2-bromo-4-methylsulfanylphenol

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

Procedure: Anhydrous paraformaldehyde (2.14 g) and anhydrous magnesium chloride (−10 mesh, 99.9%, 4.53 g) were suspended in anhydrous THF (120 mL) under nitrogen atmosphere. Freshly distilled TEA (6.7 mL) was added to the above suspended solution and stirred for 30 minutes. To the above mixture, a solution of 2-bromo-4-methylthiophenol (XXI, 5.22 g) in anhydrous THF (40 mL) was added. The resultant mixture was heated at gentle reflux and stirred for 6 h. After the mixture was cooled down to ambient temperature, ether (100 ml) was added. The organic layer was washed with 1N HCl (60 mL×3) and water (60 mL×3), and dried over MgSO4, filtered and solvent removed in vacuo. The mixture was recrystallized from hexane to afford the product (3.60 g, 61%) as a yellow solid. at gentle reflux stirred for 6 h The organic layer was washed with 1N HCl (60 mL×3) and water (60 mL×3) dried over MgSO4 filtered solvent removed in vacuo The mixture was recrystallized from hexane

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

Procedure: Anhydrous paraformaldehyde (2.14 g) and anhydrous magnesium chloride (−10 mesh, 99.9%, 4.53 g) were suspended in anhydrous THF (120 mL) under nitrogen atmosphere. Freshly distilled TEA (6.7 mL) was added to the above suspended solution and stirred for 30 minutes. To the above mixture, a solution of 2-bromo-4-methylthiophenol (XXI, 5.22 g) in anhydrous THF (40 mL) was added. The resultant mixture was heated at gentle reflux and stirred for 6 h. After the mixture was cooled down to ambient temperature, ether (100 ml) was added. The organic layer was washed with 1N HCl (60 mL×3) and water (60 mL×3), and dried over MgSO4, filtered and solvent removed in vacuo. The mixture was recrystallized from hexane to afford the product (3.60 g, 61%) as a yellow solid. at gentle reflux stirred for 6 h The organic layer was washed with 1N HCl (60 mL×3) and water (60 mL×3) dried over MgSO4 filtered solvent removed in vacuo The mixture was recrystallized from hexane

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium thiomethoxide (8.64 g) and copper (I) oxide (8.79 g) were mixed with 2-bromo-4-iodophenol (XX, 14.72 g) in anhydrous DMF (100 mL). The mixture was stirred and heated at 80° C. for 48 h under nitrogen atmosphere. Then, the resultant slurry was treated with concentrated HCl (5 mL) and EtOAc (200 mL), and was filtered and rinsed with EtOAc (200 mL). The organic layers were partitioned with 1N HCl (150 mL), water (150 mL) and brine (150 mL) and dried over MgSO4, filtered and solvent removed in vacuo. Product was purified by silica gel column chromatography, the product eluted with dichloromethane/hexane (2:3), to give the desired product (5.22 g, 39%) as a light brown oil. was filtered rinsed with EtOAc (200 mL) The organic layers were partitioned with 1N HCl (150 mL), water (150 mL) and brine (150 mL) dried over MgSO4 filtered solvent removed in vacuo Product was purified by silica gel column chromatography the product eluted with dichloromethane/hexane (2:3)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium thiomethoxide (8.64 g) and copper (I) oxide (8.79 g) were mixed with 2-bromo-4-iodophenol (XX, 14.72 g) in anhydrous DMF (100 mL). The mixture was stirred and heated at 80° C. for 48 h under nitrogen atmosphere. Then, the resultant slurry was treated with concentrated HCl (5 mL) and EtOAc (200 mL), and was filtered and rinsed with EtOAc (200 mL). The organic layers were partitioned with 1N HCl (150 mL), water (150 mL) and brine (150 mL) and dried over MgSO4, filtered and solvent removed in vacuo. Product was purified by silica gel column chromatography, the product eluted with dichloromethane/hexane (2:3), to give the desired product (5.22 g, 39%) as a light brown oil. was filtered rinsed with EtOAc (200 mL) The organic layers were partitioned with 1N HCl (150 mL), water (150 mL) and brine (150 mL) dried over MgSO4 filtered solvent removed in vacuo Product was purified by silica gel column chromatography the product eluted with dichloromethane/hexane (2:3)