oct-7-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:; See reaction.notes.procedure_details.

実験手順: Chloroacetyl chloride (0.16 ml, 2.0 mmol, 1 equiv.) was added to a stirred solution of 7-Octyn-1-ol (300 mg, 2.4 mmol, 1.2 equiv.) in CH2Cl2 (6 m-) at −5° C. The reaction mixture was allowed to warm-up to r.t., were it was stirred for 4 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%) to give the desired compound as a pale yellow liquid (450 mg, 100%). The solvent was removed under reduced pressure the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%)

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

実験手順: The same procedure for 8-nonyn-1-ol was followed with 3-octyn-1-ol (6.89 g, 54.6 mmol), KH (6.57 g, 16.4 mmol), and 1,3-diaminopropane (60 mL). This produced 6.09 g of clear yellowish liquid (88%): IR (neat)ν 3360, 2896, 2116 cm−1; 1H—NMR δ 3.44 (t, 2H, J=6.6 Hz), 3.27 (bs, 1H), 2.04 (td, 2H, J=2.6 Hz, 6.6 Hz), 1.83 (t, 1H, J=2.6 Hz), 1.39 (m, 4H), 1.25 (m, 4H); 13C NMR δ 84.5, 68.3, 62.2, 32.3, 28.3, 25.2, (2C), 18.2; MS m/z 136.00 (m++Li). Anal. Calcd for C8H14O: C, 76.14; H, 11.18. Found: C, 76.04; H, 11.16.

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dehydrated dichloromethane (20 mL) and triphenylphosphine (5.91 g, 22.5 mmol) were added to 8-hydroxy-1-octyne (1.95 g, 15 mmol). The mixture was cooled to 0° C. and was then dropwise added to dehydrated dichloromethane (10 mL) containing carbon tetrabromide (7.46 g, 22.5 mmol), followed by stirring at room temperature for 2 hours. After separation between dichloromethane (100 mL) and 5% sodium bicarbonate (150 mL), the organic layer was washed with saturated brine (150 mL). The organic layer was dried over sodium sulfate and then concentrated. The concentrated product was purified by silica gel column chromatography (dichloromethane:methanol=from 100:0 to 99:1) to yield 8-bromo-1-octyne (crude). After separation between dichloromethane (100 mL) and 5% sodium bicarbonate (150 mL) the organic layer was washed with saturated brine (150 mL) The organic layer was dried over sodium sulfate concentrated The concentrated product was purified by silica gel column chromatography (dichloromethane:methanol=from 100:0 to 99:1)

反応条件: temp:7.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To an ice-cooled solution of p-toluenesulfonyl chloride (17.4 g, 91.3 mmol) in pyridine (30 ml), 7-octyne-1-ol (9.6 g, 76.1 mmol) was added dropwise, and stirred at 5-10 ° C. for 20 hours. The reaction mixture was added with water (15 ml), stirred, then poured into water (500 ml), and extracted with ether (500 ml). The ether layer was washed with cold 1N-hydrochloric acid, saturated aqueous sodium hydrogencarbonate and water, dried over magnesium sulfate, and concentrated under reduced pressure to afford 18.3 g of 7-octynyl-p-toluenesulfonate (yield; 85.7%). was added dropwise stirred extracted with ether (500 ml) The ether layer was washed with cold 1N-hydrochloric acid, saturated aqueous sodium hydrogencarbonate and water dried over magnesium sulfate concentrated under reduced pressure

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

実験手順: A suspension of lithium acetylide ethylenediamine complex (Aldrich, 11.3 g, 122.5 mmol) and dimethyl sulfoxide (50 ml) was cooled to 5-10° C., and added dropwise with 1-bromo-6-tetrahydropyranyloxyhexane (Sigma, 25 g, 94.3 mmol) over two hours. Then, the reaction mixture was stirred at room temperature for two hours. The reaction mixture was added with water (10 ml), stirred for ten minutes, then poured into water (150 ml), and extracted with ether (300 ml). The ether layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to afford 18.1 g of 8-(tetrahydropyranyloxy)-1-octyne as oil (yield; 91.2%). Dowex 50WX8 (H+ type, 18 g) was added to a mixture of 8-(tetrahydropyranyloxy)-1-octyne (18 g, 85.6 mmol), chloroform (40 ml) and methanol (140 ml), and heated for 1 hour under reflux. After the resin was separated by filtration, the filtrate was concentrated, and the resulting residue was purified by silica gel column chromatography (eluent; hexane-ethyl acetate mixed solvent) to afford 9.6 g of 7-octyn-1-ol (yield; 88.6%). heated for 1 hour under reflux After the resin was separated by filtration the filtrate was concentrated the resulting residue was purified by silica gel column chromatography (eluent; hexane-ethyl acetate mixed solvent)

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

実験手順: A suspension of lithium acetylide ethylenediamine complex (Aldrich, 11.3 g, 122.5 mmol) and dimethyl sulfoxide (50 ml) was cooled to 5-10° C., and added dropwise with 1-bromo-6-tetrahydropyranyloxyhexane (Sigma, 25 g, 94.3 mmol) over two hours. Then, the reaction mixture was stirred at room temperature for two hours. The reaction mixture was added with water (10 ml), stirred for ten minutes, then poured into water (150 ml), and extracted with ether (300 ml). The ether layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure to afford 18.1 g of 8-(tetrahydropyranyloxy)-1-octyne as oil (yield; 91.2%). Dowex 50WX8 (H+ type, 18 g) was added to a mixture of 8-(tetrahydropyranyloxy)-1-octyne (18 g, 85.6 mmol), chloroform (40 ml) and methanol (140 ml), and heated for 1 hour under reflux. After the resin was separated by filtration, the filtrate was concentrated, and the resulting residue was purified by silica gel column chromatography (eluent; hexane-ethyl acetate mixed solvent) to afford 9.6 g of 7-octyn-1-ol (yield; 88.6%). heated for 1 hour under reflux After the resin was separated by filtration the filtrate was concentrated the resulting residue was purified by silica gel column chromatography (eluent; hexane-ethyl acetate mixed solvent)

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

実験手順: Chloroacetyl chloride (0.16 ml, 2.0 mmol, 1 equiv.) was added to a stirred solution of 7-Octyn-1-ol (300 mg, 2.4 mmol, 1.2 equiv.) in CH2Cl2 (6 m-) at −5° C. The reaction mixture was allowed to warm-up to r.t., were it was stirred for 4 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%) to give the desired compound as a pale yellow liquid (450 mg, 100%). The solvent was removed under reduced pressure the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%)

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

実験手順: Chloroacetyl chloride (0.16 ml, 2.0 mmol, 1 equiv.) was added to a stirred solution of 7-Octyn-1-ol (300 mg, 2.4 mmol, 1.2 equiv.) in CH2Cl2 (6 m-) at −5° C. The reaction mixture was allowed to warm-up to r.t., were it was stirred for 4 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%) to give the desired compound as a pale yellow liquid (450 mg, 100%). The solvent was removed under reduced pressure the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%)

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

実験手順: Chloroacetyl chloride (0.16 ml, 2.0 mmol, 1 equiv.) was added to a stirred solution of 7-Octyn-1-ol (300 mg, 2.4 mmol, 1.2 equiv.) in CH2Cl2 (6 m-) at −5° C. The reaction mixture was allowed to warm-up to r.t., were it was stirred for 4 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%) to give the desired compound as a pale yellow liquid (450 mg, 100%). The solvent was removed under reduced pressure the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%)

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

実験手順: Chloroacetyl chloride (0.16 ml, 2.0 mmol, 1 equiv.) was added to a stirred solution of 7-Octyn-1-ol (300 mg, 2.4 mmol, 1.2 equiv.) in CH2Cl2 (6 m-) at −5° C. The reaction mixture was allowed to warm-up to r.t., were it was stirred for 4 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%) to give the desired compound as a pale yellow liquid (450 mg, 100%). The solvent was removed under reduced pressure the residue was purified by column chromatography on silica eluting with EtOAc/hexane (10%)