2-Bromo-4-iodophenol

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)

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium iodide (14.2 g) and sodium hydroxide (3.8 g) were added to a solution of 2-bromophenol (XIX, 16.4 g) in methanol (250 mL). The resultant solution was chilled to 0° C. A commercial bleach solution (6% NaClO, 120 mL) was added drop wise at 0-3° C. over 2 h. After the addition, the reaction mixture was stirred for 1 h at 5° C., then treated with 10% sodium thiosulfate aqueous solution (100 mL) and acidified with concentrated HCl to pH 5-7. The mixture was extracted with EtOAc (150 mL×3). The combined organic layers were partitioned with brine, dried over MgSO4, filtered and concentrated under reduced pressure. The resultant oil was purified by silica gel column chromatography; the product eluted with dichloromethane/hexane (2:3), to afford the desired product as a colorless solid (14.76 g, 52%). After the addition The mixture was extracted with EtOAc (150 mL×3) The combined organic layers were partitioned with brine dried over MgSO4 filtered concentrated under reduced pressure The resultant oil was purified by silica gel column chromatography the product eluted with dichloromethane/hexane (2:3)

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium iodide (14.2 g) and sodium hydroxide (3.8 g) were added to a solution of 2-bromophenol (XIX, 16.4 g) in methanol (250 mL). The resultant solution was chilled to 0° C. A commercial bleach solution (6% NaClO, 120 mL) was added drop wise at 0-3° C. over 2 h. After the addition, the reaction mixture was stirred for 1 h at 5° C., then treated with 10% sodium thiosulfate aqueous solution (100 mL) and acidified with concentrated HCl to pH 5-7. The mixture was extracted with EtOAc (150 mL×3). The combined organic layers were partitioned with brine, dried over MgSO4, filtered and concentrated under reduced pressure. The resultant oil was purified by silica gel column chromatography; the product eluted with dichloromethane/hexane (2:3), to afford the desired product as a colorless solid (14.76 g, 52%). After the addition The mixture was extracted with EtOAc (150 mL×3) The combined organic layers were partitioned with brine dried over MgSO4 filtered concentrated under reduced pressure The resultant oil was purified by silica gel column chromatography the product eluted with dichloromethane/hexane (2:3)

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium iodide (14.2 g) and sodium hydroxide (3.8 g) were added to a solution of 2-bromophenol (XIX, 16.4 g) in methanol (250 mL). The resultant solution was chilled to 0° C. A commercial bleach solution (6% NaClO, 120 mL) was added drop wise at 0-3° C. over 2 h. After the addition, the reaction mixture was stirred for 1 h at 5° C., then treated with 10% sodium thiosulfate aqueous solution (100 mL) and acidified with concentrated HCl to pH 5-7. The mixture was extracted with EtOAc (150 mL×3). The combined organic layers were partitioned with brine, dried over MgSO4, filtered and concentrated under reduced pressure. The resultant oil was purified by silica gel column chromatography; the product eluted with dichloromethane/hexane (2:3), to afford the desired product as a colorless solid (14.76 g, 52%). After the addition The mixture was extracted with EtOAc (150 mL×3) The combined organic layers were partitioned with brine dried over MgSO4 filtered concentrated under reduced pressure The resultant oil was purified by silica gel column chromatography the product eluted with dichloromethane/hexane (2:3)