4-bromo-1-methylsulfanyl-2-(trifluoromethoxy)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: 4-Bromo-1-methylthio-2-trifluoromethoxybenzene was prepared from 4-bromo-2-trifluoromethoxybenzenethiol and methyl iodide by following Method C. The reaction was conducted at room temperature overnight. The crude residue was chromatographed in 20% EtOAc/Hexanes to afford 4-bromo-1-methylthio-2-trifluoromethoxybenzene (85% yield). The crude residue was chromatographed in 20% EtOAc/Hexanes

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

Procedure: 4-Bromo-1-methylthio-2-trifluoromethoxybenzene was prepared from 4-bromo-2-trifluoromethoxybenzenethiol and methyl iodide by following Method C. The reaction was conducted at room temperature overnight. The crude residue was chromatographed in 20% EtOAc/Hexanes to afford 4-bromo-1-methylthio-2-trifluoromethoxybenzene (85% yield). The crude residue was chromatographed in 20% EtOAc/Hexanes

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-1-(methylthio)-2-(trifluoromethoxy)benzene (6.63 g, 23.1 mmol) and triisopropyl borate (6.92 mL, 30.0 mmol) in tetrahydrofuran (50 mL) was added dropwise 1.6 M n-butyllithium-hexane solution (25.0 mL, 40.0 mmol) at −78° C., and the resulting mixture was stirred for 30 min. The reaction mixture was warmed to 0° C., 2 M hydrochloric acid (150 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was washed with hexane/ethyl acetate (5/1) and recrystallized from hexane/tetrahydrofuran to give the title compound (4.13 g, yield 71%) as colorless crystals. the mixture was extracted with ethyl acetate The organic layer was washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was washed with hexane/ethyl acetate (5/1) recrystallized from hexane/tetrahydrofuran

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-1-(methylthio)-2-(trifluoromethoxy)benzene (6.63 g, 23.1 mmol) and triisopropyl borate (6.92 mL, 30.0 mmol) in tetrahydrofuran (50 mL) was added dropwise 1.6 M n-butyllithium-hexane solution (25.0 mL, 40.0 mmol) at −78° C., and the resulting mixture was stirred for 30 min. The reaction mixture was warmed to 0° C., 2 M hydrochloric acid (150 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was washed with hexane/ethyl acetate (5/1) and recrystallized from hexane/tetrahydrofuran to give the title compound (4.13 g, yield 71%) as colorless crystals. the mixture was extracted with ethyl acetate The organic layer was washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was washed with hexane/ethyl acetate (5/1) recrystallized from hexane/tetrahydrofuran

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

Procedure: Following the method of example 9a, reaction of 4-bromo-2-trifluoromethoxy-benzenethiol (1.0 g, 3.48 mmol) with iodomethane (0.238 mL, 3.82 mmol) and potassium carbonate (0.528 g, 3.82 mmol) in 13 mL acetone, followed by oxidation as described in example 39c, using 4-bromo-1-methylsulfanyl-2-trifluoromethoxy-benzene (0.78 g, 2.72 mmol) and oxone® (2.17 g, 3.54 mmol), stirring over night at r.t., addition of oxone® (0.84 g, 1.37 mmol), stirring over night at r.t., addition of oxone® (0.84 g, 1.37 mmol) and stirring over three days at r.t. affords the title compound without further chromatography as a white solid (0.81 g). MS (m/e): 320 (M+H). stirring over night at r.t. stirring over three days at r.t.

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

Procedure: 4-Bromo-1-methylthio-2-trifluoromethoxybenzene was prepared from 4-bromo-2-trifluoromethoxybenzenethiol and methyl iodide by following Method C. The reaction was conducted at room temperature overnight. The crude residue was chromatographed in 20% EtOAc/Hexanes to afford 4-bromo-1-methylthio-2-trifluoromethoxybenzene (85% yield). The crude residue was chromatographed in 20% EtOAc/Hexanes

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-1-(methylthio)-2-(trifluoromethoxy)benzene (6.63 g, 23.1 mmol) and triisopropyl borate (6.92 mL, 30.0 mmol) in tetrahydrofuran (50 mL) was added dropwise 1.6 M n-butyllithium-hexane solution (25.0 mL, 40.0 mmol) at −78° C., and the resulting mixture was stirred for 30 min. The reaction mixture was warmed to 0° C., 2 M hydrochloric acid (150 mL) was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was washed with hexane/ethyl acetate (5/1) and recrystallized from hexane/tetrahydrofuran to give the title compound (4.13 g, yield 71%) as colorless crystals. the mixture was extracted with ethyl acetate The organic layer was washed with saturated brine dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was washed with hexane/ethyl acetate (5/1) recrystallized from hexane/tetrahydrofuran