4-bromo-2-(trifluoromethoxy)benzenethiol

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:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 4-bromo-2-trifluoromethoxybenzenethiol (1.76 g, 6.44 mmol) in DMF (10 mL) at 0° C. was added NaH (60% in mineral oil, 283 mg, 7.08 mmol) in small portions and the reaction mixture was slowly warmed to 23° C. over 30 minutes. The reaction vessel was evacuated and flushed with trifluoromethyl iodide gas and finally a balloon of trifluoromethyl iodide gas was attached and continued the reaction at 23° C. till the gas is consumed. The reaction mixture was heated to 80° C. with stirring for 2 h, cooled to room temperature and stirred overnight. The reaction mixture was poured into 1.0 N HCl (100 mL) and extracted with ethyl ether. The combined organic layer was washed with brine (80 mL), dried MgSO4 and concentrated in vacuo to get the crude product. This was purified by silica gel column chromatography using pentane as a eluent to afford 4-bromo-2-trifluoromethoxy-1-trifluoromethylthiobenzene (1.12 g, 51%). The reaction vessel was evacuated flushed with trifluoromethyl iodide gas the reaction at 23° C. till the gas is consumed The reaction mixture was heated to 80° C. cooled to room temperature stirred overnight The reaction mixture was poured into 1.0 N HCl (100 mL) extracted with ethyl ether The combined organic layer was washed with brine (80 mL), dried MgSO4 concentrated in vacuo to get the crude product This was purified by silica gel column chromatography

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 4-bromo-2-trifluoromethoxybenzenethiol (1.76 g, 6.44 mmol) in DMF (10 mL) at 0° C. was added NaH (60% in mineral oil, 283 mg, 7.08 mmol) in small portions and the reaction mixture was slowly warmed to 23° C. over 30 minutes. The reaction vessel was evacuated and flushed with trifluoromethyl iodide gas and finally a balloon of trifluoromethyl iodide gas was attached and continued the reaction at 23° C. till the gas is consumed. The reaction mixture was heated to 80° C. with stirring for 2 h, cooled to room temperature and stirred overnight. The reaction mixture was poured into 1.0 N HCl (100 mL) and extracted with ethyl ether. The combined organic layer was washed with brine (80 mL), dried MgSO4 and concentrated in vacuo to get the crude product. This was purified by silica gel column chromatography using pentane as a eluent to afford 4-bromo-2-trifluoromethoxy-1-trifluoromethylthiobenzene (1.12 g, 51%). The reaction vessel was evacuated flushed with trifluoromethyl iodide gas the reaction at 23° C. till the gas is consumed The reaction mixture was heated to 80° C. cooled to room temperature stirred overnight The reaction mixture was poured into 1.0 N HCl (100 mL) extracted with ethyl ether The combined organic layer was washed with brine (80 mL), dried MgSO4 concentrated in vacuo to get the crude product This was purified by silica gel column chromatography

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

実験手順: 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

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

実験手順: 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

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

実験手順: 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.

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

実験手順: 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

反応条件: temp:23.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 4-bromo-2-trifluoromethoxybenzenethiol (1.76 g, 6.44 mmol) in DMF (10 mL) at 0° C. was added NaH (60% in mineral oil, 283 mg, 7.08 mmol) in small portions and the reaction mixture was slowly warmed to 23° C. over 30 minutes. The reaction vessel was evacuated and flushed with trifluoromethyl iodide gas and finally a balloon of trifluoromethyl iodide gas was attached and continued the reaction at 23° C. till the gas is consumed. The reaction mixture was heated to 80° C. with stirring for 2 h, cooled to room temperature and stirred overnight. The reaction mixture was poured into 1.0 N HCl (100 mL) and extracted with ethyl ether. The combined organic layer was washed with brine (80 mL), dried MgSO4 and concentrated in vacuo to get the crude product. This was purified by silica gel column chromatography using pentane as a eluent to afford 4-bromo-2-trifluoromethoxy-1-trifluoromethylthiobenzene (1.12 g, 51%). The reaction vessel was evacuated flushed with trifluoromethyl iodide gas the reaction at 23° C. till the gas is consumed The reaction mixture was heated to 80° C. cooled to room temperature stirred overnight The reaction mixture was poured into 1.0 N HCl (100 mL) extracted with ethyl ether The combined organic layer was washed with brine (80 mL), dried MgSO4 concentrated in vacuo to get the crude product This was purified by silica gel column chromatography