2-壬炔-1-醇

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a round-bottom flask equipped with a stir bar and under an atmosphere of argon was added KH (4.46 g, 111 mmol). The flask was cooled to 0° C. and 1,3-diaminopropane (50 mL) was added slowly via syringe. The solution was stirred for 45 min. Then 2-nonyn-1-ol, dissolved in of 1,3-diaminopropane (30 mL), was added dropwise via syringe to the stirring solution. The reaction was stirred for an additional 30 min at 0° C. before warming to room temperature overnight. The reaction was again cooled to 0° C. before quenching with water. The compound was extracted with Et2O, washed with HCL, water, and brine, dried with MgSO4, and concentrated. This produced 4.94 g of dark orange oil which was purified by flash column chromatography on silica gel (2.5% Et2O in hexane to 50% Et2O in hexane) to give 3.21 g of clear oil (67%): IR (near) ν 3409, 2931, 2242 cm−1, 1H—NMR δ 3.59 (t, 2H, J=7.0 Hz), 2.14 (td, 2H, J=3.0 Hz, 7.0 Hz), 2.10 (s, 1H), 1.91 (t, 1H, J=3.0 Hz), 1.50 (bm, 4H), 1.30 (bm, 6H); 13C—NMR δ 84.6, 68.1, 62.8, 32.6, 28.8, 28.6, 28.3, 25.6, 18.3; MS m/z 147.10 (M++Li). Anal. Calcd for C9H16O: C, 77.09; H, 11.46. Found: C, 77.00; H, 11.46. In a round-bottom flask equipped with a stir bar and under an atmosphere of argon was added KH (4.46 g, 111 mmol) was added dropwise via syringe to the stirring solution The reaction was stirred for an additional 30 min at 0° C. before warming to room temperature overnight The reaction was again cooled to 0° C. before quenching with water The compound was extracted with Et2O washed with HCL, water, and brine dried with MgSO4 concentrated This produced 4.94 g of dark orange oil which was purified by flash column chromatography on silica gel (2.5% Et2O in hexane to 50% Et2O in hexane)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 250-mL flask equipped with a stir bar, I-Pr2NH (7.34 g, 72.5 mmol) and THF (20 mL) were stirred under argon and cooled to 0° C. A 2.5-M solution of n-BuLi in toluene (29.0 mL, 72.5 mmol) was added slowly to the stirring solution. The reaction was stirred for 30 min at 0° C. and then cooled to −78° C. in a dry ice/acetone bath. Then 1-octyne was added slowly via syringe to the reaction and a white precipitate formed. To dissolve the precipitate, HMPA (23.6 g, 132 mmol) was added in one portion. The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved. A solution of paraformaldehyde (CH2O)n (5.94 g, 198 mmol) in THF (60 mL) was stirred under argon at −78° C. The alkynyllitheate was then added via cannula with positive argon pressure to the (CH2O)n solution. The reaction was then allowed to warm slowly to room temperature. The reaction was quenched with water and extracted with Et2O. The organic layers were combined, washed with water and brine, dried with MgSO4, and concentrated. This produced 24.4 g of orange oil. The product was purified with flash column chromatography on silica gel (10% Et2O in hexane) to give 5.07 g of amber oil (55%): In a 250-mL flask equipped with a stir bar cooled to −78° C. in a dry ice/acetone bath a white precipitate formed was added in one portion The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved to warm slowly to room temperature The reaction was quenched with water extracted with Et2O washed with water and brine dried with MgSO4 concentrated The product was purified with flash column chromatography on silica gel (10% Et2O in hexane)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a cooled (0° C.) solution of 14.6 g (0.104 mole) of 2-nonyn-1-ol in 150 ml of dry methylene chloride and 23.14 ml (0.166 mole) of triethylamine there were added dropwise 10.7 ml (0.156 mole) of methanesulfonyl chloride. The reaction mixture was stirred for 30 minutes at the same temperature, diluted with methylene chloride (150 ml), washed with brine (100 ml), dried and evaporated under vacuum to provide 2-nonyn-1-ol methanesulfonate. washed with brine (100 ml) dried evaporated under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a cooled (0° C.) solution of 14.6 g (0.104 mole) of 2-nonyn-1-ol in 150 ml of dry methylene chloride and 23.14 ml (0.166 mole) of triethylamine there were added dropwise 10.7 ml (0.156 mole) of methanesulfonyl chloride. The reaction mixture was stirred for 30 minutes at the same temperature, diluted with methylene chloride (150 ml), washed with brine (100 ml), dried and evaporated under vacuum to provide 2-nonyn-1-ol methanesulfonate. washed with brine (100 ml) dried evaporated under vacuum

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a round-bottom flask equipped with a stir bar and under an atmosphere of argon was added KH (4.46 g, 111 mmol). The flask was cooled to 0° C. and 1,3-diaminopropane (50 mL) was added slowly via syringe. The solution was stirred for 45 min. Then 2-nonyn-1-ol, dissolved in of 1,3-diaminopropane (30 mL), was added dropwise via syringe to the stirring solution. The reaction was stirred for an additional 30 min at 0° C. before warming to room temperature overnight. The reaction was again cooled to 0° C. before quenching with water. The compound was extracted with Et2O, washed with HCL, water, and brine, dried with MgSO4, and concentrated. This produced 4.94 g of dark orange oil which was purified by flash column chromatography on silica gel (2.5% Et2O in hexane to 50% Et2O in hexane) to give 3.21 g of clear oil (67%): IR (near) ν 3409, 2931, 2242 cm−1, 1H—NMR δ 3.59 (t, 2H, J=7.0 Hz), 2.14 (td, 2H, J=3.0 Hz, 7.0 Hz), 2.10 (s, 1H), 1.91 (t, 1H, J=3.0 Hz), 1.50 (bm, 4H), 1.30 (bm, 6H); 13C—NMR δ 84.6, 68.1, 62.8, 32.6, 28.8, 28.6, 28.3, 25.6, 18.3; MS m/z 147.10 (M++Li). Anal. Calcd for C9H16O: C, 77.09; H, 11.46. Found: C, 77.00; H, 11.46. In a round-bottom flask equipped with a stir bar and under an atmosphere of argon was added KH (4.46 g, 111 mmol) was added dropwise via syringe to the stirring solution The reaction was stirred for an additional 30 min at 0° C. before warming to room temperature overnight The reaction was again cooled to 0° C. before quenching with water The compound was extracted with Et2O washed with HCL, water, and brine dried with MgSO4 concentrated This produced 4.94 g of dark orange oil which was purified by flash column chromatography on silica gel (2.5% Et2O in hexane to 50% Et2O in hexane)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 250-mL flask equipped with a stir bar, I-Pr2NH (7.34 g, 72.5 mmol) and THF (20 mL) were stirred under argon and cooled to 0° C. A 2.5-M solution of n-BuLi in toluene (29.0 mL, 72.5 mmol) was added slowly to the stirring solution. The reaction was stirred for 30 min at 0° C. and then cooled to −78° C. in a dry ice/acetone bath. Then 1-octyne was added slowly via syringe to the reaction and a white precipitate formed. To dissolve the precipitate, HMPA (23.6 g, 132 mmol) was added in one portion. The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved. A solution of paraformaldehyde (CH2O)n (5.94 g, 198 mmol) in THF (60 mL) was stirred under argon at −78° C. The alkynyllitheate was then added via cannula with positive argon pressure to the (CH2O)n solution. The reaction was then allowed to warm slowly to room temperature. The reaction was quenched with water and extracted with Et2O. The organic layers were combined, washed with water and brine, dried with MgSO4, and concentrated. This produced 24.4 g of orange oil. The product was purified with flash column chromatography on silica gel (10% Et2O in hexane) to give 5.07 g of amber oil (55%): In a 250-mL flask equipped with a stir bar cooled to −78° C. in a dry ice/acetone bath a white precipitate formed was added in one portion The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved to warm slowly to room temperature The reaction was quenched with water extracted with Et2O washed with water and brine dried with MgSO4 concentrated The product was purified with flash column chromatography on silica gel (10% Et2O in hexane)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 250-mL flask equipped with a stir bar, I-Pr2NH (7.34 g, 72.5 mmol) and THF (20 mL) were stirred under argon and cooled to 0° C. A 2.5-M solution of n-BuLi in toluene (29.0 mL, 72.5 mmol) was added slowly to the stirring solution. The reaction was stirred for 30 min at 0° C. and then cooled to −78° C. in a dry ice/acetone bath. Then 1-octyne was added slowly via syringe to the reaction and a white precipitate formed. To dissolve the precipitate, HMPA (23.6 g, 132 mmol) was added in one portion. The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved. A solution of paraformaldehyde (CH2O)n (5.94 g, 198 mmol) in THF (60 mL) was stirred under argon at −78° C. The alkynyllitheate was then added via cannula with positive argon pressure to the (CH2O)n solution. The reaction was then allowed to warm slowly to room temperature. The reaction was quenched with water and extracted with Et2O. The organic layers were combined, washed with water and brine, dried with MgSO4, and concentrated. This produced 24.4 g of orange oil. The product was purified with flash column chromatography on silica gel (10% Et2O in hexane) to give 5.07 g of amber oil (55%): In a 250-mL flask equipped with a stir bar cooled to −78° C. in a dry ice/acetone bath a white precipitate formed was added in one portion The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved to warm slowly to room temperature The reaction was quenched with water extracted with Et2O washed with water and brine dried with MgSO4 concentrated The product was purified with flash column chromatography on silica gel (10% Et2O in hexane)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 2-Nonyn- 1-ol (20 g, 0.4 mole) in 200 ml methyl alcohol is hydrogenated in a Parr bomb using a Lindlar catalyst (0.5 g Pd/BaSO4) and quinoline (0.5 g). The hydrogenation was monitored by gas liquid partition chromatography on diethylene glycol succinate. Hydrogenation is stopped when the concentration of the acetylenic alcohol equals that of the saturated alcohol. The hydrogenation mixture is filtered, diluted with water and extracted with ether. The ether extract is dried over anhydrous sodium sulfate, concentrated and distilled to yield 13 g of cis-2-nonen-1-ol, b.p. 60°-64°C/0.5 mm. partition chromatography on diethylene glycol succinate The hydrogenation mixture is filtered diluted with water extracted with ether The ether extract is dried over anhydrous sodium sulfate concentrated distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a cooled (0° C.) solution of 14.6 g (0.104 mole) of 2-nonyn-1-ol in 150 ml of dry methylene chloride and 23.14 ml (0.166 mole) of triethylamine there were added dropwise 10.7 ml (0.156 mole) of methanesulfonyl chloride. The reaction mixture was stirred for 30 minutes at the same temperature, diluted with methylene chloride (150 ml), washed with brine (100 ml), dried and evaporated under vacuum to provide 2-nonyn-1-ol methanesulfonate. washed with brine (100 ml) dried evaporated under vacuum

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a round-bottom flask equipped with a stir bar and under an atmosphere of argon was added KH (4.46 g, 111 mmol). The flask was cooled to 0° C. and 1,3-diaminopropane (50 mL) was added slowly via syringe. The solution was stirred for 45 min. Then 2-nonyn-1-ol, dissolved in of 1,3-diaminopropane (30 mL), was added dropwise via syringe to the stirring solution. The reaction was stirred for an additional 30 min at 0° C. before warming to room temperature overnight. The reaction was again cooled to 0° C. before quenching with water. The compound was extracted with Et2O, washed with HCL, water, and brine, dried with MgSO4, and concentrated. This produced 4.94 g of dark orange oil which was purified by flash column chromatography on silica gel (2.5% Et2O in hexane to 50% Et2O in hexane) to give 3.21 g of clear oil (67%): IR (near) ν 3409, 2931, 2242 cm−1, 1H—NMR δ 3.59 (t, 2H, J=7.0 Hz), 2.14 (td, 2H, J=3.0 Hz, 7.0 Hz), 2.10 (s, 1H), 1.91 (t, 1H, J=3.0 Hz), 1.50 (bm, 4H), 1.30 (bm, 6H); 13C—NMR δ 84.6, 68.1, 62.8, 32.6, 28.8, 28.6, 28.3, 25.6, 18.3; MS m/z 147.10 (M++Li). Anal. Calcd for C9H16O: C, 77.09; H, 11.46. Found: C, 77.00; H, 11.46. In a round-bottom flask equipped with a stir bar and under an atmosphere of argon was added KH (4.46 g, 111 mmol) was added dropwise via syringe to the stirring solution The reaction was stirred for an additional 30 min at 0° C. before warming to room temperature overnight The reaction was again cooled to 0° C. before quenching with water The compound was extracted with Et2O washed with HCL, water, and brine dried with MgSO4 concentrated This produced 4.94 g of dark orange oil which was purified by flash column chromatography on silica gel (2.5% Et2O in hexane to 50% Et2O in hexane)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 250-mL flask equipped with a stir bar, I-Pr2NH (7.34 g, 72.5 mmol) and THF (20 mL) were stirred under argon and cooled to 0° C. A 2.5-M solution of n-BuLi in toluene (29.0 mL, 72.5 mmol) was added slowly to the stirring solution. The reaction was stirred for 30 min at 0° C. and then cooled to −78° C. in a dry ice/acetone bath. Then 1-octyne was added slowly via syringe to the reaction and a white precipitate formed. To dissolve the precipitate, HMPA (23.6 g, 132 mmol) was added in one portion. The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved. A solution of paraformaldehyde (CH2O)n (5.94 g, 198 mmol) in THF (60 mL) was stirred under argon at −78° C. The alkynyllitheate was then added via cannula with positive argon pressure to the (CH2O)n solution. The reaction was then allowed to warm slowly to room temperature. The reaction was quenched with water and extracted with Et2O. The organic layers were combined, washed with water and brine, dried with MgSO4, and concentrated. This produced 24.4 g of orange oil. The product was purified with flash column chromatography on silica gel (10% Et2O in hexane) to give 5.07 g of amber oil (55%): In a 250-mL flask equipped with a stir bar cooled to −78° C. in a dry ice/acetone bath a white precipitate formed was added in one portion The cloudy solution was stirred under argon at −78° C. for 30 minutes before warming to 0° C. when the precipitate dissolved to warm slowly to room temperature The reaction was quenched with water extracted with Et2O washed with water and brine dried with MgSO4 concentrated The product was purified with flash column chromatography on silica gel (10% Et2O in hexane)