1-氟-8-溴辛烷

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 3-butyn-1-yl tetrahydropyranyl ether (0.4815 g, 3.05 mmol) (prepared as in Example 1 above) in dry tetrahydrofuran (15 mL) at -78° C. is added n-butyllithium (3.05 mmol, 2.80 mL of 1.09M n-BuLi in hexane). The resulting yellow mixture is stirred for 1 hour at -78° C., warmed to -5° C. for about 5 min and then a solution of 8-bromo-1-fluorooctane (0.7716 g, 3.65 mmol, 1.2 eq.) in HMPA (10 mL) is added dropwise over 45 minutes (Hendry et al., J. Chem. Ecol., 1, 317, 1975). After the addition is completed, the reaction is allowed to warm to room temperature and stirred overnight. After quenching the solution by the dropwise addition of water (about 10 mL), the aqueous solution is extracted with pentane (4×50 ml) and the combined pentane extracts are washed with saturated sodium chloride (50 mL) and dried (MgSO4). The volatiles are removed in vacuo and the crude product is flash chromatographed using hexane/ethyl acetate (9:1, v/v) to give 12-fluoro-3-dodecyn-1-yl tetrahydropyranyl ether (0.526 g, 60%) as a clear colorless oil: Rf=0.60, hexane/ethyl acetate (7:3, v/v); IR (film) ν2850-3000 (alkane CH) and 1H-NMR (CDCl3) δ1.20-1.90 (m, 18H), 2.05-2.20 (m, 2H), 2.30-2.55 (m,2H), 3.30-3.95(m, 4, 4.42 (dt, J=48 Hz, 6 Hz, 2H), 4.60 (br s, 1H). warmed to -5° C. for about 5 min After the addition to warm to room temperature stirred overnight After quenching the solution by the dropwise addition of water (about 10 mL) the aqueous solution is extracted with pentane (4×50 ml) the combined pentane extracts are washed with saturated sodium chloride (50 mL) dried (MgSO4) The volatiles are removed in vacuo chromatographed

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 8-bromooctan-1-ol (Hendry et al., J. Chem. Ecol., 1, 317, 1975), (2.50 g, 11.9 mmol) in methylene chloride (about 3 ml) is slowly added to a stirred solution of diethylaminosulfur trifluoride (DAST) (Middleton, J. Org. Chem, 40, 574, 1975) (1.5 mL, 11.9 mmol) in methylene chloride (10 mL), cooled to -78° C. After the addition is completed, the reaction mixture is warmed to 25° C. and saturated aqueous sodium bicarbonate (about 5 mL) is added, followed by dilution with ether (about 200 mL). The organic layer is then separated, and washed with water (20 mL), saturated sodium bicarbonate (20 mL) and then dried (MgSO4). The volatiles are removed in vacuo and the crude product is purified by flash chromatography using hexane/ethyl acetate, (95.5, v/v) to afford 8-bromo-fluoro-octane (1.54 g, 61%) as a clear colorless liquid: Rf=0.70, hexane/ethyl acetate (7:3, v/v); IR (film) ν2850-3000 (alkane CH) and 1H-NMR (CDCl3) δ1.15-2.0 (m, 12H), 3.39 (t, J=6 Hz, 2H), 4.42 (dt, J=48 Hz, 6 Hz, 2H). After the addition the reaction mixture is warmed to 25° C. The organic layer is then separated washed with water (20 mL), saturated sodium bicarbonate (20 mL) dried (MgSO4) The volatiles are removed in vacuo the crude product is purified by flash chromatography