Pyridine → 4-Bromo-3-(tetrahydropyran-2-yloxy)benzyl bromide

Beteiligte Stoffe

Reaktionsbedingungen

Reaktionsschritte

The title compound was prepared adapting the method reported by Wada et al.[Wada, 1979] with the following modifications. To a solution of 4-bromo-3-(tetrahydropyran-2-yloxy)benzyl alcohol (3.0 g, 10.45 mmol), carbon tetrabromide (6.93 g, 20.90 mmol) and anhydrous pyridine (0.85 mL, 10.45 mmol) in anhydrous Et2O (50 mL) at 0° C. was added dropwise a solution of triphenylphosphine (5.48 g, 20.90 mmol) in anhydrous Et2O (10 mL). The mixture was stirred at 0° C. for 1 h and then at room temperature overnight. The solvent was removed in vacuo and the residue suspended in n-hexane and filtered. The filtered solid was washed with n-hexane and the combined filtrates concentrated in vacuo to ca. 10 mL. The residue was purified by flash column chromatography [SiO2, EtOAc/n-hexane (5:95)] to give 4-bromo-3-(tetrahydropyran-2-yloxy)benzyl bromide as a pale yellow oil (2.82 g, 77%) which slowly darkened on exposure to light and air; ¤H (270 MHz, CDCl3) 1.58-2.12 (m, 6H), 3.58-3.65 (m, 1H), 3.83-3.92 (m, 1H), 4.41 (d, J=12.6, 2H), 5.53 (m, 1H), 6.89 (dd, J=7.9, 2.0, 1H), 7.16 (d, J=2.2, 1H), 7.48 (d, J=8.2, 1H); LC-MS (APCI−): tR=4.71 min, m/z 266.95 (48, C12H1481Br2O4—C5H8O—H), 264.93 (100, C12H14Br2O4—C5H8O—H), 262.92 (50, C12H1479Br2O4—C5H8O—H); HPLC: tR=3.91 min (94%)

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