Sodium Thiosulfate Pentahydrate → HCID 10573186, compound

Participants

Reaction Steps

To a mixture of crude (R)-3-(2-phenylethyl)-3-[(4-phenylphenoxy)methoxy]hexanol (XI, EXAMPLE 8, 91.1 wt %, 15.40 g, 34.68 mmol) in methylene chloride (47 ml) at 0° is added a solution of potassium bromide (0.4057 35 g, 3.409 mmol, 0.098 equiv) and sodium bicarbonate (1.557 g, 18.53 mmol, 0.53 equiv) in water (20.5 ml) followed by 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy, free radical (0.3060 g, 1.776 mmol, 0.051 equiv). Aqueous sodium hypochlorite (13.4 wt %/vol, 26.6 ml, 47.88 mmol, 1.38 equiv) is then added by syringe pump over 1 hr while maintaining 1-5°. A solution of sodium thiosulfate pentahydrate (0.5182 g, 2.088 mmol, 0.0602 equiv) in water (14 ml) is then added. The phases are separated at 0° and the aqueous phase is washed with 2×50 ml methylene chloride. The organic phases are immediately filtered through magnesol (50.25 g) and rinsed through with methylene chloride (400 ml). The extracts are concentrated to an oil (30 g) and hexane (500 ml) is added. The mixture is concentrated to 250 g net weight and hexane (100 ml) added. The mixture is concentrated to 186 g net weight and pentane (300 ml) added. The resultant slurry is cooled to -50° and the desired product collected by vacuum filtration, washed with -50° pentane (100 ml) and dried to give a solid, analytically pure to give the title compound, mp=47.0-48.5°; TLC Rf=0.41 (ethyl acetate/hexane, 10/90); HPLC rt=10.95 min; NMR (CDCl3) 9.79, 7.53, 7.40, 7.26, 7.20-7.08, 5.40, 2.67, 2.65-2.56, 1.99, 1.76, 1.38, 0.93 δ; CMR (CDCl3) 201.83, 156.90, 141.69, 140.68, 134.82, 128.72, 128.47, 128.29, 128.24, 126.77, 125.99, 116.03, 87.19, 80.36, 50.14, 39.21, 39.14, 29.74, 16.86, 14.45 δ; MS (CI, NH3) m/z (relative intensity) 420 (3.5), 220 (100); [α]25D =14 (C=1.0, methylene chloride).

Provenance & Evidence