8-chlorooct-1-yne

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:47.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g: 1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 8-chloro-1-octyne (144.6 g: 1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over one hour, and then stirred at from 60 to 65° C. for 5 hours. A solution of triethyl orthoformate (177.8 g: 1.2 mol) in toluene (120.0 g) was then dropwise added thereto at a reaction mixture of from 80 to 85° C. over 30 minutes, and stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 9-chloro-1,1-diethoxy-2-nonyne [bp: 138-142° C./0.13 KPa, 185.8 g, 0.75 mol]. [Yield: 75.3%] In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel stirred at from 60 to 65° C. for 5 hours at a reaction mixture of from 80 to 85° C. over 30 minutes stirred at from 90 to 95° C. for 6 hours were added to the reaction mixture The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g) The organic phase was subjected to removal of the solvent under reduced pressure the residue was distilled under reduced pressure

反応条件: temp:47.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g: 1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 8-chloro-1-octyne (144.6 g: 1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over one hour, and then stirred at from 60 to 65° C. for 5 hours. A solution of triethyl orthoformate (177.8 g: 1.2 mol) in toluene (120.0 g) was then dropwise added thereto at a reaction mixture of from 80 to 85° C. over 30 minutes, and stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 9-chloro-1,1-diethoxy-2-nonyne [bp: 138-142° C./0.13 KPa, 185.8 g, 0.75 mol]. [Yield: 75.3%] In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel stirred at from 60 to 65° C. for 5 hours at a reaction mixture of from 80 to 85° C. over 30 minutes stirred at from 90 to 95° C. for 6 hours were added to the reaction mixture The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g) The organic phase was subjected to removal of the solvent under reduced pressure the residue was distilled under reduced pressure

反応条件: temp:47.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g: 1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 8-chloro-1-octyne (144.6 g: 1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over one hour, and then stirred at from 60 to 65° C. for 5 hours. A solution of triethyl orthoformate (177.8 g: 1.2 mol) in toluene (120.0 g) was then dropwise added thereto at a reaction mixture of from 80 to 85° C. over 30 minutes, and stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 9-chloro-1,1-diethoxy-2-nonyne [bp: 138-142° C./0.13 KPa, 185.8 g, 0.75 mol]. [Yield: 75.3%] In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel stirred at from 60 to 65° C. for 5 hours at a reaction mixture of from 80 to 85° C. over 30 minutes stirred at from 90 to 95° C. for 6 hours were added to the reaction mixture The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g) The organic phase was subjected to removal of the solvent under reduced pressure the residue was distilled under reduced pressure

反応条件: temp:47.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g:1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 8-chloro-1-octyne (144.6 g:1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over one hour, and then stirred at from 60 to 65° C. for 5 hours. A solution of triethyl orthoformate (177.8 g:1.2 mol) in toluene (120.0 g) was then dropwise added thereto at a reaction mixture of from 80 to 85° C. over 30 minutes, and stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 9-chloro-1,1-diethoxy-2-nonyne [bp: 138-142° C./0.13 KPa, 185.8 g, 0.75 mol]. [Yield: 75.3%] In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel stirred at from 60 to 65° C. for 5 hours at a reaction mixture of from 80 to 85° C. over 30 minutes stirred at from 90 to 95° C. for 6 hours were added to the reaction mixture The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g) The organic phase was subjected to removal of the solvent under reduced pressure the residue was distilled under reduced pressure

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

実験手順: A solution of 12.0 g. of 1-chlorooct-7-yne in 20 ml. of tetrahydrofuran is added to a mixture of 27 ml. of 3N ethyl magnesium bromide in ether and 50 ml. of tetrahydrofuran. The mixture is stirred and heated under reflux for 30 min. under nitrogen, then 0.45 g. of powdered cuprous chloride is added and heating and stirring is continued for 20 min. A solution of 20.0 g. of 1-bromo-2,6-dimethyl-2,5-undecadiene in 15-ml. of tetrahydrofuran is added and the mixture is heated under reflux for 10 hrs., then allowed to stand for about 18 hrs., and poured into saturated aqueous ammonium chloride and ether. The mixture is filtered and the ether solution is separated, washed with water, dried over sodium sulfate, and evaporated to leave a residue comprising 1-chloro-10,14-dimethylnonadeca-10,13-dien-7-yne. heated under reflux for 30 min. under nitrogen heating stirring the mixture is heated under reflux for 10 hrs to stand for about 18 hrs The mixture is filtered the ether solution is separated washed with water dried over sodium sulfate evaporated

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

実験手順: To 21 ml. of 3M ethereal methyl magnesium bromide in 47.5 ml. of dry tetrahydrofuran under nitrogen was added 9.2 g. of 1-chloro-7-octyne in 15 ml. of tetrahydrofuran. The mixture was heated under reflux for 30 min., then was allowed to cool to room temperature during another 30 minutes after which 365 mg. of cuprous chloride was added. The mixture was heated under reflux for 20 min., then a solution of 14 g. of 1-bromo-6-methyl-undec-2-yn-5-ene in 12.9 ml. of tetrahydrofuran was added. The mixture was heated under reflux for 10 hrs. then cooled in an ice bath and 250 ml. saturated aqueous ammonium chloride was added. Ether was added and the mixture was filtered through Celite (diatomaceous earth filter ald) and separated. The thus obtained ether layer was washed with saturated aqueous sodium chloride, dried with magnesium sulfate, and evaporated. The thus obtained residue was distilled through a rocking short-path distillation apparatus, collecting 11.5 g. of a mixture comprising 1-chloro-14-methylnonadeca-7,10-dlyn-13-ene at a bath temperature of 180°-190°/0.005 mm. The mixture was heated under reflux for 30 min. The mixture was heated under reflux for 20 min. The mixture was heated under reflux for 10 hrs then cooled in an ice bath the mixture was filtered through Celite (diatomaceous earth filter ald) separated The thus obtained ether layer was washed with saturated aqueous sodium chloride dried with magnesium sulfate evaporated The thus obtained residue was distilled through a rocking short-path distillation apparatus collecting 11.5 g temperature of 180°-190°/0.005 mm

反応条件: temp:0.00; pressure:0.00; stir: