2,2,2-trifluoroacetonitrile

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: To a 1 liter, four-necked flask equipped with nitrogen inlet, thermometer, and mechanical stirrer was charged 499.74 g (490 ml, 3.84 mol) of methyl acetoacetate and 12.9 g (0.115 mol) of potassium t-butoxide. The resulting mixture was stirred while 391 g (4.04 mol) of trifluoroacetonitrile was added. The reaction mixture was washed with hexane and the resulting solid was dried in vacuo affording 535 g (62%) of the enamine as a yellow solid; mp 63°-65° C. To a 1 liter, four-necked flask equipped with nitrogen inlet was added The reaction mixture was washed with hexane the resulting solid was dried in vacuo

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 1 liter, four-necked flask equipped with nitrogen inlet, thermometer, and mechanical stirrer was charged 499.74 g (490 ml, 3.84 mol) of ethyl acetoacetate and 12.9 g (0.115 mol) of potassium-t-butoxide. The resulting mixture was stirred while 391 g (4.04 mol) of trifluoroaceto-nitrile was added. The reaction mixture was washed with hexane and the resulting solid was dried in vacuo affording 535 g (62%) of the enamine as a yellow solid; mp 63°-65° C. To a 1 liter, four-necked flask equipped with nitrogen inlet was added The reaction mixture was washed with hexane the resulting solid was dried in vacuo

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

実験手順: To a 1 liter, four-necked flask equipped with nitrogen inlet, thermometer, and mechanical stirrer was charged 499.74 g (490 ml, 3.84 mol) of ethyl acetoacetate and 12.9 g (0.115 mol) of potassium-t-butoxide. The resulting mixture was stirred while 391 g (4.04 mol) of trifluoroaceto-nitrile was added. The reaction mixture was washed with hexane and the resulting solid was dried in vacuo affording 535 g (62%) of the enamine as a yellow solid; mp 63°-65° C. To a 1 liter, four-necked flask equipped with nitrogen inlet was added The reaction mixture was washed with hexane the resulting solid was dried in vacuo

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dimethyl 1,3-acetonedicarboxylate (34.8 g, 0.2 mol) is slowly added to a solution of potassium t-butoxide (22.4 g, 0.2 mol) in THF (300 mL) at 60° C. After addition, the reaction mixture is stirred at 60° C. for 2 hours. The reaction is allowed to cool to 40° C. and trifluoroacetonitrile gas (100 g, 1.05 mol) is slowly bubbled slowly into the above mixture. The reaction temperature is maintained at 50° C. overnight. The volatile material is removed in vacuo. The residue is dissolved in water (200 mL) and the solution is poured into hydrogen chloride solution (conc. HCl/water 80 mL: 200 mL). The white solid is collected by filtration and dried. After being triturated with chloroform (200 mL), the title product is obtained as a white solid. 1H NMR: (CDCl3) 6.29 (s, 1H), 3.76 (s, 3H). After addition to cool to 40° C. The reaction temperature is maintained at 50° C. overnight The volatile material is removed in vacuo The residue is dissolved in water (200 mL) the solution is poured into hydrogen chloride solution (conc. HCl/water 80 mL: 200 mL) The white solid is collected by filtration dried After being triturated with chloroform (200 mL)

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dimethyl 1,3-acetonedicarboxylate (34.8 g, 0.2 mol) is slowly added to a solution of potassium t-butoxide (22.4 g, 0.2 mol) in THF (300 mL) at 60° C. After addition, the reaction mixture is stirred at 60° C. for 2 hours. The reaction is allowed to cool to 40° C. and trifluoroacetonitrile gas (100 g, 1.05 mol) is slowly bubbled slowly into the above mixture. The reaction temperature is maintained at 50° C. overnight. The volatile material is removed in vacuo. The residue is dissolved in water (200 mL) and the solution is poured into hydrogen chloride solution (conc. HCl/water 80 mL: 200 mL). The white solid is collected by filtration and dried. After being triturated with chloroform (200 mL), the title product is obtained as a white solid. 1H NMR: (CDCl3) 6.29 (s, 1H), 3.76 (s, 3H). After addition to cool to 40° C. The reaction temperature is maintained at 50° C. overnight The volatile material is removed in vacuo The residue is dissolved in water (200 mL) the solution is poured into hydrogen chloride solution (conc. HCl/water 80 mL: 200 mL) The white solid is collected by filtration dried After being triturated with chloroform (200 mL)

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

実験手順: To a mechanically stirred mixture of 100 g (0.632 mol) of ethyl butyrylacetate, 52 g of sodium acetate, 100 ml of ethanol and 100 ml of water at 70° C. was passed 63 g of trifluoroacetonitrile in 1 day. The reaction mixture was poured into ice water. The oil precipitate was extracted into ether. The ether solution was dried and concentrated. The residue was kugelrohr distilled at 133 Pa (pot temperature 70°-110° C.). The distillate was further distilled through a Vigreaux column at 106 Pa to give 90.9 g (36.3%) of product, bp 90°-97° C., nD25 1.4585. in 1 day The oil precipitate was extracted into ether The ether solution was dried concentrated The residue was kugelrohr distilled at 133 Pa (pot temperature 70°-110° C.) The distillate was further distilled through a Vigreaux column at 106 Pa

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

実験手順: To a mechanically stirred mixture of 100 g (0.632 mol) of ethyl butyrylacetate, 52 g of sodium acetate, 100 ml of ethanol and 100 ml of water at 70° C. was passed 63 g of trifluoroacetonitrile in 1 day. The reaction mixture was poured into ice water. The oil precipitate was extracted into ether. The ether solution was dried and concentrated. The residue was kugelrohr distilled at 133 Pa (pot temperature 70°-110° C.). The distillate was further distilled through a Vigreaux column at 106 Pa to give 90.9 g (36.3%) of product, bp 90°-97° C., nD25 1.4585. in 1 day The oil precipitate was extracted into ether The ether solution was dried concentrated The residue was kugelrohr distilled at 133 Pa (pot temperature 70°-110° C.) The distillate was further distilled through a Vigreaux column at 106 Pa