methyl 2-methylsulfanylbenzoate

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: A solution of methyl 2-(methylthio)benzoate (4.0 g, 22.00 mmol) in THF (60 mL) was added to a solution of freshly prepared LDA (2M in THF, 17.5 mL, 35 mmol) placed at −78° C. The reaction mixture was stirred for 1 hour at −78° C., then overnight at room temperature. The reaction mixture was diluted by addition of a saturated solution of ammonium chloride (50 mL). The aqueous phase was separated and extracted with ethyl acetate (3×70 mL). The combined organic phases were washed with a saturated solution of sodium chloride (40 mL), dried over sodium sulfate, filtered and concentrated to dryness. The residue was purified by chromatography on silica gel using petroleum ether/ethyl acetate (95:5 to 9:1) as eluent. The title product was obtained as a pink solid (1.74 g, 53%). placed at −78° C overnight at room temperature The aqueous phase was separated extracted with ethyl acetate (3×70 mL) The combined organic phases were washed with a saturated solution of sodium chloride (40 mL) dried over sodium sulfate filtered concentrated to dryness The residue was purified by chromatography on silica gel

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

Procedure: A solution of methyl 2-(methylthio)benzoate (4.0 g, 22.00 mmol) in THF (60 mL) was added to a solution of freshly prepared LDA (2M in THF, 17.5 mL, 35 mmol) placed at −78° C. The reaction mixture was stirred for 1 hour at −78° C., then overnight at room temperature. The reaction mixture was diluted by addition of a saturated solution of ammonium chloride (50 mL). The aqueous phase was separated and extracted with ethyl acetate (3×70 mL). The combined organic phases were washed with a saturated solution of sodium chloride (40 mL), dried over sodium sulfate, filtered and concentrated to dryness. The residue was purified by chromatography on silica gel using petroleum ether/ethyl acetate (95:5 to 9:1) as eluent. The title product was obtained as a pink solid (1.74 g, 53%). placed at −78° C overnight at room temperature The aqueous phase was separated extracted with ethyl acetate (3×70 mL) The combined organic phases were washed with a saturated solution of sodium chloride (40 mL) dried over sodium sulfate filtered concentrated to dryness The residue was purified by chromatography on silica gel

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

Procedure: To a solution of methyl thiosalicylate (4.0 g, 23.8 mmol) in DMF (25 mL) is added K2CO3 (4.0 g, 28.94 mmol) followed by methyl iodide (2.3 mL, 36.9 mmol). The resulting mixture is stirred at ambient temperature for 1 h. The mixture is diluted with EtOAc and washed with 1N HCl (3×) and water (1×). The organic phase is dried over MgSO4, filtered and concentrated to afford 2-methylsulfanylbenzoic acid methyl ester. washed with 1N HCl (3×) and water (1×) The organic phase is dried over MgSO4 filtered concentrated

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

Procedure: A solution of methyl 2-(methylthio)benzoate (4.0 g, 22.00 mmol) in THF (60 mL) was added to a solution of freshly prepared LDA (2M in THF, 17.5 mL, 35 mmol) placed at −78° C. The reaction mixture was stirred for 1 hour at −78° C., then overnight at room temperature. The reaction mixture was diluted by addition of a saturated solution of ammonium chloride (50 mL). The aqueous phase was separated and extracted with ethyl acetate (3×70 mL). The combined organic phases were washed with a saturated solution of sodium chloride (40 mL), dried over sodium sulfate, filtered and concentrated to dryness. The residue was purified by chromatography on silica gel using petroleum ether/ethyl acetate (95:5 to 9:1) as eluent. The title product was obtained as a pink solid (1.74 g, 53%). placed at −78° C overnight at room temperature The aqueous phase was separated extracted with ethyl acetate (3×70 mL) The combined organic phases were washed with a saturated solution of sodium chloride (40 mL) dried over sodium sulfate filtered concentrated to dryness The residue was purified by chromatography on silica gel

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

Procedure: To a solution of 2-methylsulfanylbenzoic acid methyl ester (0.30 g, 1.7 mmol) in toluene (3.0 mL), diisobutylaluminum hydride (0.94 mol/L toluene solution, 3.9 mL, 3.7 mmol) was added dropwise at −78° C. and the solution was stirred for 3.5 hours. The reaction mixture was added with 2-propanol (0.20 mL), warmed to 0° C., and added with saturated aqueous potassium sodium tartrate solution to separate the mixture into organic layer and aqueous layer. The obtained organic layer was concentrated under reduced pressure and the residue was purified by silica gel chromatography (hexane/ethyl acetate=90/10 to 70/30) to obtain (2-methylsulfanylphenyl)methanol (0.22 g, 87%). to separate the mixture into organic layer and aqueous layer The obtained organic layer was concentrated under reduced pressure the residue was purified by silica gel chromatography (hexane/ethyl acetate=90/10 to 70/30)

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

Procedure: A solution of methyl 2-(methylthio)benzoate (4.0 g, 22.00 mmol) in THF (60 mL) was added to a solution of freshly prepared LDA (2M in THF, 17.5 mL, 35 mmol) placed at −78° C. The reaction mixture was stirred for 1 hour at −78° C., then overnight at room temperature. The reaction mixture was diluted by addition of a saturated solution of ammonium chloride (50 mL). The aqueous phase was separated and extracted with ethyl acetate (3×70 mL). The combined organic phases were washed with a saturated solution of sodium chloride (40 mL), dried over sodium sulfate, filtered and concentrated to dryness. The residue was purified by chromatography on silica gel using petroleum ether/ethyl acetate (95:5 to 9:1) as eluent. The title product was obtained as a pink solid (1.74 g, 53%). placed at −78° C overnight at room temperature The aqueous phase was separated extracted with ethyl acetate (3×70 mL) The combined organic phases were washed with a saturated solution of sodium chloride (40 mL) dried over sodium sulfate filtered concentrated to dryness The residue was purified by chromatography on silica gel

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

Procedure: To a solution of 160 mg (2.97 mmol) of sodium methoxide in 10 mL of methanol was added at 0°, 0.4 mL (2.97 mmol) of methyl thiosalicylate, 0.37 mL (5.97 mmol) of iodomethane and stirred at room temperature for 1 h. The reaction mixture was concentrated in vacuo, taken up in ethyl acetate, washed with water, brine, dried over sodium sulfate, and concentrated in vacuo to give 2.10 g of the title compound. The reaction mixture was concentrated in vacuo washed with water, brine dried over sodium sulfate concentrated in vacuo

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

Procedure: A solution of methyl 2-(methylthio)benzoate (4.0 g, 22.00 mmol) in THF (60 mL) was added to a solution of freshly prepared LDA (2M in THF, 17.5 mL, 35 mmol) placed at −78° C. The reaction mixture was stirred for 1 hour at −78° C., then overnight at room temperature. The reaction mixture was diluted by addition of a saturated solution of ammonium chloride (50 mL). The aqueous phase was separated and extracted with ethyl acetate (3×70 mL). The combined organic phases were washed with a saturated solution of sodium chloride (40 mL), dried over sodium sulfate, filtered and concentrated to dryness. The residue was purified by chromatography on silica gel using petroleum ether/ethyl acetate (95:5 to 9:1) as eluent. The title product was obtained as a pink solid (1.74 g, 53%). placed at −78° C overnight at room temperature The aqueous phase was separated extracted with ethyl acetate (3×70 mL) The combined organic phases were washed with a saturated solution of sodium chloride (40 mL) dried over sodium sulfate filtered concentrated to dryness The residue was purified by chromatography on silica gel