Hydrochloric Acid → 2,2-bis[(4-methylphenyl)sulfonyloxymethyl]butyl 4-methylbenzenesulfonate

Participants

Reaction Steps

1,1,1-Tris(hydroxymethyl)propane (1; 10.01 g, 74.6 mmol) was added to a stirring solution of pyridine (82.5 mL) at −5° C. p-Toluenesulfonyl chloride (71.04 g, 372.63 mmol) was then slowly added. After 2 hours the reaction was brought to room temperature and stirred for approximately 2 days. The reaction progress was followed by silica gel TLC with dichloromethane (DCM) as the mobile phase and visualized using UV-Vis, iodine, and KMnO4 (ditosylate, Rf≈0.2; 2, Rf≈0.55; p-toluenesulfonyl chloride, Rf≈0.95). The reaction was poured into cold 2 M HCl (600 mL) to precipitate the crude product. The precipitate was washed with several portions of 2 M HCl (3×100 mL), dissolved into ethyl acetate (200 mL), and washed with 2 M HCl (1×50 mL), saturated sodium bicarbonate (3×100 mL), and brine (1×50 mL), dried over anhydrous MgSO4, filtered, and taken to dryness under vacuum to give the product as a white solid. Yield: 42.94 g, 96.5%. 1H NMR (CDCl3; 500 MHz) δ ppm: 0.64 (t, 3H, CH3), 1.35 (q, 2H, CCH2), 2.46 (s, 9H, ArCH3), 3.77 (s, 6H, OCH2), 7.36 (d, 6H, ArH), 7.71 (d, 6H, ArH). 13C NMR (CDCl3 d6; 125.8 MHz) δ ppm: 6.71 (CH3), 21.72 (ArCH3), 21.85 (CCH2), 42.05 (C), 67.81 (OCH2), 128.10 (ArC), 130.23 (ArC), 132.00 (ArC),) 145.52 (ArC). ESI-MS (m/z) 619.30 (619.08 calcd for [M+Na]+ of [C27H32O9S3]). Elemental Anal. calc'd (found) for C27H32O9S3: C, 54.35 (54.40); H, 5.41 (5.47); S, 16.02 (16.12).

Provenance & Evidence