ethyl 2-amino-2-cyanoacetate

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:

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 solution of ethyl 2-amino-2-cyanoacetate (0.20 g, 1.56 mmol) and triethyl formate (0.30 mL, 1.72 mmol) in acetonitrile (5 mL) was refluxed for 1 h. After concentrating the residue was dissolved in a solution of acetonitrile (5 mL) and n-butylamine (0.17 mL, 1.72 mmol). The resulting mixture was stirred at reflux for 1 h. The solvents were removed under reduced pressure and the residue was partitioned between water and ethyl acetate. The organic layer was separated and washed with brine and dried (Na2SO4). After removing the solvent under reduced pressure, flash chromatography (1:1 ethyl acetate/hexane) of the residue gave 0.12 g, 40% of the title compound as an oil: 1H NMR (250 MHz, CDCl3)δ 6.97 (s, 1H), 5.10 (s, 2H), 4.31 (q, 2H), 3.75 (t, 2H), 1.65 (m, 2H), 1.35 (m, 5H), 0.97 (t, 3H); MS(ESI) m/e 212.2 [M+H]+. After concentrating the residue at reflux for 1 h The solvents were removed under reduced pressure the residue was partitioned between water and ethyl acetate The organic layer was separated washed with brine dried (Na2SO4) After removing the solvent under reduced pressure, flash chromatography (1:1 ethyl acetate/hexane) of the residue

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

実験手順: To aluminum foil (25 g) was added a solution of mercury(II) chloride (10 g, 0.37 mol) in water (1 L). The mixture was swirled for 5 min, and then the turbid solution was decanted off. The resulting aluminum amalgam was washed successively with water, methanol and diethyl ether. To amalgam suspended in diethyl ether (500 mL) at 0° C., was added a solution of ethyl 2-hydroxyimino-2-cyanoacetate (100 g, 0.70 mol) in diethyl ether (300 mL), followed by water (50 mnL), maintaining a gentle reflux. After 1 h of stirring, the mixture was filtered and the filtrate was washed with water, brine and dried (Na2SO4). Removal of the solvent gave the title compound as a white solid (67 g, 74%). 1H NMR (250 MHz, CD3OD)δ 4.45 (m, 2H), 2.49 (s, 1H), 1.38 (m, 3H). the turbid solution was decanted off The resulting aluminum amalgam was washed successively with water, methanol and diethyl ether suspended in diethyl ether (500 mL) at 0° C. maintaining a gentle reflux the mixture was filtered the filtrate was washed with water, brine dried (Na2SO4) Removal of the solvent

反応条件: temp:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 119 g of sodium dithionite are added in portions (15 min) at room temperature to 35 g (0.246 mol) of ethyl 2-cyanoglyoxylate-2-oxime in 350 ml of H2O and 280 ml of saturated sodium hydrogen carbonate solution. The mixture is then warmed at 35° C. for 1 hour; it is then saturated with NaCl and extracted 5 times with dichloromethane. After drying with calcium chloride, the organic phase is concentrated. 11.8 g of the title compound are obtained as an oil. saturated with NaCl and extracted 5 times with dichloromethane After drying with calcium chloride the organic phase is concentrated

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:

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

実験手順: To a stirred mixture of 2-amino-2-cyanoacetic acid ethyl ester (19.7 g) and pyridine (12.2 g) in water (123 ml) was added portionwise benzyloxycarbonyl chloride (27.9 g) under ice cooling. The resulting mixture was stirred under ice cooling for 1 hour. Precipitated crystals were collected, washed thoroughly with water, and recrystallized from ethanol to give the title compound (24.2 g, 60.2%) as colorless crystals, mp 111°-112° C. Precipitated crystals were collected washed thoroughly with water recrystallized from ethanol

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

実験手順: To a stirred mixture of 2-amino-2-cyanoacetic acid ethyl ester (19.7 g) and pyridine (12.2 g) in water (123 ml) was added portionwise benzyloxycarbonyl chloride (27.9 g) under ice cooling. The resulting mixture was stirred under ice cooling for 1 hour. Precipitated crystals were collected, washed thoroughly with water, and recrystallized from ethanol to give the title compound (24.2 g, 60.2%) as colorless crystals, mp 111°-112° C. Precipitated crystals were collected washed thoroughly with water recrystallized from ethanol