Thiophenol → 2-Bromo-6-phenylsulfanylpyridine

To sodium hydride, 0.91 g, (22.3 mmol) (washed with hexane) is added, under nitrogen, 8 ml of tetrahydrofuran. The suspension is then cooled in an ice bath. Thiophenol (2.32 g, 21.1 mmol) in 8 ml of tetrahydrofuran is added dropwise over 30 minutes, after which 4 ml of hexamethylphosphorictriamide is added. The solution is added dropwise over 15 hr to 5 g (21.1 mmol) 2,6-dibromopyridine in 8 ml tetrahydrofuran and 2 ml hexamethylphosphorictriamide at 24°. The reaction mixture is stirred overnight under nitrogen. After addition of 2 ml hexamethylphosphorictriamide, the solution is refluxed for 3 days, then diluted with water and extracted with ether, washed with 5% sodium hydroxide (2×), water (3×) and brine, dried over magnesium sulfate and concentrated. The residue is finally washed with 100 ml cold (ice bath) hexane to give 2-bromo-6-phenylthiopyridine, m.p. 47°.