1-bromo-4-(2-methoxyethoxy)benzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To an ice-cooled solution of 4-bromophenoxyethanol (5 g, 23.0 mmol) in THF (30 ml) was added a suspension of sodium hydride (1.10 g, 46.1 mmol) in THF (30 ml), with stirring. After 20 minutes dimethyl sulfate (4.37 ml, 46.1 mmol) was added dropwise. The reaction mixture was stirred for 4 hours at room temperature then quenched slowly with saturated aq. ammonium chloride (50 ml). The mixture was extracted with ethyl acetate (100 ml) and the organic extract was washed successively with 1M hydrochloric acid (50 ml) and brine (50 ml), dried over anhydrous magnesium sulfate and filtered. The solvent was removed under reduced pressure to leave 4-(2-methoxy-ethoxy)-bromobenzene (5.5 g, ca. quant.) as a pale brown oil. 1H-NMR; δ (CDCl3), 7.36 (2H, d, J=9.1 Hz), 6.80 (2H, d, J=9.1 Hz), 4.09 (2H, t, J=4.7 Hz), 3.74 (2H, t, J=4.7 Hz) and 3.45 (3H, s). was added The reaction mixture was stirred for 4 hours at room temperature then quenched slowly with saturated aq. ammonium chloride (50 ml) The mixture was extracted with ethyl acetate (100 ml) the organic extract was washed successively with 1M hydrochloric acid (50 ml) and brine (50 ml) dried over anhydrous magnesium sulfate filtered The solvent was removed under reduced pressure

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Potassium carbonate (2.4 g, 17.3 mmol) was suspended in N,N-dimethyl formamide (15 mL). 4-bromophenol (1.00 g, 5.78 mmol) and 1-bromo-2-methoxyethane (0.964 g, 6.94 mmol) were added into the reaction sequentially and the resulting mixture was stirred at 60° C. for 17 hours. The reaction mixture was diluted with water and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with brine (50 mL) dried over sodium sulfate and evaporated to give the title compound (1.3 g, 99%) as a yellow oil. extracted with ethyl acetate (3×50 mL) The combined organic layers were washed with brine (50 mL) dried over sodium sulfate evaporated

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To a solution of 5-(4,4,5,5,-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine (1.1 g, 4.3 mmol) in tetrahydro ran (40 mL) was added 1-bromo-4-(2-methoxy-ethoxy)-benzene (80, 1.50 g, 6.49 mmol) and tetrakis(triphenylphosphine)palladium (0) (0.25 g, 0.21 mmol). The reaction mixture was stirred with potassium carbonate solution (10 mL, 1.0 M) and warmed to reflux overnight. The biphasic reaction mixture was diluted with ethyl acetate (50 mL) and saturated sodium carbonate solution (20 mL). The organic layer was separated, washed with brine, dried over magnesium sulfate and purified by silica gel column chromatography (50-100% ethyl acetate in hexanes) to give the desired compound as a colorless solid (81, 782 mg, 67%). MS (ESI) [M+H+]+=267.4. warmed to reflux overnight The biphasic reaction mixture The organic layer was separated washed with brine dried over magnesium sulfate purified by silica gel column chromatography (50-100% ethyl acetate in hexanes)

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

Procedure: To a solution of 5-(4,4,5,5,-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine (1.1 g, 4.3 mmol) in tetrahydro ran (40 mL) was added 1-bromo-4-(2-methoxy-ethoxy)-benzene (80, 1.50 g, 6.49 mmol) and tetrakis(triphenylphosphine)palladium (0) (0.25 g, 0.21 mmol). The reaction mixture was stirred with potassium carbonate solution (10 mL, 1.0 M) and warmed to reflux overnight. The biphasic reaction mixture was diluted with ethyl acetate (50 mL) and saturated sodium carbonate solution (20 mL). The organic layer was separated, washed with brine, dried over magnesium sulfate and purified by silica gel column chromatography (50-100% ethyl acetate in hexanes) to give the desired compound as a colorless solid (81, 782 mg, 67%). MS (ESI) [M+H+]+=267.4. warmed to reflux overnight The biphasic reaction mixture The organic layer was separated washed with brine dried over magnesium sulfate purified by silica gel column chromatography (50-100% ethyl acetate in hexanes)

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

Procedure: To a solution of 4-bromophenol (79, 5.0 g, 28.9 mmol) in dimethylformamide (15 mL) were added potassium carbonate (4.40 g, 31.8 mmol) and 1-bromo-2-methoxyethane (5.00 g, 36.0 mmol) under an atmosphere of nitrogen. The reaction mixture was stirred at ambient temperature overnight and concentrated under reduced pressure. The residue was slurried in ethyl acetate (50 mL) and filtered. The filtrate was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate and filtered. Silica gel column chromatography (0-10% ethyl acetate in hexanes) gave the desired compound as a colorless oil (80, 3.2 g, 48%). concentrated under reduced pressure filtered The filtrate was washed with saturated sodium bicarbonate solution dried over magnesium sulfate filtered

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

Procedure: To a solution of 4-bromophenol (79, 5.0 g, 28.9 mmol) in dimethylformamide (15 mL) were added potassium carbonate (4.40 g, 31.8 mmol) and 1-bromo-2-methoxyethane (5.00 g, 36.0 mmol) under an atmosphere of nitrogen. The reaction mixture was stirred at ambient temperature overnight and concentrated under reduced pressure. The residue was slurried in ethyl acetate (50 mL) and filtered. The filtrate was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate and filtered. Silica gel column chromatography (0-10% ethyl acetate in hexanes) gave the desired compound as a colorless oil (80, 3.2 g, 48%). concentrated under reduced pressure filtered The filtrate was washed with saturated sodium bicarbonate solution dried over magnesium sulfate filtered

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

Procedure: To a solution of 4-bromophenol (646, 5.0 g, 28.9 mmol) in dimethylformamide (15 mL) were added potassium carbonate (4.40 g, 31.8 mmol) and 1-bromo-2-methoxyethane (5.00 g, 36.0 mmol) under an atmosphere of nitrogen. The reaction mixture was stirred at ambient temperature overnight and concentrated under reduced pressure. The residue was slurried in ethyl acetate (50 mL) and filtered. The filtrate was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate and filtered. Silica gel column chromatography (0-10% ethyl acetate in hexanes) gave the desired compound as a colorless oil (647, 3.2 g, 48%). concentrated under reduced pressure filtered The filtrate was washed with saturated sodium bicarbonate solution dried over magnesium sulfate filtered

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

Procedure: To a solution of 4-bromophenol (646, 5.0 g, 28.9 mmol) in dimethylformamide (15 mL) were added potassium carbonate (4.40 g, 31.8 mmol) and 1-bromo-2-methoxyethane (5.00 g, 36.0 mmol) under an atmosphere of nitrogen. The reaction mixture was stirred at ambient temperature overnight and concentrated under reduced pressure. The residue was slurried in ethyl acetate (50 mL) and filtered. The filtrate was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate and filtered. Silica gel column chromatography (0-10% ethyl acetate in hexanes) gave the desired compound as a colorless oil (647, 3.2 g, 48%). concentrated under reduced pressure filtered The filtrate was washed with saturated sodium bicarbonate solution dried over magnesium sulfate filtered