1-dimethoxyphosphoryloctan-2-one

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: To a benzene suspension of 194 mg of 80% NaH in mineral oil, a solution of 1.62 g of dimethyl-(2-oxo-octyl)phosphonate in 5 ml of benzene was added dropwise and continually stirred until there was no more evolution of hydrogen. The 1.24 g of N-bromo-caprolactam were added to form the carbanion of dimethyl-(1-bromo-2-oxo-octyl)-phosphonate. After 15 minutes the solution of the aldehyde, prepared as described above, was added and the reaction mixture stirred for 15 minutes.

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

実験手順: n-Butyllithiium (130 ml. of 1.6 M. solution) is slowly added to a solution of dimethyl methylphosphonate (25.6 g.) in 475 ml. of tetrahydrofuran (THF) at about -65° C. To the mixture is added a solution of ethyl heptanoate (18.4 g.) in 50 ml. of THF, annd the resulting mixture is stirred at about -70° C. for 2 hrs. Then, 16 ml. of acetic acid is added, and the mixture is concentrated under reduced pressure. The residue is mixed with dichloromethane (about 400 ml.) and water (about 50 ml.) shaken, and separated. The organic phase is dried over magnesium sulfate and concentrated. Distillation yields the title compound. at about -65° C the mixture is concentrated under reduced pressure The residue is mixed with dichloromethane (about 400 ml.) and water (about 50 ml.) separated The organic phase is dried over magnesium sulfate concentrated Distillation

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

実験手順: n-Butyllithiium (130 ml. of 1.6 M. solution) is slowly added to a solution of dimethyl methylphosphonate (25.6 g.) in 475 ml. of tetrahydrofuran (THF) at about -65° C. To the mixture is added a solution of ethyl heptanoate (18.4 g.) in 50 ml. of THF, annd the resulting mixture is stirred at about -70° C. for 2 hrs. Then, 16 ml. of acetic acid is added, and the mixture is concentrated under reduced pressure. The residue is mixed with dichloromethane (about 400 ml.) and water (about 50 ml.) shaken, and separated. The organic phase is dried over magnesium sulfate and concentrated. Distillation yields the title compound. at about -65° C the mixture is concentrated under reduced pressure The residue is mixed with dichloromethane (about 400 ml.) and water (about 50 ml.) separated The organic phase is dried over magnesium sulfate concentrated Distillation

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: By following the procedure as in Reference Example 1(a) using 1.2 g of 4-benzyloxy-3-methoxybenzaldehyde and 1.53 g of dimethyl 2-oxooctylphosphonate, 1.27 g of 1-(4-benzyloxy-3-methoxyphenyl)-1-nonen-3-one was obtained. Melting point 78°-81° C.

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

実験手順: To a mixture of 400 mg of oily sodium hydride (60%) and 50 ml of 1,2-dimethoxyethane was added dropwise a mixture of 3.06 g of dimethyl 2-oxooctylphosphonate and 10 ml of dimethoxyethane with stirring under ice-cooling. After adding thereto 5 ml of dimethyl sulfoxide and stirring the mixture for one hour at room temperature, a mixture of 2.22 g of 3,4-diacetoxybenzaldehyde and 10 ml of dimethoxyethane was added dropwise to the mixture. After stirring the resultant mixture for 4 hours at room temperature, 400 ml of water was added to the reaction mixture and the product was extracted twice each time with 50 ml of ether. The extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was applied to silica gel (120 g) column chromatography and eluted with a mixture of toluene and ethyl acetate (20:1) to provide 2.67 g of 1-(3,4-diacetoxyphenyl)-1-nonen-3-one. was added dropwise cooling After adding was added dropwise to the mixture the product was extracted twice each time with 50 ml of ether The extract was washed with water dried over anhydrous magnesium sulfate concentrated under reduced pressure eluted with a mixture of toluene and ethyl acetate (20:1)

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

実験手順: To a benzene suspension of 194 mg of 80% NaH in mineral oil, a solution of 1.62 g of dimethyl-(2-oxo-octyl)phosphonate in 5 ml of benzene was added dropwise and continually stirred until there was no more evolution of hydrogen. The 1.24 g of N-bromo-caprolactam were added to form the carbanion of dimethyl-(1-bromo-2-oxo-octyl)-phosphonate. After 15 minutes the solution of the aldehyde, prepared as described above, was added and the reaction mixture stirred for 15 minutes.

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

実験手順: n-Butyllithiium (130 ml. of 1.6 M. solution) is slowly added to a solution of dimethyl methylphosphonate (25.6 g.) in 475 ml. of tetrahydrofuran (THF) at about -65° C. To the mixture is added a solution of ethyl heptanoate (18.4 g.) in 50 ml. of THF, annd the resulting mixture is stirred at about -70° C. for 2 hrs. Then, 16 ml. of acetic acid is added, and the mixture is concentrated under reduced pressure. The residue is mixed with dichloromethane (about 400 ml.) and water (about 50 ml.) shaken, and separated. The organic phase is dried over magnesium sulfate and concentrated. Distillation yields the title compound. at about -65° C the mixture is concentrated under reduced pressure The residue is mixed with dichloromethane (about 400 ml.) and water (about 50 ml.) separated The organic phase is dried over magnesium sulfate concentrated Distillation