2-(1-ethoxypropylidene)propanedinitrile

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: 5.21 g (34.66 mmol) of 2-(1-ethoxy-propylidene)-malononitrile and 5.00 g (34.66 mmol) of (1-methyl-heptyl)-hydrazine are refluxed for 4 hours in 40 ml of methanol. After the solvent has been removed in vacuo, 8.60 g of a red oil are obtained. The latter is dissolved in 250 ml of ethanol and, after 300 ml of concentrated NH3 solution (25% strength) and 70 ml of hydrogen peroxide solution (30%) have been added, the mixture is stirred for 48 hours at room temperature. After the non-aqueous solvents have been removed, the mixture is extracted three times with dichloromethane, and the organic phase is dried over sodium sulphate and evaporated on a rotary evaporator. This gives 7.45 g (71%) of a red solid. After the solvent has been removed in vacuo, 8.60 g of a red oil are obtained After the non-aqueous solvents have been removed the mixture is extracted three times with dichloromethane the organic phase is dried over sodium sulphate evaporated on a rotary evaporator

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

実験手順: 16.41 g (249 mmol) of malononitrile and 43.8 g (249 mmol) of triethyl orthopropionate are refluxed for 4.5 hours. The reaction mixture is cooled to room temperature and distilled in vacuo. distilled in vacuo

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

実験手順: Cyclopentylhydrazine hydrochloride (20.9 g, 0.1 moles), 97% sodium methoxide (5.6 g, 0.1 moles) and ethanol (100 ml) were combined and stirred at room temperature under argon for 2.5 hours. (1-Ethoxypropylidene)malononitrile was added to the reaction mixture and the mixture was refluxed for 21 hours. The reaction mixture was cooled and the solvent was removed in vacuo. The residue was treated with water (150 ml) and the obtained precipitate was collected by filtration, washed with water and dried in a vacuum oven for 24 hours to afford 14.2 g (70%) of 1-cyclopentyl-3-ethyl-5-amino-1H-pyrazole-4-carbonitrile as a brown powder, m.p. 171°-173° C. the mixture was refluxed for 21 hours The reaction mixture was cooled the solvent was removed in vacuo The residue was treated with water (150 ml) the obtained precipitate was collected by filtration washed with water dried in a vacuum oven for 24 hours

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

実験手順: Triethyl orthopropionate (1000 g, 5.5 mole) and malononitrile (363 g, 5.5 mole) were combined and refluxed for 5 hours. The reaction mixture was cooled to room temperature and the residue was distilled at 125°-143° C. (3-7 mm Hg) to afford 768.1 g (93%) of (1-ethoxypropylidene)malononitrile as an orange liquid. refluxed for 5 hours the residue was distilled at 125°-143° C. (3-7 mm Hg)

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

実験手順: Triethyl orthopropionate (1000 g, 5.5 mole) and malononitrile (363 g, 5.5 mole) were combined and refluxed for 5 hours. The reaction mixture was cooled to room temperature and the residue was distilled at 125°-143° C. (3-7 mm Hg) to afford 768.1 g (93%) of (1-ethoxypropylidene)malononitrile as an orange liquid. refluxed for 5 hours the residue was distilled at 125°-143° C. (3-7 mm Hg)

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: 33.03 g (0.5 mol) of malonodinitrile and 88.13 g (99.02 ml, 0.5 mol) of triethyl orthopropionate are heated at 100° C. for two hours, and the ethanol which is formed during this is distilled off overhead. The reaction mixture is left to cool and added to ca. 500 ml of water. The aqueous phase is extracted with ethyl acetate, then the organic phase is dried with sodium sulfate and, after filtering off the drying agent, is concentrated by evaporation. The resulting 72 g (purity ca. 90%) of (1-ethoxy-propylidene)malononitrile are used in the subsequent step without further purification. this is distilled off overhead The reaction mixture is left to cool added to ca. 500 ml of water The aqueous phase is extracted with ethyl acetate the organic phase is dried with sodium sulfate after filtering off the drying agent is concentrated by evaporation The resulting 72 g (purity ca. 90%) of (1-ethoxy-propylidene)malononitrile are used in the subsequent step without further purification

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In portions, 7.56 g of cyanamide are added to a solution of 32.38 g (33.4 ml, density=0.97 g/l) of 30% sodium methanolate solution and 100 ml of ethanol and the mixture is stirred at 25° C. for ca. 5 minutes; then, over the course of ca. 25 minutes, 30 g (ca. 90% strength, 180 mmol) of (1-ethoxypropylidene)malononitrile are added dropwise. The mixture is stirred for two hours, then the volatile constituents are largely removed by distillation, and the remaining residue is taken up in methylene chloride. The methylene chloride phase is separated off and the remaining 37.57 g of sodium cyano[1-(dicyanomethylidene)propyl]azanide with ca. 80% purity are used in the following stage. The mixture is stirred for two hours the volatile constituents are largely removed by distillation The methylene chloride phase is separated off

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

実験手順: Ethanol, (11.0 L), 2-(1-ethoxy-propylidene)-malononitrile, (2.003 kg, 13.34 moles, 1.0 eq), ethyl-2-mercaptoacetate (1.652 kg, 13.34 moles, 1.0 eq.), and potassium acetate (1.983 kg, 20.0 moles, 1.5 eq.) are charged to a 22L 3-neck reaction flask equipped with an addition funnel, thermocouple, overhead stirrer, and condenser. The reaction mixture becomes dark red and exotherms to 72° C. The mixture is stirred for 1.25 hours while cooling to 60° C. Deionized water (2.6 L), is added to the reaction mixture over 30 minutes while cooling to 53° C. The reaction mixture is then cooled to 10° C. over 3.5 hours. The resulting suspension is filtered to recover the precipitate, and the filter cake is rinsed with a chilled mixture of 1.1 L ethanol and 3.9 L water. The filter cake is vacuum dried at room temperature, affording the title compound (2.552 kg) in 85.3% yield. equipped with an addition funnel exotherms to 72° C while cooling to 53° C The reaction mixture is then cooled to 10° C. over 3.5 hours The resulting suspension is filtered to recover the precipitate the filter cake is rinsed with a chilled mixture of 1.1 L ethanol and 3.9 L water dried at room temperature