methyl (E)-4,4,4-trifluorobut-2-enoate

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

実験手順: In a round-bottomed flask was added sodium hydride (3.24 mmol, 78 mg) in Et2O (5 mL). A mixture of p-toluenesulfonylmethyl isocyanide (3.24 mmol, 634 mg) and (E)-methyl 4,4,4-trifluorobut-2-enoate (3.24 mmol, 500 mg) were added in a 2:1 mixture of Et2O/DMSO (22.5 mL). The reaction mixture was stirred for a further 30 min then quenched with H2O (10 mL) and extracted with Et2O (×3). The Et2O layers were combined and washed with brine, dried over MgSO4, filtered and the solvent removed to give a yellow/orange solid. Purification by flash chromatography (1:4 EtOAc:Hept) the desired product (154 mg, 0.80 mmol, 24.6%). 1H NMR (400 MHz, CD3OD) δ 3.79 (s, 3H) 7.20 (s, 1H) 7.50 (s, 1H). then quenched with H2O (10 mL) extracted with Et2O (×3) washed with brine dried over MgSO4 filtered the solvent removed to give a yellow/orange solid

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

実験手順: In a round-bottomed flask was added sodium hydride (3.24 mmol, 78 mg) in Et2O (5 mL). A mixture of p-toluenesulfonylmethyl isocyanide (3.24 mmol, 634 mg) and (E)-methyl 4,4,4-trifluorobut-2-enoate (3.24 mmol, 500 mg) were added in a 2:1 mixture of Et2O/DMSO (22.5 mL). The reaction mixture was stirred for a further 30 min then quenched with H2O (10 mL) and extracted with Et2O (×3). The Et2O layers were combined and washed with brine, dried over MgSO4, filtered and the solvent removed to give a yellow/orange solid. Purification by flash chromatography (1:4 EtOAc:Hept) the desired product (154 mg, 0.80 mmol, 24.6%). 1H NMR (400 MHz, CD3OD) δ 3.79 (s, 3H) 7.20 (s, 1H) 7.50 (s, 1H). then quenched with H2O (10 mL) extracted with Et2O (×3) washed with brine dried over MgSO4 filtered the solvent removed to give a yellow/orange solid

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

実験手順: In a round-bottomed flask was added sodium hydride (3.24 mmol, 78 mg) in Et2O (5 mL). A mixture of p-toluenesulfonylmethyl isocyanide (3.24 mmol, 634 mg) and (E)-methyl 4,4,4-trifluorobut-2-enoate (3.24 mmol, 500 mg) were added in a 2:1 mixture of Et2O/DMSO (22.5 mL). The reaction mixture was stirred for a further 30 min then quenched with H2O (10 mL) and extracted with Et2O (×3). The Et2O layers were combined and washed with brine, dried over MgSO4, filtered and the solvent removed to give a yellow/orange solid. Purification by flash chromatography (1:4 EtOAc:Hept) the desired product (154 mg, 0.80 mmol, 24.6%). 1H NMR (400 MHz, CD3OD) δ 3.79 (s, 3H) 7.20 (s, 1H) 7.50 (s, 1H). then quenched with H2O (10 mL) extracted with Et2O (×3) washed with brine dried over MgSO4 filtered the solvent removed to give a yellow/orange solid

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

実験手順: 7.47 g (138.39 mmol) of sodium methoxide in methanol (85 ml) were initially charged with ice cooling, and 6.04 g (91.44 mmol) of malononitrile were added in portions. Subsequently, 11.84 g (76.84 mmol) of methyl 4,4,4-trifluorocrotonate were added dropwise while stirring, and the mixture was stirred at room temperature for 30 min and then heated to reflux for 1 h. Thereafter, the mixture was concentrated to dryness under reduced pressure. The residue was admixed with water and extracted four times with ethyl acetate. The combined organic phases were dried over sodium sulfate, filtered and concentrated. Further purification was effected by chromatography on silica gel (3:1 cyclohexane-ethyl acetate). This gave 1.95 g of the target compound (11% of theory). were added in portions the mixture was stirred at room temperature for 30 min heated to reflux for 1 h Thereafter, the mixture was concentrated to dryness under reduced pressure extracted four times with ethyl acetate The combined organic phases were dried over sodium sulfate filtered concentrated Further purification

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

実験手順: With ice cooling, 7.47 g (138.39 mmol) of sodium methoxide in methanol (85 ml) were initially charged, and 6.04 g (91.44 mmol) of malononitrile were added. With stirring, 11.84 g (76.84 mmol) of methyl 4,4,4-trifluorocrotonate were then added dropwise, and the mixture was stirred at RT for 30 min and then heated at reflux for 1 h. Under reduced pressure, the mixture was then concentrated to dryness. Water was added to the residue, and the mixture was extracted four times with ethyl acetate. The combined organic phases were dried with sodium sulphate, filtered and concentrated. Further purification was carried out by chromatography on silica gel (cyclohexane/ethyl acetate 3:1). This gave 1.95 g of the title compound (11% of theory). the mixture was stirred at RT for 30 min heated at reflux for 1 h Under reduced pressure, the mixture was then concentrated to dryness Water was added to the residue the mixture was extracted four times with ethyl acetate The combined organic phases were dried with sodium sulphate filtered concentrated Further purification