fluoromethylsulfanylbenzene

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

Procedure: Fluoromethyl phenyl sulphide (85 g, 351.63 mmol) was added to a mixture of methanol (250 ml) and water (50 mL). The resulting mixture was cooled to a temperature between 0° C. and 5° C. NBS (75.10 g, 1.2 eq) was added in small portions maintaining the same temperature range. The reaction mixture was stirred until the reaction was complete, and then, was quenched with Na2SO3 solution (10%, 150 mL). The pH of the reaction mixture was adjusted to a value between 7 and 8 with NaHCO3 saturated solution. The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C. The residue was extracted with dichloromethane (200 mL, 300 mL). The combined organic layer was washed with water (2×300 mL) and concentrated to ⅓ of the volume. Heptane (50 mL) was added and the resulting mixture was concentrated again. The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70) to give 49.8 g (89.6%) of the desired product as colourless oil at rt, which is a white solid at −20° C. The resulting mixture was cooled to a temperature between 0° C. and 5° C maintaining the same temperature range was quenched with Na2SO3 solution (10%, 150 mL) The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C The residue was extracted with dichloromethane (200 mL, 300 mL) The combined organic layer was washed with water (2×300 mL) concentrated Heptane (50 mL) was added the resulting mixture was concentrated again The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70)

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

Procedure: Fluoromethyl phenyl sulphide (85 g, 351.63 mmol) was added to a mixture of methanol (250 ml) and water (50 mL). The resulting mixture was cooled to a temperature between 0° C. and 5° C. NBS (75.10 g, 1.2 eq) was added in small portions maintaining the same temperature range. The reaction mixture was stirred until the reaction was complete, and then, was quenched with Na2SO3 solution (10%, 150 mL). The pH of the reaction mixture was adjusted to a value between 7 and 8 with NaHCO3 saturated solution. The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C. The residue was extracted with dichloromethane (200 mL, 300 mL). The combined organic layer was washed with water (2×300 mL) and concentrated to ⅓ of the volume. Heptane (50 mL) was added and the resulting mixture was concentrated again. The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70) to give 49.8 g (89.6%) of the desired product as colourless oil at rt, which is a white solid at −20° C. The resulting mixture was cooled to a temperature between 0° C. and 5° C maintaining the same temperature range was quenched with Na2SO3 solution (10%, 150 mL) The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C The residue was extracted with dichloromethane (200 mL, 300 mL) The combined organic layer was washed with water (2×300 mL) concentrated Heptane (50 mL) was added the resulting mixture was concentrated again The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70)

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

Procedure: Cesium fluoride (191.50 g, 2 eq) was added to a mixture of PEG400 (100 mL) and acetonitrile (600 mL). The mixture was stirred for a few minutes under an argon atmosphere and then acetonitrile (100 mL) was removed by distillation. Chloromethyl phenyl sulfide (100 g, 630.32 mmol) was added and the resulting mixture was stirred for 6 hours at a temperature between 80° C. and 85° C. The mixture was filtered and the filtrate was concentrated. The crude product was purified by distillation to give 52.46 g (58.5%) of the desired product as slightly yellow oil (bp: 43° C. at 40 Pa). acetonitrile (100 mL) was removed by distillation the resulting mixture was stirred for 6 hours at a temperature between 80° C. and 85° C The mixture was filtered the filtrate was concentrated The crude product was purified by distillation

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

Procedure: Fluoromethyl phenyl sulphide (85 g, 351.63 mmol) was added to a mixture of methanol (250 ml) and water (50 mL) The resulting mixture was cooled to a temperature between 0° C. and 5° C. NBS (75.10 g, 1.2 eq) was added in small portions maintaining the same temperature range. The reaction mixture was stirred until the reaction was complete, and then, was quenched with Na2SO3 solution (10%, 150 mL). The pH of the reaction mixture was adjusted to a value between 7 and 8 with NaHCO3 saturated solution. The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C. The residue was extracted with dichloromethane (200 mL, 300 mL). The combined organic layer was washed with water (2×300 mL) and concentrated to 1/3 of the volume. Heptane (50 mL) was added and the resulting mixture was concentrated again. The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70) to give 49.8 g (89.6%) of the desired product as colourless oil at rt, which is a white solid at −20° C. was cooled to a temperature between 0° C. and 5° C maintaining the same temperature range was quenched with Na2SO3 solution (10%, 150 mL) The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C The residue was extracted with dichloromethane (200 mL, 300 mL) The combined organic layer was washed with water (2×300 mL) concentrated to 1/3 of the volume Heptane (50 mL) was added the resulting mixture was concentrated again The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70)

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

Procedure: Cesium fluoride (191.50 g, 2 eq) was added to a mixture of PEG400 (100 mL) and acetonitrile (600 mL). The mixture was stirred for a few minutes under an argon atmosphere and then acetonitrile (100 mL) was removed by distillation. Chloromethyl phenyl sulfide (100 g, 630.32 mmol) was added and the resulting mixture was stirred for 6 hours at a temperature between 80° C. and 85° C. The mixture was filtered and the filtrate was concentrated. The crude product was purified by distillation to give 52.46 g (58.5%) of the desired product as slightly yellow oil (bp: 43° C. at 40 Pa). acetonitrile (100 mL) was removed by distillation the resulting mixture was stirred for 6 hours at a temperature between 80° C. and 85° C The mixture was filtered the filtrate was concentrated The crude product was purified by distillation

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

Procedure: To a stirred solution of (methylsulfinyl)benzene (23.0 g, 164 mmol) in chloroform (80 mL) under argon at room temperature was added diethylaminosulfur trifluoride (43.0 mL, 328 mmol) dropwise and the reaction mixture was stirred for 2 days at this temperature then at 60° C. overnight. The mixture was added dropwise to a stirred solution of saturated aqueous sodium hydrogen carbonate at 0° C. then extracted 3 times with dichloromethane. The combined organic layers were dried over sodium sulfate and concentrated to give (fluoromethyl)(phenyl)sulfane (20.0 g, 86%) as a yellow oil. at 60° C. overnight then extracted 3 times with dichloromethane The combined organic layers were dried over sodium sulfate concentrated

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

Procedure: Fluoromethyl phenyl sulphide (85 g, 351.63 mmol) was added to a mixture of methanol (250 ml) and water (50 mL). The resulting mixture was cooled to a temperature between 0° C. and 5° C. NBS (75.10 g, 1.2 eq) was added in small portions maintaining the same temperature range. The reaction mixture was stirred until the reaction was complete, and then, was quenched with Na2SO3 solution (10%, 150 mL). The pH of the reaction mixture was adjusted to a value between 7 and 8 with NaHCO3 saturated solution. The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C. The residue was extracted with dichloromethane (200 mL, 300 mL). The combined organic layer was washed with water (2×300 mL) and concentrated to ⅓ of the volume. Heptane (50 mL) was added and the resulting mixture was concentrated again. The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70) to give 49.8 g (89.6%) of the desired product as colourless oil at rt, which is a white solid at −20° C. The resulting mixture was cooled to a temperature between 0° C. and 5° C maintaining the same temperature range was quenched with Na2SO3 solution (10%, 150 mL) The mixture was concentrated under vacuum at a temperature between 20° C. and 25° C The residue was extracted with dichloromethane (200 mL, 300 mL) The combined organic layer was washed with water (2×300 mL) concentrated Heptane (50 mL) was added the resulting mixture was concentrated again The crude product was purified by flash chromatography (Ethyl Acetate/Hexane 30:70)

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

Procedure: Cesium fluoride (191.50 g, 2 eq) was added to a mixture of PEG400 (100 mL) and acetonitrile (600 mL). The mixture was stirred for a few minutes under an argon atmosphere and then acetonitrile (100 mL) was removed by distillation. Chloromethyl phenyl sulfide (100 g, 630.32 mmol) was added and the resulting mixture was stirred for 6 hours at a temperature between 80° C. and 85° C. The mixture was filtered and the filtrate was concentrated. The crude product was purified by distillation to give 52.46 g (58.5%) of the desired product as slightly yellow oil (bp: 43° C. at 40 Pa). acetonitrile (100 mL) was removed by distillation the resulting mixture was stirred for 6 hours at a temperature between 80° C. and 85° C The mixture was filtered the filtrate was concentrated The crude product was purified by distillation

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