1-bromo-3-iodo-5-methoxybenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Bromo-3-iodo-5-methoxy-benzene (6.29 g, 20.1 mmol) was suspended in a solution of hydrogen bromide in acetic acid (33%, 150 mL). Tetrabutylammonium bromide (0.5 g, 1.55 mmol) was added and the mixture was heated to reflux under vigorous stirring for 2 d. After cooling to room temperature the mixture was extracted with methylene chloride (3×100 mL). The combined organic layers were washed with water (50 mL), dried (MgSO4) and concentrated to give the crude product which was purified by flash chromatography on silica gel (300 g, AcOEt/heptane 1:9). 3-Bromo-5-iodo-phenol (21.2 g, 96%) was obtained as pale brown solid. the mixture was heated to reflux was extracted with methylene chloride (3×100 mL) The combined organic layers were washed with water (50 mL) dried (MgSO4) concentrated to give the crude product which was purified by flash chromatography on silica gel (300 g, AcOEt/heptane 1:9)

反応条件: temp:-5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 1.6 M solution of n-butyllithium in hexane (5.65 mL, 9.04 mmol) was dissolved in dry toluene (50 mL) under dry argon and cooled to −5° C. Then a 2M solution of n-butylmagnesium chloride (2.26 mL, 4.52 mmol) was added slowly with the temperature held below 0° C. over a period of 15 min. Stirring was continued for 45 min at −5° C., followed by drop wise addition of a solution of 1,3-dibromo-5-methoxy-benzene (3.00 g, 11.3 mmol) in toluene (30 mL) with the temperature held below 0° C. The mixture was stirred for 45 min at −5° C. A solution of iodine chloride (1.83 g, 11.3 mmol) in methylene chloride (20 mL) was added in the described manner and stirring continued for additional 20 min at −5° C. The mixture was warmed to room temperature. Water (50 mL) and toluene (50 mL) were added and the layers were separated. The organic layer was washed with a saturated aqueous solution of Na2S2O3 (2×30 mL), water and brine (30 mL). The organic layer was dried (MgSO4) and concentrated to give the crude product which was purified by flash chromatography on silica gel (100 g, AcOEt/heptane 1:9). 1-Bromo-3-iodo-5-methoxy-benzene (2.12 g, 60%) was obtained as a yellow oil, which crystallized quickly upon standing. was continued for 45 min at −5° C. held below 0° C The mixture was stirred for 45 min at −5° C stirring continued for additional 20 min at −5° C The mixture was warmed to room temperature the layers were separated The organic layer was washed with a saturated aqueous solution of Na2S2O3 (2×30 mL), water and brine (30 mL) The organic layer was dried (MgSO4) concentrated to give the crude product which was purified by flash chromatography on silica gel (100 g, AcOEt/heptane 1:9)