dimethyl 2-[(4-hydroxyphenyl)methylidene]propanedioate

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: A mixture of 0.1 mole 2-(4-chloromethylphenyl)benzoxazole (C) and 0.1 mole dimethyl 4-hydroxybenzylidenemalonate (D) in 300 ml. 2-butanone containing 100 g. potassium carbonate was refluxed for 18 hours and poured onto 1,000 g. ice/water. Filtration, washing with water and recrystallization from methyl cellosolve/isopropyl alcohol gave a 41% yield of the light tan crystalline product II. ##STR5## poured onto 1,000 g Filtration washing with water and recrystallization from methyl cellosolve/isopropyl alcohol

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(5-Methyl-2-phenyl-4-oxazolyl)ethyl methanesulfonate obtained in Example 4 (compound [7]; 24.4 g) and dimethyl 2-(4-hydroxybenzylidene)malonate obtained in Preparation Example 1 (compound [8]; 20.5 g) were mixed with tetrabutylammonium bromide (1.4 g) and toluene (210 mL). The mixture was heated to 90° C. and dissolved. Then potassium carbonate (13.2 g) was added and the mixture was stirred at 110° C. for 6 hr. The reaction mixed was ice-cooled and water (210 mL) was added, which was followed by stirring. After standing still, the aqueous layer was removed and 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring. The reaction mixture was allowed to stand and the aqueous layer was removed. The organic layer was concentrated and the concentrated residue was dissolved in methanol (150 mL) under heating. The reaction mixture was cooled to 10° C. or less and the reaction mixture was stirred for 1 hr. The obtained crystals were collected by filtration and washed with methanol (65 mL) to give the title compound (compound [9]; 31.1 g, yield 85.0%). dissolved The reaction mixed cooled by stirring the aqueous layer was removed 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring the aqueous layer was removed The organic layer was concentrated the concentrated residue was dissolved in methanol (150 mL) under heating The reaction mixture was cooled to 10° C. or less the reaction mixture was stirred for 1 hr The obtained crystals were collected by filtration washed with methanol (65 mL)

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

実験手順: To a mixture of 4-hydroxybenzaldehyde (280.9 g), dimethyl malonate (289.2 mL) and toluene (1.12 mL) were successively added acetic acid (13.2 mL) and piperidine (11.4 mL). After dehydration under refluxing at internal temperature of 70° C.-75° C. for about 4 hr, the mire was cooled to internal temperature of not more than 10° C. and stirred further for 1 hr. The precipitated crystals were collected by filtration and washed with toluene (350 mL) to give the title compound (compound [8]; 523.7 g, yield 96.4%). After dehydration under refluxing at internal temperature of 70° C.-75° C. for about 4 hr the mire was cooled to internal temperature of not more than 10° C. The precipitated crystals were collected by filtration washed with toluene (350 mL)

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(5-Methyl-2-phenyl-4-oxazolyl)ethyl methanesulfonate obtained in Example 4 (compound [7]; 24.4 g) and dimethyl 2-(4-hydroxybenzylidene)malonate obtained in Preparation Example 1 (compound [8]; 20.5 g) were mixed with tetrabutylammonium bromide (1.4 g) and toluene (210 mL). The mixture was heated to 90° C. and dissolved. Then potassium carbonate (13.2 g) was added and the mixture was stirred at 110° C. for 6 hr. The reaction mixture was ice-cooled and water (210 mL) was added, which was followed by stirring. After standing still, the aqueous layer was removed and 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring. The reaction mixture was allowed to stand and the aqueous layer was removed. The organic layer was concentrated and the concentrated residue was dissolved in methanol (150 mL) under heating. The reaction mixture was cooled to 10° C. or less and the reaction mixture was stirred for 1 hr. The obtained crystals were collected by filtration and washed with methanol (65 mL) to give the title compound (compound [9]; 31.1 g, yield 85.0%). dissolved cooled by stirring the aqueous layer was removed 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring the aqueous layer was removed The organic layer was concentrated the concentrated residue was dissolved in methanol (150 mL) under heating The reaction mixture was cooled to 10° C. or less the reaction mixture was stirred for 1 hr The obtained crystals were collected by filtration washed with methanol (65 mL)

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

実験手順: To a mixture of 4-hydroxybenzaldehyde (280.9 g), dimethyl malonate (289.2 mL) and toluene (1.12 mL) were successively added acetic acid (13.2 mL) and piperidine (11.4 mL). After dehydration under refluxing at internal temperature of 70° C.–75° C. for about 4 hr, the mixture was cooled to internal temperature of not more than 10° C. and stirred further for 1 hr. The precipitated crystals were collected by filtration and washed with toluene (350 mL) to give the title compound (compound [8]; 523.7 g, yield 96.4%). After dehydration under refluxing at internal temperature of 70° C.–75° C. for about 4 hr the mixture was cooled to internal temperature of not more than 10° C. The precipitated crystals were collected by filtration washed with toluene (350 mL)

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

実験手順: A mixture of 0.1 mole 2-(4-chloromethylphenyl)benzoxazole (C) and 0.1 mole dimethyl 4-hydroxybenzylidenemalonate (D) in 300 ml. 2-butanone containing 100 g. potassium carbonate was refluxed for 18 hours and poured onto 1,000 g. ice/water. Filtration, washing with water and recrystallization from methyl cellosolve/isopropyl alcohol gave a 41% yield of the light tan crystalline product II. ##STR5## poured onto 1,000 g Filtration washing with water and recrystallization from methyl cellosolve/isopropyl alcohol

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

実験手順: A mixture of 0.1 mole 2-(4-chloromethylphenyl)benzoxazole (C) and 0.1 mole dimethyl 4-hydroxybenzylidenemalonate (D) in 300 ml. 2-butanone containing 100 g. potassium carbonate was refluxed for 18 hours and poured onto 1,000 g. ice/water. Filtration, washing with water and recrystallization from methyl cellosolve/isopropyl alcohol gave a 41% yield of the light tan crystalline product II. ##STR5## poured onto 1,000 g Filtration washing with water and recrystallization from methyl cellosolve/isopropyl alcohol

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

実験手順: A mixture of 0.1 mole 2-(4-chloromethylphenyl)benzoxazole (C) and 0.1 mole dimethyl 4-hydroxybenzylidenemalonate (D) in 300 ml. 2-butanone containing 100 g. potassium carbonate was refluxed for 18 hours and poured onto 1,000 g. ice/water. Filtration, washing with water and recrystallization from methyl cellosolve/isopropyl alcohol gave a 41% yield of the light tan crystalline product II. ##STR5## poured onto 1,000 g Filtration washing with water and recrystallization from methyl cellosolve/isopropyl alcohol

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(5-Methyl-2-phenyl-4-oxazolyl)ethyl methanesulfonate obtained in Example 4 (compound [7]; 24.4 g) and dimethyl 2-(4-hydroxybenzylidene)-malonate obtained in Preparation Example 1 (compound [8]; 20.5 g) were mixed with tetrabutylammonium bromide (1.4 g) and toluene (210 mL). The mixture was heated to 90° C. and dissolved. Then potassium carbonate (13.2 g) was added and the mixture was stirred at 110° C. for 6 hr. The reaction mixture was ice-cooled and water (210 mL) was added, which was followed by stirring. After standing still, the aqueous layer was removed and 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring. The reaction mixture was allowed to stand and the aqueous layer was removed. The organic layer was concentrated and the concentrated residue was dissolved in methanol (150 mL) under heating. The reaction mixture was cooled to 10° C. or less and the reaction mixture was stirred for 1 hr. The obtained crystals were collected by filtration and washed with methanol (65 mL) to give the title compound (compound [9]; 31.1 g, yield 85.0%). dissolved cooled by stirring the aqueous layer was removed 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring the aqueous layer was removed The organic layer was concentrated the concentrated residue was dissolved in methanol (150 mL) under heating The reaction mixture was cooled to 10° C. or less the reaction mixture was stirred for 1 hr The obtained crystals were collected by filtration washed with methanol (65 mL)

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(5-Methyl-2-phenyl-4-oxazolyl)ethyl methanesulfonate obtained in Example 4 (compound [7]; 24.4 g) and dimethyl 2-(4-hydroxybenzylidene)-malonate obtained in Preparation Example 1 (compound [8]; 20.5 g) were mixed with tetrabutylammonium bromide (1.4 g) and toluene (210 mL). The mixture was heated to 90° C. and dissolved. Then potassium carbonate (13.2 g) was added and the mixture was stirred at 110° C. for 6 hr. The reaction mixture was ice-cooled and water (210 mL) was added, which was followed by stirring. After standing still, the aqueous layer was removed and 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring. The reaction mixture was allowed to stand and the aqueous layer was removed. The organic layer was concentrated and the concentrated residue was dissolved in methanol (150 mL) under heating. The reaction mixture was cooled to 10° C. or less and the reaction mixture was stirred for 1 hr. The obtained crystals were collected by filtration and washed with methanol (65 mL) to give the title compound (compound [9]; 31.1 g, yield 85.0%). dissolved cooled by stirring the aqueous layer was removed 10% aqueous sodium chloride solution (210 mL) was added to the organic layer with stirring the aqueous layer was removed The organic layer was concentrated the concentrated residue was dissolved in methanol (150 mL) under heating The reaction mixture was cooled to 10° C. or less the reaction mixture was stirred for 1 hr The obtained crystals were collected by filtration washed with methanol (65 mL)

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

実験手順: K2CO3 was added to a solution of 4-hydroxybenzylidene-malonic acid dimethyl ester (6.95 mmol) and 4-methyoxybenzyl chloride (7.64 mmol) in DMF (15 ml). It was stirred at room temperature overnight. The reaction was poured into water, and the product was extracted with ethyl acetate twice. The organic layer was washed with water and saturated brine, dried over Na2SO4, and concentrated in vacuo. The resulting residue was purified using silica gel column chromatography (hexane/ethyl acetate=2/1) to give compound 33.1 as a white solid (3.2 mmol). the product was extracted with ethyl acetate twice The organic layer was washed with water and saturated brine dried over Na2SO4 concentrated in vacuo The resulting residue was purified