4-chloro-2-iodo-1-methylsulfanylbenzene

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 0° C. solution of concentrated sulfuric acid (0.3 mL, 5.0 mmol) in 5.0 mL water and 5.0 mL acetonitrile was added 5-chloro-2-(methylthio)aniline (472 mg, 2.72 mmol), followed by slow addition of sodium nitrite (210 mg, 3.0 mmol) as a solution in 1 mL water. The reaction mixture was stirred at 0° C. for 30 minutes. This mixture was then slowly added to a 0° C. solution of potassium iodide (691.7 mg, 4.167 mmol) in 5 mL water. The reaction was stirred for 1 hour, allowing the ice bath to warm to room temperature. The reaction mixture was then partitioned between water and ethyl acetate. The organic layer was dried with brine and magnesium sulfate and concentrated. The crude product was purified by flash chromatography on silica gel (0 to 30% ethyl acetate in dichloromethane) to yield 598.4 mg (77%) of (4-chloro-2-iodophenyl)(methyl)sulfane. LCMS (ESI) no m/z signal; 1H NMR (400 MHz, DMSO-d6) δ: 7.87 (d, 1H), 7.47 (dd, 1H), 7.20 (d, 1H), 2.47 (s, 3H). The reaction was stirred for 1 hour to warm to room temperature The reaction mixture was then partitioned between water and ethyl acetate The organic layer was dried with brine and magnesium sulfate concentrated The crude product was purified by flash chromatography on silica gel (0 to 30% ethyl acetate in dichloromethane)