2-(trifluoromethylsulfanyl)phenol

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

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

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

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 1-hydroxy-2-trifluoromethylthiobenzene (16 mmol, 1.0 eq.) in CH2Cl2 (40 mL) at −78° C. was added a solution of Br2 (0.83 mL, 16 mmol, 1.0 eq.) in CH2Cl2 (18 mL) slowly. The resulting mixture was stirred at −78° C. for 2 h and then warmed to room temperature overnight. The reaction mixture was diluted with water (300 mL) and extracted with CH2Cl2 (3×150 mL). The combined organic layer was washed with brine (400 mL), dried (Na2SO4) and concentrated in vacuo. The crude product was purified by column chromatography using 0-10% EtOAc in hexanes as an eluent to afford 4-bromo-1-hydroxy-2-trifluoromethylthiobenzene in 93% yield as a crystalline solid. warmed to room temperature overnight extracted with CH2Cl2 (3×150 mL) The combined organic layer was washed with brine (400 mL) dried (Na2SO4) concentrated in vacuo The crude product was purified by column chromatography

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 1-hydroxy-2-trifluoromethylthiobenzene (16 mmol, 1.0 eq.) in CH2Cl2 (40 mL) at −78° C. was added a solution of Br2 (0.83 mL, 16 mmol, 1.0 eq.) in CH2Cl2 (18 mL) slowly. The resulting mixture was stirred at −78° C. for 2 h and then warmed to room temperature overnight. The reaction mixture was diluted with water (300 mL) and extracted with CH2Cl2 (3×150 mL). The combined organic layer was washed with brine (400 mL), dried (Na2SO4) and concentrated in vacuo. The crude product was purified by column chromatography using 0-10% EtOAc in hexanes as an eluent to afford 4-bromo-1-hydroxy-2-trifluoromethylthiobenzene in 93% yield as a crystalline solid. warmed to room temperature overnight extracted with CH2Cl2 (3×150 mL) The combined organic layer was washed with brine (400 mL) dried (Na2SO4) concentrated in vacuo The crude product was purified by column chromatography

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

Procedure: A mixture of 4.69 g of 2-methoxyphenyl trifluoromethyl sulfide, obtained according to Example 3, 20 ml of 48% strength by weight aqueous hydrobromic acid, and 20 ml of 96% strength by weight acetic acid was boiled under reflux for 24 hours. The completion of the reaction was then checked by gas chromatography. After cooling, the reaction mixture was poured into water. The organic phase was separated off and the aqueous phase was extracted with dichloromethane. The extract was combined with the organic phase. Drying over magnesium sulfate, concentration, and vacuum distillation gave 2.01 g (46% of theory) of 2-hydroxyphenyl trifluoromethyl sulfide (boiling point 65-66° C. at 26 mbar, melting point 35-37° C.). obtained under reflux for 24 hours After cooling The organic phase was separated off the aqueous phase was extracted with dichloromethane Drying over magnesium sulfate, concentration, and vacuum distillation

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

Procedure: A mixture of 4.69 g of 2-methoxyphenyl trifluoromethyl sulfide, obtained according to Example 3, 20 ml of 48% strength by weight aqueous hydrobromic acid, and 20 ml of 96% strength by weight acetic acid was boiled under reflux for 24 hours. The completion of the reaction was then checked by gas chromatography. After cooling, the reaction mixture was poured into water. The organic phase was separated off and the aqueous phase was extracted with dichloromethane. The extract was combined with the organic phase. Drying over magnesium sulfate, concentration, and vacuum distillation gave 2.01 g (46% of theory) of 2-hydroxyphenyl trifluoromethyl sulfide (boiling point 65-66° C. at 26 mbar, melting point 35-37° C.). obtained under reflux for 24 hours After cooling The organic phase was separated off the aqueous phase was extracted with dichloromethane Drying over magnesium sulfate, concentration, and vacuum distillation

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 1-hydroxy-2-trifluoromethylthiobenzene (16 mmol, 1.0 eq.) in CH2Cl2 (40 mL) at −78° C. was added a solution of Br2 (0.83 mL, 16 mmol, 1.0 eq.) in CH2Cl2 (18 mL) slowly. The resulting mixture was stirred at −78° C. for 2 h and then warmed to room temperature overnight. The reaction mixture was diluted with water (300 mL) and extracted with CH2Cl2 (3×150 mL). The combined organic layer was washed with brine (400 mL), dried (Na2SO4) and concentrated in vacuo. The crude product was purified by column chromatography using 0-10% EtOAc in hexanes as an eluent to afford 4-bromo-1-hydroxy-2-trifluoromethylthiobenzene in 93% yield as a crystalline solid. warmed to room temperature overnight extracted with CH2Cl2 (3×150 mL) The combined organic layer was washed with brine (400 mL) dried (Na2SO4) concentrated in vacuo The crude product was purified by column chromatography

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

Procedure: A mixture of 4.69 g of 2-methoxyphenyl trifluoromethyl sulfide, obtained according to Example 3, 20 ml of 48% strength by weight aqueous hydrobromic acid, and 20 ml of 96% strength by weight acetic acid was boiled under reflux for 24 hours. The completion of the reaction was then checked by gas chromatography. After cooling, the reaction mixture was poured into water. The organic phase was separated off and the aqueous phase was extracted with dichloromethane. The extract was combined with the organic phase. Drying over magnesium sulfate, concentration, and vacuum distillation gave 2.01 g (46% of theory) of 2-hydroxyphenyl trifluoromethyl sulfide (boiling point 65-66° C. at 26 mbar, melting point 35-37° C.). obtained under reflux for 24 hours After cooling The organic phase was separated off the aqueous phase was extracted with dichloromethane Drying over magnesium sulfate, concentration, and vacuum distillation