2-ethenyl-4-fluorophenol

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

実験手順: A mixture of 2-ethenyl-4-fluorophenol (C16) (1.03 g, 7.46 mmol) and potassium carbonate (3.12 g, 22.4 mmol) in acetone (35 mL) was treated with benzyl bromide (1.78 mL, 14.9 mmol) and stirred at reflux for 3 hours. The mixture was concentrated in vacuo, ethyl acetate (100 mL) was added and the mixture was washed with water (2×50 mL) and saturated aqueous sodium chloride solution (50 mL). The organic layer was dried over magnesium sulfate, and concentrated in vacuo. Purification via silica gel chromatography (Gradient: 0% to 15% ethyl acetate in heptane) afforded the title compound as a colorless oil. Yield: 1.64 g, 7.23 mmol, 97%. GCMS m/z 228 (M+). 1H NMR (400 MHz, CDCl3) δ 5.08 (s, 2H), 5.33 (dd, J=11.1, 1.0 Hz, 1H), 5.76 (dd, J=17.8, 1.0 Hz, 1H), 6.85-6.95 (m, 2H), 7.11 (ddd, J=17.8, 11.1, 1.5 Hz, 1H), 7.23 (dd, J=9.4, 2.9 Hz, 1H), 7.33-7.48 (m, 5H). at reflux for 3 hours The mixture was concentrated in vacuo, ethyl acetate (100 mL) was added the mixture was washed with water (2×50 mL) and saturated aqueous sodium chloride solution (50 mL) The organic layer was dried over magnesium sulfate concentrated in vacuo Purification via silica gel chromatography (Gradient: 0% to 15% ethyl acetate in heptane)

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Nitrogen was bubbled through a mixture of 2-bromo-4-fluorophenol (1.6 g, 8.38 mmol), vinylboronic anhydride pyridine complex (95%, 806 mg, 3.35 mol) and potassium carbonate (1.17 g, 8.38 mmol) in 1,2-dimethoxyethane (15 mL) for 30 minutes. To this mixture was added palladium tetrakis(triphenylphosphine) (97.2 mg, 0.084 mmol). The reaction was allowed to stir at 90° C. for 16 hours. Water (50 mL) was added, and the mixture was extracted with ethyl acetate (2×100 mL). The combined organic layers were washed with aqueous sodium hydroxide solution (1 N, 100 mL) and saturated aqueous sodium chloride solution (100 mL), dried over magnesium sulfate and concentrated in vacuo. Purification via silica gel chromatography (Gradient: 0% to 30% ethyl acetate in heptanes) afforded the title compound as a white solid. Yield: 1.03 g, 7.46 mmol, 89%. 1H NMR (400 MHz, CDCl3) δ 4.91 (br s, 1H), 5.41 (dd, J=11.1, 1.0 Hz, 1H), 5.74 (dd, J=17.6, 1.0 Hz, 1H), 6.74 (dd, J=8.8, 4.7 Hz, 1H), 6.82-6.95 (m, 2H), 7.10 (dd, J=9.5, 3.0 Hz, 1H). the mixture was extracted with ethyl acetate (2×100 mL) The combined organic layers were washed with aqueous sodium hydroxide solution (1 N, 100 mL) and saturated aqueous sodium chloride solution (100 mL) dried over magnesium sulfate concentrated in vacuo Purification via silica gel chromatography (Gradient: 0% to 30% ethyl acetate in heptanes)