Carbon Tetrachloride → 1-(Chloromethyl)-3-methanesulfonylbenzene

Triphenylphosphine (7.5 g, 29 mmol), carbon tetrachloride (11.0 mL, 114 mmol) and tetrahydrofuran (18 mL) were combined and stirred at room temperature for 10 minutes. A suspension of (3-methanesulfonyl-phenyl)-methanol (2.68 g, 14.3 mmol) in 18 mL tetrahydrofuran was added, then the reaction mixture was heated at 75° C. for 3 hours. The reaction mixture was cooled to room temperature, then partitioned between ethyl acetate and water. The organic phase was dried over MgSO4, filtered, and concentrated to give the crude product as an oily solid. A solution of this crude product and dichloromethane was evaporated over silica gel, and the resulting silica gel supported crude product was loaded onto an Analogix SuperFlash™ column. Flash chromatography (15%-35% ethyl acetate in hexanes) afforded 2.26 g (77%) of 3-(methanesulfonyl)benzyl chloride as a white solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 8.01 (s, 1 H), 7.91 (d, J=7.8 Hz, 1 H), 7.81 (d, J=7.8 Hz, 1 H), 7.68 (t, J=7.8 Hz, 1 H), 4.90 (s, 2 H), 3.24 (s, 3 H). HRMS (EI+) cald. for C8H9ClO2S [M+] 204.0012, obsd. 204.0012.