methyl 3-sulfanylbenzoate

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:0.00; pressure:0.00; stir:

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

実験手順: To a room temperature solution of 1-{4-[3-(2,6-dichloro-phenyl)-5-isopropyl-3H-[1,2,3]triazol-4-ylmethoxy]-2-methyl-phenyl}-ethanol (70 mg, 0.167 mmol) in toluene (2 mL) are added 3-mercapto-benzoic acid methyl ester (28 mg, 0.167 mmol) and tri-N-butylphosphine (62 μL, 0.251 mmol). The reaction mixture is cooled to 0° C. To the reaction mixture is added 1,1′-(azocarbonyl)-dipiperidine (63 mg, 0.251 mmol). The reaction mixture is warmed to room temperature and stirred overnight. The reaction mixture is concentrated and the residue is chromatographed (40 g SiO2, 0% to 30% EtOAc/Hexanes) to yield 3-(1-{4-[3-(2,6-Dichloro-phenyl)-5-isopropyl-3H-[1,2,3]triazol-4-ylmethoxy]-2-methyl-phenyl}-ethylsulfanyl)-benzoic acid methyl ester (62 mg, 65%). The reaction mixture is warmed to room temperature The reaction mixture is concentrated the residue is chromatographed (40 g SiO2, 0% to 30% EtOAc/Hexanes)

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

実験手順: 3-Mercaptobenzoic acid (10.0 g) was suspended in methanol (310 mL), added with sulfuric acid (0.3 mL), and stirred for 24 hours under reflux with heating. After cooling to room temperature, the solvent was evaporated under reduced pressure and water was added to residues. After adjusting to pH 8 by using a saturated aqueous solution of sodium hydrogen carbonate, it was extracted with ethyl acetate and dried over anhydrous sodium sulfate. After distilling the solvent under reduced pressure, the residues were purified by silica gel column chromatography (10% ethyl acetate/hexane) to obtain the title compound as a colorless oil. under reflux with heating the solvent was evaporated under reduced pressure and water was added to residues was extracted with ethyl acetate dried over anhydrous sodium sulfate After distilling the solvent under reduced pressure the residues were purified by silica gel column chromatography (10% ethyl acetate/hexane)

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

実験手順: 3-(2,2,2-Trifluoroethylthio)benzoic acid methyl ester was prepared 3-mercaptobenzoic acid methyl ester and trifluoroethyl iodide by following Method C. The reaction was conducted at room temperature overnight. The crude residue was chromatographed in 10-20% EtOAc/hexanes to afford 3-(2,2,2-trifluoroethylthio)benzoic acid methyl ester (82% yield). The crude residue was chromatographed in 10-20% EtOAc/hexanes

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 3-mercaptobenzoic acid methyl ester (2.32 g, 13.8 mmol) in DMF (15 mL) at 0° C. was added NaH (60% dispersion in mineral oil, 608 mg, 15.2 mmol) in small portions. After stirring for 10 min at 0° C., and a further 30 min at room temperature, perfluoroisopropyl iodide (2.16 mL, 15.2 mmol, 1.1) was added to the reaction. Following the addition, the reaction was stirred for 10 min at room temperature and then heated to 60° C. After 90 min at 60° C. the reaction was cooled to room temperature, diluted with ethyl ether (150 mL), washed with brine (2×200 mL), saturated aqueous NaHCO3 (200 mL), brine (100 mL), dried over MgSO4 and then concentrated in vacuo. The residue was purified by flash column chromatography on silica gel using 5% EtOAc in hexanes as an eluent to furnish 3-(1,2,2,2-tetrafluoro-1-trifluoromethylethylthio)benzoic acid methyl ester (3.13 g). the addition the reaction was stirred for 10 min at room temperature heated to 60° C After 90 min at 60° C. the reaction was cooled to room temperature washed with brine (2×200 mL), saturated aqueous NaHCO3 (200 mL), brine (100 mL) dried over MgSO4 concentrated in vacuo The residue was purified by flash column chromatography on silica gel using 5% EtOAc in hexanes as an eluent

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of methyl 3-sulfanylbenzoate (375 mg) and potassium carbonate (616 mg) in DMF (11 mL) was added 2-chloro-1,3-thiazole (533 mg), and the mixture was stirred overnight at 100° C., and cooled to room temperature. A sodium hydride 60% dispersion in mineral oil (89 mg) was added thereto, and the mixture was stirred at 100° C. for 3 hr. The reaction mixture was poured into water at room temperature, and the mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (76 mg). cooled to room temperature the mixture was stirred at 100° C. for 3 hr the mixture was extracted with ethyl acetate The extract was washed successively with water and saturated brine dried over anhydrous magnesium sulfate the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography (ethyl acetate/hexane)