methylsulfinylbenzene

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:0.00; pressure:0.00; stir:

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A complex (4) (1.9 mg, 1 mol %) was weighed out in a Schlenk flask, to which racemic phenylmethylsulfoxide (28 mg, 0.2 mmol) was added. Water (0.5 mL) was added, followed by stirring for 10 minutes at 20° C. A 30% hydrogen peroxide solution (9 μL, 0.4 eq) was added, followed by stirring the resultant mixture for 3 hours at room temperature. To the reaction mixture, water (5 mL) was added, followed by extraction using ethyl acetate. An organic phase was dried over anhydrous sodium sulfate, followed by filtration and then it was concentrated under reduced pressure. By purifying the concentrate using silica gel column chromatography (ethyl acetate), 6.5 mg (21% yield) of phenylmethylsulfone was obtained, and 22.1 mg of phenylmethylsulfoxide (79%) was recovered. Optical purity was determined to be 12% ee for a S form after measured by HPLC analysis. was added followed by extraction An organic phase was dried over anhydrous sodium sulfate followed by filtration it was concentrated under reduced pressure By purifying the concentrate

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

Procedure: A solution of methyl phenyl sulfoxide (140 mg, 1 mmol) in CH2Cl2 (5.0 mL) was added to bis(methoxyethyl)aminosulfur trifluoride (332 mg, 1.5 mmol ) under N2 and stirred for 16 h at room temperature. After work-up as above fluoromethyl phenyl sulfide (70% yield as determined by NMR) was obtained. 1H NMR (CDCl3) d 7.5-7.0 (m, 5H), 3.3 (d, 2H). 19F

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of n-butyllithium (2.7 ml of a 1.6M solution in hexanes, 4.3 mmol) in dry tetrahydrofuran (5 ml) cooled to -78° C. under nitrogen was added dropwise a solution of diisopropylamine (0.44 g, 4.3 mmol) in dry tetrahydrofuran (5 ml). The mixture was allowed to warm to -20° C., and was maintained at this temperature for 15 min. After cooling to -78° C. a solution of methyl phenyl sulphoxide (0.55 g, 3.9 mmol) in dry tetrahydrofuran (2 ml) was added dropwise while maintaining the temperature below -65° C. The reaction was stirred for a further 5 rain and then a solution of (±) 1-azabicyclo[2.2.2] oct-3-yl-N-methyl-N-methoxycarboxamide (EP 322182, Description 22) (0.65 g, 3.3 mmol) in dry tetrahydrofuran (5 ml) was added rapidly while ensuring that the temperature did not rise above -60° C. After stirring at -78° C. for 1 h, the reaction was allowed to warm to -30° C., and maintained at this temperature for 30 min. The reaction was then poured into vigorously stirred orthophosphoric acid (20ml of a 5% H3PO4 solution) cooled below 0° C. The aqueous layer was separated, washed with ether (3×20 ml) and then saturated with potassium carbonate. After extraction with chloroform (3×25 ml) the combined organic extracts were dried over sodium sulphate and concentrated in vacuo to give the title compound (D1) as an oil (1.0 g) consisting of a 1:1 mixture of diastereomeric keto sulphoxides. 1H NMR (CDCl3) δ: was maintained at this temperature for 15 min was added dropwise while maintaining the temperature below -65° C did not rise above -60° C After stirring at -78° C. for 1 h to warm to -30° C. maintained at this temperature for 30 min cooled below 0° C The aqueous layer was separated washed with ether (3×20 ml) After extraction with chloroform (3×25 ml) the combined organic extracts were dried over sodium sulphate concentrated in vacuo

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

Procedure: A solution of thioanisole (2.48 g, 20 mmol) in methanol (100 mL) in a 250-mL flask was cooled in an ice bath. Stabilized BrCl solution (15 wt. % solution, 18 mL, ~28 mmol) was then added dropwise, with stirring. After the addition, the ice bath was removed, the reaction mixture was allowed to stand at room temperature and the progress of the reaction was monitored by gas chromatography (GC). In less than one hour, the starting material was totally converted to product and the orange-reddish solution turned light yellow. The reaction mixture was quenched with a few drops of sodium sulfite solution, diluted with ethylene dichloride (EDC, 100 mL), and washed with water (100 mL). After phase separation, the colorless organic layer was dried (Na2SO4) and concentrated under reduced pressure to furnish 2.44 g (~87% yield) of methyl phenyl sulfoxide as a colorless oil. GC analysis indicated the presence of ~2% of the corresponding sulfone. After the addition the ice bath was removed to stand at room temperature In less than one hour The reaction mixture was quenched with a few drops of sodium sulfite solution diluted with ethylene dichloride (EDC, 100 mL) washed with water (100 mL) After phase separation the colorless organic layer was dried (Na2SO4) concentrated under reduced pressure

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl phenyl sulfoxide (21.644 g, 154.4 mmol) was dissolved in anhydrous pyridine (27.4 mL, 2.2 eq) and dry acetonitrile (100 mL). The solution was cooled to −40° C. under an argon atmosphere. A solution of bromine (49.4 g, 2 eq) in dry acetonitrile (50 mL) was added slowly, maintaining the same temperature. The mixture was stirred at −40° C. for 1 h and then overnight at room temperature. The solvent was evaporated under vacuum and the residue was dissolved in dichloromethane. The organic layer was washed with Na2S2O3 20%, dried over anhydrous Na2SO4 and concentrated to dryness. maintaining the same temperature overnight at room temperature The solvent was evaporated under vacuum the residue was dissolved in dichloromethane The organic layer was washed with Na2S2O3 20% dried over anhydrous Na2SO4 concentrated to dryness

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

Procedure: Methyl phenyl sulphide (20 g, 161.03 mmol) was added to a mixture of methanol (100 ml) and water (20 mL). NBS (34.39 g, 1.2 eq) was added in portions maintaining the temperature between 0° and 5° C. The mixture was stirred at the same temperature until the reaction was complete. Thereafter, the reaction mixture was quenched by the addition of Na2SO3 (10%, 60 ml). The pH of the resulting reaction mixture was adjusted to a value between 7 and 8 with saturated NaHCO3 solution. The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C. The residue was extracted with dichloromethane (2×125 mL). The combined organic layer was washed with water (2×125 mL) and concentrated to ⅓ of the volume. Heptane (20 mL) was added and then removed by distillation to give 21.64 g (95.9%) of the desired product as colourless oil. maintaining the temperature between 0° and 5° C Thereafter, the reaction mixture was quenched by the addition of Na2SO3 (10%, 60 ml) The pH of the resulting reaction mixture The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C The residue was extracted with dichloromethane (2×125 mL) The combined organic layer was washed with water (2×125 mL) concentrated Heptane (20 mL) was added removed by distillation

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

Procedure: A solution of methyl phenyl sulfoxide (4.0 g, 147 mmol) in CH2Cl2 is cooled to −78° C., treated dropwise with trifluoroacetic anhydride (4.0 mL, 5.99 g, 28.5 mmol), stirred for 30 min at −78° C., treated with a solution of indole (1.82 g, 15.6 mmol) in CH2Cl2, stirred for 30 min at −78° C., treated with triethylamine (20 mL, 145 mmol), stirred for 4 days at ambient temperatures and diluted with water. The phases are separated. The organic phase is dried over MgSO4 and concentrated in vacuo. The resultant residue is chromatographed (1:99 methanol:CH2Cl2) to give the title product as a white solid, 3.08 g (88% yield), mp 149–151° C., characterized by mass spectral and HNMR analyses. stirred for 30 min at −78° C. stirred for 4 days at ambient temperatures The phases are separated The organic phase is dried over MgSO4 concentrated in vacuo The resultant residue is chromatographed (1:99 methanol:CH2Cl2)

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

Procedure: A solution of methyl phenyl sulfoxide (4.0 g, 147 mmol) in CH2Cl2 is cooled to −78° C., treated dropwise with trifluoroacetic anhydride (4.0 mL, 5.99 g, 28.5 mmol), stirred for 30 min at −78° C., treated with a solution of indole (1.82 g, 15.6 mmol) in CH2Cl2, stirred for 30 min at −78° C., treated with triethylamine (20 mL, 145 mmol), stirred for 4 days at ambient temperatures and diluted with water. The phases are separated. The organic phase is dried over MgSO4 and concentrated in vacuo. The resultant residue is chromatographed (1:99 methanol:CH2Cl2) to give the title product as a white solid, 3.08 g (88% yield), mp 149-151° C., characterized by mass spectral and HNMR analyses. stirred for 30 min at −78° C. stirred for 4 days at ambient temperatures The phases are separated The organic phase is dried over MgSO4 concentrated in vacuo The resultant residue is chromatographed (1:99 methanol:CH2Cl2)