4-bromo-2-chloro-1-ethenoxybenzene

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To an ice-cooled solution of diethylzinc solution (1.0 M in hexanes) (8.25 mL, 8.25 mmol, 2.75 eq.) in DCM (15 mL), trifluoroacetic acid (0.6 mL, 7.80 mmol, 2.60 eq.) was added slowly (gas evolution). Upon addition completion, the mixture was stirred at 0° C. for 10 min. Methyleniodid (0.7 mL, 8.70 mmol, 2.90 eq.) was added dropwise and the mixture was stirred at 0° C. for 10 min. A solution of 4-bromo-2-chloro-1-vinyloxy-benzene (700 mg, 3.00 mmol, 1.00 eq.) in DCM (5 mL) was added dropwise. The reaction mixture was stirred at 0° C. for 30 min and further at r.t. for 1 hour, then quenched with 2N aq. HCl soln. (15 mL) and water (5 mL). The layers were separated. The aq. layer was extracted with DCM (1×25 mL). The comb. org. phases were dried over MgSO4 and concentrated in vacuo. The residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 30 fractions of 45 mL, Heptane to Heptane+5% AcOEt) to yield 4-bromo-2-chloro-1-cyclopropoxy-benzene as a colorless oil. was added slowly (gas evolution) Upon addition completion the mixture was stirred at 0° C. for 10 min The reaction mixture was stirred at 0° C. for 30 min and further at r.t. for 1 hour quenched with 2N aq. HCl soln The layers were separated The aq. layer was extracted with DCM (1×25 mL) phases were dried over MgSO4 concentrated in vacuo The residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 30 fractions of 45 mL, Heptane to Heptane+5% AcOEt)

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

実験手順: To a solution of 4-bromo-2-chloro-1-(2-chloro-ethoxy)-benzene (5.84 g, 17.4 mmol, 1 eq.) in DMF (22 mL), sodium hydride 60% dispersion in mineral oil (1.40 g, 34.9 mmol, 2 eq.) was added portionwise at r.t. The resulting mixture was stirred at r.t. for 18 hours. The mixture was partitioned between water (70 mL) and AcOEt (250 mL). The layers were separated and the org. layer was washed with water (4×100 mL), dried over MgSO4, filtered, and concentrated in vacuo. To a solution of the residue in DMF (22 mL), sodium hydride 60% dispersion in mineral oil (1.40 g, 34.9 mmol, 2 eq.) was added portionwise at r.t. The resulting mixture was stirred at r.t. for 48 hours. The mixture was partitioned between water (70 mL) and AcOEt (250 mL). The layers were separated and the org. layer was washed with water (4×100 mL), dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 30 fractions of 45 mL, Heptane 100% to Heptane+5% AcOEt) to give 4-bromo-2-chloro-1-vinyloxy-benzene as a colorless oil. The mixture was partitioned between water (70 mL) and AcOEt (250 mL) The layers were separated layer was washed with water (4×100 mL) dried over MgSO4 filtered concentrated in vacuo The resulting mixture was stirred at r.t. for 48 hours The mixture was partitioned between water (70 mL) and AcOEt (250 mL) The layers were separated layer was washed with water (4×100 mL) dried over MgSO4 filtered concentrated in vacuo The residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 30 fractions of 45 mL, Heptane 100% to Heptane+5% AcOEt)