloromethane. The organic extracts were washed with water and saturated with NaCl, followed by drying over anhydrous sodium sulfate. Analytically pure product was obtained after removal of the solvent in quantitative yield. was then extracted with dichloromethane The organic extracts were washed with water and saturated with NaCl by drying over anhydrous sodium sulfate Analytically pure product was obtained after removal of the solvent in quantitative yield

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

実験手順: A stirred suspension of 2,2′-dimethoxybenzophenone (20.72 g, 0.0855 mol) and 20 mL (0.412 mol) of hydrazine monohydrate in 25 mL of 1-butanol was heated to reflux overnight. After cooling to room temperature the two phase reaction mixture was poured into water and cooled to induce crystallization. The white precipitate was filtered, washed with water and petroleum ether and dried in vacuo to yield 2,2′-dimethoxybenzophenone hydrazone (1). was heated to reflux overnight the two phase reaction mixture cooled crystallization The white precipitate was filtered washed with water and petroleum ether dried in vacuo

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

実験手順: 2,2'-Dimethoxybenzophenone (24.2 g, 0.14 mole) and 400 ml of ether were placed in a 1 1 flask and stirred at ambient temperature and methyl magnesium bromide (40 ml of 3.0 M solution in ether) was added dropwise. The resulting mixture was stirred overnight and then a few ml of water were added to quench the Grignard reagent. About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added and the mixture was shaken. The organic layer was next recovered, extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain 25.6 g (98 percent of theory) of the title compound as a white solid melting at 122°-123° C. The proton NMR spectrum was consistent with the assigned structure. The resulting mixture was stirred overnight to quench the Grignard reagent About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added the mixture was shaken extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure

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

実験手順: 2,2'-Dimethoxybenzophenone (24.2 g, 0.14 mole) and 400 ml of ether were placed in a 1 1 flask and stirred at ambient temperature and methyl magnesium bromide (40 ml of 3.0 M solution in ether) was added dropwise. The resulting mixture was stirred overnight and then a few ml of water were added to quench the Grignard reagent. About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added and the mixture was shaken. The organic layer was next recovered, extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain 25.6 g (98 percent of theory) of the title compound as a white solid melting at 122°-123° C. The proton NMR spectrum was consistent with the assigned structure. The resulting mixture was stirred overnight to quench the Grignard reagent About 300 ml of ethyl acetate and 250 ml of 10 percent hydrochloric acid were then added the mixture was shaken extracted with 100 ml of water and 100 ml of saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure

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

実験手順: Sodium hydride (4.4 g of 60 percent oil dispersion) was placed in a flask with 140 ml of dimethoxyethane. This mixture was cooled with an ice bath and 22.3 g of triethyl phosphonoacetate was added dropwise with stirring over a 30 min period. A murky yellow solution was obtained. 2,2'-Dimethoxybenzophenone (20.2 g) was added and the resulting mixture was heated at reflux with stirring for 20 hours. It was then allowed to cool to ambient temperature and was diluted with 500 ml of ether. The resulting mixture was washed with 3-200 ml portions of 1 N hydrochloric acid and with saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain a turbid, viscous yellow oil. This material was found by gas chromatagraphy to be about 79 percent one compound. It was dissolved in 100 ml of tetrahydrofuran and the solution added dropwise with stirring to a slurry of 4.70 g of lithium aluminum hydride in 100 ml of tetrahydrofuran over a 40 min period. An exothermic reaction ensued. The mixture was heated at reflux for 3 hours and allowed to stand at ambient temperature overnight. About 100 ml of 10 percent sulfuric acid was added carefully with stirring to quench the excess lithium aluminum hydride. About 700 ml of ether was then added and the layers were separated. The ether layer was extracted with water, 10 percent hydrochloric acid, 10 percent potassium hydroxide, and brine. It was then dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure. The residue was purified by filtration chromatography on silica eluting with a 10:90 mixture of ether and hexane. The solvents were removed by evaporation under reduced pressure to obtain 5.6 g (26 percent of theory) of the title compound as pale yellow crystals melting at 146°-149° C. The carbon-13 and proton nmr spectra were in agreement with the assigned structure. This mixture was cooled with an ice bath A murky yellow solution was obtained the resulting mixture was heated at reflux with stirring for 20 hours The resulting mixture was washed with 3-200 ml portions of 1 N hydrochloric acid and with saturated sodium bicarbonate dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure to obtain a turbid, viscous yellow oil the solution added dropwise An exothermic reaction The mixture was heated at reflux for 3 hours to stand at ambient temperature overnight with stirring to quench the excess lithium aluminum hydride About 700 ml of ether was then added the layers were separated The ether layer was extracted with water, 10 percent hydrochloric acid, 10 percent potassium hydroxide, and brine It was then dried over magnesium sulfate filtered concentrated by evaporation under reduced pressure The residue was purified by filtration chromatography on silica eluting with a 10:90 mixture of ether and hexane The solvents were removed by evaporation under reduced pressure