2-(1-chloro-2-methylpropylidene)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:

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

実験手順: A solution of (1-chloro-2-methylpropylidene)methane-1,1-dicarbonitrile (9.4 g, 61 mmol) in THF (250 mL) was treated with 2,6-dichlorophenylhydrazine hydrochloride (13.0 g, 61 mmol) followed by triethylamine (12.3 g, 122 mmol). The reaction was then heated to reilux for 18 h. The reaction was then cooled to room temp and partitioned between EtOAc (150 mL) and 1N NaOH (100 mL). The aqueous layer was extracted with EtOAc (2×150 mL) and the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL). The organic layer was dried (MgSO4), filtered, and evaporated. The crude product was recrystallized from EtOAc/hexane to yield the desired pyrazole (11.2 g, 62%). The reaction was then heated partitioned between EtOAc (150 mL) and 1N NaOH (100 mL) The aqueous layer was extracted with EtOAc (2×150 mL) the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL) The organic layer was dried (MgSO4) filtered evaporated The crude product was recrystallized from EtOAc/hexane

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

実験手順: A solution of (1-chloro-2-methylpropylidene)methane-1,1-dicarbonitrile (9.4 g, 61 mmol) in THF (250 mL) was treated with 2,6-dichlorophenylhydrazine hydrochloride (13.0 g, 61 mmol) followed by triethylamine (12.3 g, 122 mmol). The reaction was then heated to reflux for 18 h. The reaction was then cooled to room temp and partitioned between EtOAc (150 mL) and 1N NaOH (100 mL). The aqueous layer was extracted with EtOAc (2×150 mL) and the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL). The organic layer was dried (MgSO4), filtered, and evaporated. The crude product was recrystallized from EtOAc/hexane to yield the desired pyrazole (11.2 g, 62%). The reaction was then heated to reflux for 18 h partitioned between EtOAc (150 mL) and 1N NaOH (100 mL) The aqueous layer was extracted with EtOAc (2×150 mL) the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL) The organic layer was dried (MgSO4) filtered evaporated The crude product was recrystallized from EtOAc/hexane

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

実験手順: A solution of 191.3 g of 3-chloro-2-cyano-4-methyl- 2-pentenenitrile in 300 ml of ethanol was added slowly, maintaining the temperature below 40°, during 1.3 hours, to a mixture of 800 ml of concentrated ammonium hydroxide and 1000 ml of ethanol. The mixture was stirred for 3 hours, then poured over 2000 ml of ice. The solid was collected, washed with water and dried to obtain 122.0 g of 3-amino-2-cyano-4-methyl-2-pentenenitrile, mp 186°-188°. maintaining the temperature below 40° The solid was collected washed with water dried

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

実験手順: A solution of 530.5 g of 3-chloro-2-cyano-4-methyl-2-pentenenitrile in 515 ml of ethanol was added dropwise during one hour to a stirred solution of 2,400 ml of concentrated ammonium hydroxide in 1,560 ml of ethanol while maintaining the reaction mixture at 35°-40° with an ice-water bath. The reaction mixture was stirred for 3.5-4 hours and was poured into 6.5 liters of ice and water. The mixture was stirred until all the ice had melted (approximately thirty minutes). The precipitate was collected by filtration. The filter cake was washed with two 1500-ml portions of water and air-dried on the filter. After the drying the 400 g of 3-amino-2-cyano-4-methyl-2-pentenenitrile, mp 182°-184°, was used in the next synthesis step without further purification. while maintaining the reaction mixture at 35°-40° with an ice-water bath (approximately thirty minutes) The precipitate was collected by filtration The filter cake was washed with two 1500-ml portions of water air-dried on the filter After the drying the 400 g of 3-amino-2-cyano-4-methyl-2-pentenenitrile, mp 182°-184°, was used in the next synthesis step without further purification

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

実験手順: A solution of 530.5 g of 3-chloro-2-cyano-4-methyl-2-pentenenitrile in 515 ml of ethanol was added dropwise during one hour to a stirred solution of 2,400 ml of concentrated ammonium hydroxide in 1,560 ml of ethanol while maintaining the reaction mixture at 35°-40° with an ice-water bath. The reaction mixture was stirred for 3.5-4 hours and was poured into 6.5 liters of ice and water. The mixture was stirred until all the ice had melted (approximately thirty minutes). The precipitate was collected by filtration. The filter cake was washed with two 1500-ml portions of water and air-dried on the filter. After the drying the 400 g of 3-amino-2-cyano-4-methyl-2-pentenenitrile, mp 182°-184°, was used in the next synthesis step without further purification. while maintaining the reaction mixture at 35°-40° with an ice-water bath (approximately thirty minutes) The precipitate was collected by filtration The filter cake was washed with two 1500-ml portions of water air-dried on the filter After the drying the 400 g of 3-amino-2-cyano-4-methyl-2-pentenenitrile, mp 182°-184°, was used in the next synthesis step without further purification

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

実験手順: A solution of (1-chloro-2-methylpropylidene)methane-1,1-dicarbonitrile (9.4 g, 61 mmol) in THF (250 mL) was treated with 2,6-dichlorophenylhydrazine hydrochloride (13.0 g, 61 mmol) followed by triethylamine (12.3 g, 122 mmol). The reaction was then heated to reilux for 18 h. The reaction was then cooled to room temp and partitioned between EtOAc (150 mL) and 1N NaOH (100 mL). The aqueous layer was extracted with EtOAc (2×150 mL) and the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL). The organic layer was dried (MgSO4), filtered, and evaporated. The crude product was recrystallized from EtOAc/hexane to yield the desired pyrazole (11.2 g, 62%). The reaction was then heated partitioned between EtOAc (150 mL) and 1N NaOH (100 mL) The aqueous layer was extracted with EtOAc (2×150 mL) the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL) The organic layer was dried (MgSO4) filtered evaporated The crude product was recrystallized from EtOAc/hexane

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

実験手順: A solution of (1-chloro-2-methylpropylidene)methane-1,1-dicarbonitrile (9.4 g, 61 mmol) in THF (250 mL) was treated with 2,6-dichlorophenylhydrazine hydrochloride (13.0 g, 61 mmol) followed by triethylamine (12.3 g, 122 mmol). The reaction was then heated to reilux for 18 h. The reaction was then cooled to room temp and partitioned between EtOAc (150 mL) and 1N NaOH (100 mL). The aqueous layer was extracted with EtOAc (2×150 mL) and the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL). The organic layer was dried (MgSO4), filtered, and evaporated. The crude product was recrystallized from EtOAc/hexane to yield the desired pyrazole (11.2 g, 62%). The reaction was then heated partitioned between EtOAc (150 mL) and 1N NaOH (100 mL) The aqueous layer was extracted with EtOAc (2×150 mL) the combined organic layers were washed with 10% aq. citric acid (150 mL), sat. aq. NaHCO3 (150 mL), and brine (150 mL) The organic layer was dried (MgSO4) filtered evaporated The crude product was recrystallized from EtOAc/hexane

反応条件: temp:0.00; pressure:0.00; stir: