methyl 4-bromo-2-(2-methylpropoxy)benzoate

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

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of methyl 4-bromo-2-isobutoxybenzoate (12.0 g), bis(pinacolato)diboron (12.2 g), dichloropalladium-triphenylphosphine (1:2, 2.05 g) and potassium acetate (12.3 g) in 1,4-dioxane (120 ml) was stirred at 90° C. for 1.5 hours. After cooling to room temperature, the reaction mixture was poured into ethyl acetate (500 ml) and water (500 ml) and the mixture was filtered through a Celite cake. The organic layer was separated and washed with water (500 ml) and brine (500 ml). The separated organic layer was concentrated under reduced pressure to ca. 150 ml. To the solution were added water (150 ml), acetic acid ammoniate (14.4 g) and sodium periodate (31.2 g) and the reaction mixture was stirred at room temperature for 3.5 hours. The reaction mixture was filtered and washed with ethyl acetate. The filtrate was extracted with ethyl acetate (twice) and the combined organic layer was washed with water and brine and dried over magnesium sulfate. Filtration followed by evaporation under reduced pressure gave a crude product followed by purification by column chromatography on silica gel (eluent: chloroform/methanol=98/2) to give [3-isobutoxy-4-(methoxycarbonyl)phenyl]boronic acid (7.58 g) as a purple solid. After cooling to room temperature the mixture was filtered through a Celite cake The organic layer was separated washed with water (500 ml) and brine (500 ml) The separated organic layer was concentrated under reduced pressure to ca. 150 ml To the solution were added water (150 ml), acetic acid ammoniate (14.4 g) and sodium periodate (31.2 g) the reaction mixture was stirred at room temperature for 3.5 hours The reaction mixture was filtered washed with ethyl acetate The filtrate was extracted with ethyl acetate (twice) and the combined organic layer was washed with water and brine dried over magnesium sulfate Filtration followed by evaporation under reduced pressure gave a crude product followed by purification by column chromatography on silica gel (eluent: chloroform/methanol=98/2)

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of methyl 4-bromo-2-isobutoxybenzoate (12.0 g), bis(pinacolato)diboron (12.2 g), dichloropalladium-triphenylphosphine (1:2, 2.05 g) and potassium acetate (12.3 g) in 1,4-dioxane (120 ml) was stirred at 90° C. for 1.5 hours. After cooling to room temperature, the reaction mixture was poured into ethyl acetate (500 ml) and water (500 ml) and the mixture was filtered through a Celite cake. The organic layer was separated and washed with water (500 ml) and brine (500 ml). The separated organic layer was concentrated under reduced pressure to ca. 150 ml. To the solution were added water (150 ml), acetic acid ammoniate (14.4 g) and sodium periodate (31.2 g) and the reaction mixture was stirred at room temperature for 3.5 hours. The reaction mixture was filtered and washed with ethyl acetate. The filtrate was extracted with ethyl acetate (twice) and the combined organic layer was washed with water and brine and dried over magnesium sulfate. Filtration followed by evaporation under reduced pressure gave a crude product followed by purification by column chromatography on silica gel (eluent: chloroform/methanol=98/2) to give [3-isobutoxy-4-(methoxycarbonyl)phenyl]boronic acid (7.58 g) as a purple solid. After cooling to room temperature the mixture was filtered through a Celite cake The organic layer was separated washed with water (500 ml) and brine (500 ml) The separated organic layer was concentrated under reduced pressure to ca. 150 ml To the solution were added water (150 ml), acetic acid ammoniate (14.4 g) and sodium periodate (31.2 g) the reaction mixture was stirred at room temperature for 3.5 hours The reaction mixture was filtered washed with ethyl acetate The filtrate was extracted with ethyl acetate (twice) and the combined organic layer was washed with water and brine dried over magnesium sulfate Filtration followed by evaporation under reduced pressure gave a crude product followed by purification by column chromatography on silica gel (eluent: chloroform/methanol=98/2)

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

Procedure: To a solution of 4-bromo-2-isobutoxybenzoic acid (14.0 g) in N,N-dimethylformamide (70 ml) were added dipotassium carbonate (14.2 g) and iodomethane (4.79 ml). The mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered and the filtrate was extracted with ethyl acetate-hexane (1/1, 600 ml) and washed with water (500 ml). The water layer was extracted with ethyl acetate-hexane (1/1, 200 ml) and the extract was washed with water (200 ml). The combined organic layer was washed with brine and dried over magnesium sulfate. Filtration followed by evaporation under reduced pressure gave methyl 4-bromo-2-isobutoxybenzoate (12.0 g) as a pale yellow oil. The reaction mixture was filtered the filtrate was extracted with ethyl acetate-hexane (1/1, 600 ml) washed with water (500 ml) The water layer was extracted with ethyl acetate-hexane (1/1, 200 ml) the extract was washed with water (200 ml) The combined organic layer was washed with brine dried over magnesium sulfate Filtration followed by evaporation under reduced pressure

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

Procedure: To a solution of 4-bromo-2-isobutoxybenzoic acid (14.0 g) in N,N-dimethylformamide (70 ml) were added dipotassium carbonate (14.2 g) and iodomethane (4.79 ml). The mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered and the filtrate was extracted with ethyl acetate-hexane (1/1, 600 ml) and washed with water (500 ml). The water layer was extracted with ethyl acetate-hexane (1/1, 200 ml) and the extract was washed with water (200 ml). The combined organic layer was washed with brine and dried over magnesium sulfate. Filtration followed by evaporation under reduced pressure gave methyl 4-bromo-2-isobutoxybenzoate (12.0 g) as a pale yellow oil. The reaction mixture was filtered the filtrate was extracted with ethyl acetate-hexane (1/1, 600 ml) washed with water (500 ml) The water layer was extracted with ethyl acetate-hexane (1/1, 200 ml) the extract was washed with water (200 ml) The combined organic layer was washed with brine dried over magnesium sulfate Filtration followed by evaporation under reduced pressure