oct-2-yn-1-ol

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 2-octyne-1-ol (37.8 g) in ether (150 mL) containing pyridine (3 ml) was cooled to -35° and treated with a solution of phosphorous tribromide (28.9 g) over 45 min. The mixture was then stirred at -30° for 2 hours, 3 hours at room temperature and 1/2 hour at 40°. The reaction mixture was then cooled to room temperature, poured onto ice and extracted with ether. The combined ether extracts were washed with aqueous NaHCO3 solution, brine and dried (MgSO4). Removal of the solvents and distillation of the residue yielded 1-bromo-2-octyne (40.9 g), bp, 106°-110° (25 mmHg). was cooled to -35° The reaction mixture was then cooled to room temperature poured onto ice extracted with ether The combined ether extracts were washed with aqueous NaHCO3 solution, brine dried (MgSO4) Removal of the solvents and distillation of the residue

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

実験手順: Under argon atmosphere, anhydrous pyridine (0.4 ml, 4.9 mmol) was added to a solution of 2-octyne-1-ol (9.4658 g, 75.0 mmol) in anhydrous ether (50 ml). To the mixture was added dropwise phosphorus tribromide (2.35 ml, 25.0 mmol) at -30° to -35° C. and the mixture was stirred at the same temperature for one hour and then stirred for one hour at room temperature under argon atmosphere. To the resulting mixture was added brine (100 ml), and the mixture was then extracted with ether (50 ml×4). The combined ether layers were washed with an aqueous saturated solution of sodium bicarbonate (150 ml), with water (150 ml) and with brine (150 ml), dried over anhydrous sodium sulfate (40 g), and concentrated. Distillation of the residue gave a colorless oily product of 1-bromo-2-octyne (9.1493 g, 65%, B.p.: 53°-58° C./0.39 mmHg). The product was assigned the structure by the following data. stirred for one hour at room temperature under argon atmosphere the mixture was then extracted with ether (50 ml×4) The combined ether layers were washed with an aqueous saturated solution of sodium bicarbonate (150 ml), with water (150 ml) and with brine (150 ml) dried over anhydrous sodium sulfate (40 g) concentrated Distillation of the residue

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

実験手順: Under argon atmosphere, a piece of lithium was added to a liquid ammonia (250 ml) in a three neck distillation flask. After the reaction mixture had became dark blue, a catalytic amount of ferric nitrate nonahydrate was added thereto under argon atmosphere. A piece of lithium (2.75 g, 396 mmol) was successively added over 30 min. and the mixture was stirred for one hour. Propargyl alcohol (8.16 g, 146 mmol) was then added and the mixture was stirred for 30 min. Further, n-pentyl bromide (20 g, 132 mmol) was added and the mixture was stirred for 10 min. and allowed to stand overnight at room temperature. To the resulting mixture were added hydrated ether (50 ml) and water (200 ml), and the mixture was then extracted with ether (200 ml, 100 ml, 50 ml×3). The combined ether layers were washed with water (400 ml) and with brine (400 ml), dried over anhydrous sodium sulfate (50 g), and concentrated. Distillation of the residue gave a colorless oily product of 2-octyne-1-ol (9.5758 g, 52%, B.p.: 58°-61° C./0.3 mmHg). The product was assigned the structure by the following data. the mixture was stirred for 30 min the mixture was stirred for 10 min. to stand overnight at room temperature the mixture was then extracted with ether (200 ml, 100 ml, 50 ml×3) The combined ether layers were washed with water (400 ml) and with brine (400 ml) dried over anhydrous sodium sulfate (50 g) concentrated Distillation of the residue

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

実験手順: Under argon atmosphere, a piece of lithium was added to a liquid ammonia (250 ml) in a three neck distillation flask. After the reaction mixture had became dark blue, a catalytic amount of ferric nitrate nonahydrate was added thereto under argon atmosphere. A piece of lithium (2.75 g, 396 mmol) was successively added over 30 min. and the mixture was stirred for one hour. Propargyl alcohol (8.16 g, 146 mmol) was then added and the mixture was stirred for 30 min. Further, n-pentyl bromide (20 g, 132 mmol) was added and the mixture was stirred for 10 min. and allowed to stand overnight at room temperature. To the resulting mixture were added hydrated ether (50 ml) and water (200 ml), and the mixture was then extracted with ether (200 ml, 100 ml, 50 ml×3). The combined ether layers were washed with water (400 ml) and with brine (400 ml), dried over anhydrous sodium sulfate (50 g), and concentrated. Distillation of the residue gave a colorless oily product of 2-octyne-1-ol (9.5758 g, 52%, B.p.: 58°-61° C./0.3 mmHg). The product was assigned the structure by the following data. the mixture was stirred for 30 min the mixture was stirred for 10 min. to stand overnight at room temperature the mixture was then extracted with ether (200 ml, 100 ml, 50 ml×3) The combined ether layers were washed with water (400 ml) and with brine (400 ml) dried over anhydrous sodium sulfate (50 g) concentrated Distillation of the residue

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

実験手順: Under argon atmosphere, anhydrous pyridine (0.4 ml, 4.9 mmol) was added to a solution of 2-octyne-1-ol (9.4658 g, 75 mmol) in anhydrous ether (50 ml). To the mixture, there was dropwise added phosphorus tribromide (2.35 ml, 25.0 mmol) at -30° C. to -35° C., and the resulting reaction mixture was stirred for one hour. The mixture was then stirred at room temperature for one hour. Brine (100 ml) was added to the reaction mixture followed by extraction with ether (50 ml×4). The organic layers were combined, washed with saturated aqueous sodium hydrogencarbonate solution (150 ml), with water (150 ml) and with brine (150 ml), and dried over anhydrous sodium sulfate (40 g) to concentrate. The residue was distilled (b.p.=53°-58° C. at 0.39 mmHg), yielding a colorless oil, 1-bromo-2-octyne (9.1493 g, 63% yield). The structure was confirmed by the following data. at -30° C. to -35° C. the resulting reaction mixture The mixture was then stirred at room temperature for one hour followed by extraction with ether (50 ml×4) washed with saturated aqueous sodium hydrogencarbonate solution (150 ml), with water (150 ml) and with brine (150 ml) dried over anhydrous sodium sulfate (40 g) to concentrate The residue was distilled (b.p.=53°-58° C. at 0.39 mmHg)

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

実験手順: Under argon atmosphere, a small amount of lithium pieces was added to liquid ammonia (250 ml). The reaction mixture became dark blue in color. A catalytic amount of ferric nitrate nonahydrate was added and the mixture was stirred until the dark blue color disappeared. Lithium pieces (2.75 g, 396 mmol) were further added and the reaction mixture was stirred for one hour. Subsequently, propargyl alcohol (8.16 g, 146 mmol) was added and the mixture was stirred for 30 minutes. Then, n-pentyl bromide (20 g, 132 mmol) was added, and the mixture was stirred for 10 minutes and allowed to stand overnight at room temperature. Water-containing ether (50 ml) and water (200 ml) were added and the resulting mixture was extracted with ether (200 ml, 100 ml, 50 ml×3). The organic layers were combined, washed with water (400 ml) and with brine (400 ml), dried over anhydrous sodium sulfate (50 g) to concentrate. The residue was distilled (b.p.=58°-61° C. at 0.3 mmHg), yielding a colorless oil, 2-octyne-1-ol (9.5758 g, 52% yield). The above described structure of this product was confirmed by the following data. the reaction mixture was stirred for one hour the mixture was stirred for 30 minutes the mixture was stirred for 10 minutes were added the resulting mixture was extracted with ether (200 ml, 100 ml, 50 ml×3) washed with water (400 ml) and with brine (400 ml) dried over anhydrous sodium sulfate (50 g) to concentrate The residue was distilled (b.p.=58°-61° C. at 0.3 mmHg)

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

実験手順: A solution of 2-octyne-1-ol (37.8 g) in ether (150 mL) containing pyridine (3 ml) was cooled to -35° and treated with a solution of phosphorous tribromide (28.9 g) over 45 min. The mixture was then stirred at -30° for 2 hours, 3 hours at room temperature and 1/2 hour at 40°. The reaction mixture was then cooled to room temperature, poured onto ice and extracted with ether. The combined ether extracts were washed with aqueous NaHCO3 solution, brine and dried (MgSO4). Removal of the solvents and distillation of the residue yielded 1-bromo-2-octyne (40.9 g), bp, 106°-110° (25 mmHg). was cooled to -35° The reaction mixture was then cooled to room temperature poured onto ice extracted with ether The combined ether extracts were washed with aqueous NaHCO3 solution, brine dried (MgSO4) Removal of the solvents and distillation of the residue

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

実験手順: Under argon atmosphere, anhydrous pyridine (0.4 ml, 4.9 mmol) was added to a solution of 2-octyne-1-ol (9.4658 g, 75.0 mmol) in anhydrous ether (50 ml). To the mixture was added dropwise phosphorus tribromide (2.35 ml, 25.0 mmol) at -30° to -35° C. and the mixture was stirred at the same temperature for one hour and then stirred for one hour at room temperature under argon atmosphere. To the resulting mixture was added brine (100 ml), and the mixture was then extracted with ether (50 ml×4). The combined ether layers were washed with an aqueous saturated solution of sodium bicarbonate (150 ml), with water (150 ml) and with brine (150 ml), dried over anhydrous sodium sulfate (40 g), and concentrated. Distillation of the residue gave a colorless oily product of 1-bromo-2-octyne (9.1493 g, 65%, B.p.: 53°-58° C./0.39 mmHg). The product was assigned the structure by the following data. stirred for one hour at room temperature under argon atmosphere the mixture was then extracted with ether (50 ml×4) The combined ether layers were washed with an aqueous saturated solution of sodium bicarbonate (150 ml), with water (150 ml) and with brine (150 ml) dried over anhydrous sodium sulfate (40 g) concentrated Distillation of the residue

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

実験手順: Under argon atmosphere, a piece of lithium was added to a liquid ammonia (250 ml) in a three neck distillation flask. After the reaction mixture had became dark blue, a catalytic amount of ferric nitrate nonahydrate was added thereto under argon atmosphere. A piece of lithium (2.75 g, 396 mmol) was successively added over 30 min. and the mixture was stirred for one hour. Propargyl alcohol (8.16 g, 146 mmol) was then added and the mixture was stirred for 30 min. Further, n-pentyl bromide (20 g, 132 mmol) was added and the mixture was stirred for 10 min. and allowed to stand overnight at room temperature. To the resulting mixture were added hydrated ether (50 ml) and water (200 ml), and the mixture was then extracted with ether (200 ml, 100 ml, 50 ml×3). The combined ether layers were washed with water (400 ml) and with brine (400 ml), dried over anhydrous sodium sulfate (50 g), and concentrated. Distillation of the residue gave a colorless oily product of 2-octyne-1-ol (9.5758 g, 52%, B.p.: 58°-61° C./0.3 mmHg). The product was assigned the structure by the following data. the mixture was stirred for 30 min the mixture was stirred for 10 min. to stand overnight at room temperature the mixture was then extracted with ether (200 ml, 100 ml, 50 ml×3) The combined ether layers were washed with water (400 ml) and with brine (400 ml) dried over anhydrous sodium sulfate (50 g) concentrated Distillation of the residue