diethyl 2-formylbutanedioate

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: 10.8 g. (0.1 mole) of 3-methyl-2-amino-pyridine are admixed with 20.2 g. (0.1 mole) of 2-formyl-succinic acid diethyl ester. The reaction mixture warms up to 40°-50° C. The mixture is stirred for an hour, whereupon it is allowed to stand at room temperature overnight. The α-(ethoxycarbonyl-methyl)-β-(3-methyl-2-pyridyl-amino)-acrylic acid ethyl ester thus obtained is recrystallized from 50% aqueous ethanol. Yield: 65-70%, m.p.: 62° C. warms up to 40°-50° C

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

実験手順: Ethanol (20 cm3) was added portionwise to a suspension of finely divided sodium (10.0 g) in dry toluene (100 cm3). On completion of the addition the mixture was heated for 3.5 hours at 80° C. To the resulting yellow suspension, cooled to 20° C., was added dropwise, over a period of 1 hour, a mixture of diethyl succinate (70.0 g) and ethyl formate (35.0 g), whilst the temperature of the mixture was maintained in the range 20° to 30° C. The mixture was kept at the ambient temperature for 16 hours after which water (100 cm3) was added carefully. On completion of the addition the mixture To the resulting yellow suspension, cooled to 20° C. was added dropwise, over a period of 1 hour whilst the temperature of the mixture was maintained in the range 20° to 30° C

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

実験手順: Ethanol (20 cm3) was added portionwise to a suspension of finely divided sodium (10.0 g) in dry toluene (100 cm3). On completion of the addition the mixture was heated for 3.5 hours at 80° C. To the resulting yellow suspension, cooled to 20° C., was added dropwise, over a period of 1 hour, a mixture of diethyl succinate (70.0 g) and ethyl formate (35.0 g), whilst the temperature of the mixture was maintained in the range 20° to 30° C. The mixture was kept at the ambient temperature for 16 hours after which water (100 cm3) was added carefully. On completion of the addition the mixture To the resulting yellow suspension, cooled to 20° C. was added dropwise, over a period of 1 hour whilst the temperature of the mixture was maintained in the range 20° to 30° C

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

実験手順: Sodium metal (0.754 mol) was dissolved in absolute ethanol (100 ml) and the resulting solution was added dropwise to a solution of methoxyacetamidine hydrochloride (0.703 mol) in ethanol (100 ml). After 15 minutes the reaction mixture was filtered and the filtrate was added to a solution of diethyl formylsuccinate (0.703 mol), which was prepared according to H. Nakao et al. Ann. Sankyo Res. Lab., 18, 33-37 (1966). The reaction was refluxed for 15 hours, cooled to room temperature and was then concentrated to obtain a crude solid. This solid was crystallized from isopropanol to obtain the title compound (43% yield), m.p. 142°-143° C. After 15 minutes the reaction mixture was filtered was prepared The reaction was refluxed for 15 hours was then concentrated to obtain a crude solid This solid was crystallized from isopropanol

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

実験手順: 10.8 g. (0.1 mole) of 3-methyl-2-amino-pyridine are admixed with 20.2 g. (0.1 mole) of 2-formyl-succinic acid diethyl ester. The reaction mixture warms up to 40°-50° C. The mixture is stirred for an hour, whereupon it is allowed to stand at room temperature overnight. The α-(ethoxycarbonyl-methyl)-β-(3-methyl-2-pyridyl-amino)-acrylic acid ethyl ester thus obtained is recrystallized from 50% aqueous ethanol. Yield: 65-70%, m.p.: 62° C. warms up to 40°-50° C

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of sodium (333 mg, 14 mmol, 1.2 eq) in diethyl ether (7 mL) were added succinic acid diethyl ester (2.1 g, 12 mmol, 1 eq) and formic acid ethyl ester (1.7 mL, 20 mmol, 1.7 eq). The mixture was stirred at 40° C. for 5 h. Water (10 mL) was added and the aqueous layer was washed with diethyl ether (2×10 mL). The aqueous layer was then acidified with a 6N solution of hydrochloric acid and extracted with diethyl ether (3×10 mL). The organic layers were dried over magnesium sulfate, filtered and evaporated in vacuo to afford the expected compound as orange oil (2.6 g, quant. yield). the aqueous layer was washed with diethyl ether (2×10 mL) extracted with diethyl ether (3×10 mL) The organic layers were dried over magnesium sulfate filtered evaporated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suspension of sodium (333 mg, 14 mmol, 1.2 eq) in diethyl ether (7 mL) were added succinic acid diethyl ester (2.1 g, 12 mmol, 1 eq) and formic acid ethyl ester (1.7 mL, 20 mmol, 1.7 eq). The mixture was stirred at 40° C. for 5 h. Water (10 mL) was added and the aqueous layer was washed with diethyl ether (2×10 mL). The aqueous layer was then acidified with a 6N solution of hydrochloric acid and extracted with diethyl ether (3×10 mL). The organic layers were dried over magnesium sulfate, filtered and evaporated in vacuo to afford the expected compound as orange oil (2.6 g, quant. yield). the aqueous layer was washed with diethyl ether (2×10 mL) extracted with diethyl ether (3×10 mL) The organic layers were dried over magnesium sulfate filtered evaporated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a mixture of 2-(4-nitrophenyl)ethanimidamide hydrochloride (6.06 g, 28.12 mmol) and diethyl 2-formylsuccinate (6.54 g, 32.34 mmol) in methanol (100 mL) was added sodium methoxide (28% in methanol, 11.2 mL, 56.25 mmol) at room temperature, and the reaction mixture was stirred at 90° C. overnight. After the cooling to room temperature, the reaction was quenched with acetic acid (3.38 mL, 59.06 mmol) and water (100 mL) was added to. The resulting precipitates were collected by filtration and washed with water and acetone/diisopropyl ether (3/2) to give methyl [4-hydroxy-2-(4-nitrobenzyl)pyrimidin-5-yl]acetate (5.41 g, 64%) as brown solid. was added to The resulting precipitates were collected by filtration washed with water and acetone/diisopropyl ether (3/2)