[difluoro(phenylsulfanyl)methyl]-trimethylsilane

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

実験手順: Into a mixture of 0.22 g (9.2 mmol) Mg turnings, 1.99 g (18.3 mmol) of TMSCl and 20 ml DMF at room temperature, was added 1.1 g (4.6 mmol) bromodifluoromethyl phenyl sulfide (24). The reaction was stirred at room temperature for another 1 h. Excess TMSCl was removed under vacuum (˜10 mmHg). The residue was washed with ice water and then extracted with dichloromethane (20 mL×3). The organic phase was further washed with brine and water successively, and dried over MgSO4. After solvent removal, the crude product was further purified by silica gel chromatography (pentane as eluent) to give 905 mg (85% yield) product 21 as colorless liquid, b.p. 86˜87° C./4 Torr. 1H NMR (500 MHz, CDCl3): δ0.25 (s, 9H); 7.37 (m, 3H); 7.59 (d, 2H). 13C NMR (125 MHz, CDCl3): δ−4.2; 126.3 (t, 3JC-F=4.1 Hz); 128.8; 129.3; 134.0 (t, 1JC-F=300.1 Hz); 136.2. 19F NMR (470 MHz, CDCl3): δ−88.1 (s). 29Si NMR (99 MHz, CDCl3): 7.7 (t, 2JSi-F=31.28 Hz). IR (neat): 3064; 2965; 2904; 1884; 1585; 1475; 1441; 1414; 1307; 1255; 1076; 1025; 962; 884; 850; 825; 744; 703; 690; 631; 607; 496 cm−1. GC-MS (m/z): 232 (M+), 109 (PhS+), 73 (Me3Si+). HRMS (DEI): m/z calculated for C10H14F2SSi (M+) 232.0553, found 232.0545. Excess TMSCl was removed under vacuum (˜10 mmHg) The residue was washed with ice water extracted with dichloromethane (20 mL×3) The organic phase was further washed with brine and water successively dried over MgSO4 After solvent removal the crude product was further purified by silica gel chromatography (pentane as eluent)

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

実験手順: A solution of sulfur dioxide was prepared by bubbling sulfur dioxide (3.9 g, 61 mmol) in a solution of anhydrous acetonitrile (20 ml) at ambient temperature. This solution was added to PhSCF2SiMe3 (4.3 g, 18.4 mmol, obtained according to the procedure from example 6) and stirred at ambient temperature under an inert atmosphere. Anhydrous CsF (2.8 g, 18.5 mmol) was then added to the reaction mixture, which was stirred at ambient temperature overnight. The reaction was monitored by TLC and by 19F NMR (CDCl3) until the disappearance of PhSCF2SiMe3. F-TEDA (7.15 g, 20 mmol) was added to the mixture, at −20° C., which was then stirred for 1 h at ambient temperature. The mixture was concentrated and the solid residue washed with ethyl ether (10×50 ml). The filtrate was evaporated and the product purified by bulb-to-bulb distillation. The product difluoro(phenylsulfanyl)methanesulfonyl fluoride was obtained in the form of a colorless liquid (2.5 g, 57%). obtained was stirred at ambient temperature overnight which was then stirred for 1 h at ambient temperature The mixture was concentrated the solid residue washed with ethyl ether (10×50 ml) The filtrate was evaporated the product purified by bulb-to-bulb distillation

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

実験手順: A solution of sulfur dioxide was prepared by bubbling sulfur dioxide (3.9 g, 61 mmol) in a solution of anhydrous acetonitrile (20 ml) at ambient temperature. This solution was added to PhSCF2SiMe3 (4.3 g, 18.4 mmol, obtained according to the procedure from example 6) and stirred at ambient temperature under an inert atmosphere. Anhydrous CsF (2.8 g, 18.5 mmol) was then added to the reaction mixture, which was stirred at ambient temperature overnight. The reaction was monitored by TLC and by 19F NMR (CDCl3) until the disappearance of PhSCF2SiMe3. F-TEDA (7.15 g, 20 mmol) was added to the mixture, at −20° C., which was then stirred for 1 h at ambient temperature. The mixture was concentrated and the solid residue washed with ethyl ether (10×50 ml). The filtrate was evaporated and the product purified by bulb-to-bulb distillation. The product difluoro(phenylsulfanyl)methanesulfonyl fluoride was obtained in the form of a colorless liquid (2.5 g, 57%). obtained was stirred at ambient temperature overnight which was then stirred for 1 h at ambient temperature The mixture was concentrated the solid residue washed with ethyl ether (10×50 ml) The filtrate was evaporated the product purified by bulb-to-bulb distillation

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

実験手順: Into a mixture of 0.22 g (9.2 mmol) Mg turnings, 1.99 g (18.3 mmol) of TMSCl and 20 ml DMF at room temperature, was added 1.1 g (4.6 mmol) bromodifluoromethyl phenyl sulfide (24). The reaction was stirred at room temperature for another 1 h. Excess TMSCl was removed under vacuum (˜10 mmHg). The residue was washed with ice water and then extracted with dichloromethane (20 mL×3). The organic phase was further washed with brine and water successively, and dried over MgSO4. After solvent removal, the crude product was further purified by silica gel chromatography (pentane as eluent) to give 905 mg (85% yield) product 21 as colorless liquid, b.p. 86˜87° C./4 Torr. 1H NMR (500 MHz, CDCl3): δ0.25 (s, 9H); 7.37 (m, 3H); 7.59 (d, 2H). 13C NMR (125 MHz, CDCl3): δ−4.2; 126.3 (t, 3JC-F=4.1 Hz); 128.8; 129.3; 134.0 (t, 1JC-F=300.1 Hz); 136.2. 19F NMR (470 MHz, CDCl3): δ−88.1 (s). 29Si NMR (99 MHz, CDCl3): 7.7 (t, 2JSi-F=31.28 Hz). IR (neat): 3064; 2965; 2904; 1884; 1585; 1475; 1441; 1414; 1307; 1255; 1076; 1025; 962; 884; 850; 825; 744; 703; 690; 631; 607; 496 cm−1. GC-MS (m/z): 232 (M+), 109 (PhS+), 73 (Me3Si+). HRMS (DEI): m/z calculated for C10H14F2SSi (M+) 232.0553, found 232.0545. Excess TMSCl was removed under vacuum (˜10 mmHg) The residue was washed with ice water extracted with dichloromethane (20 mL×3) The organic phase was further washed with brine and water successively dried over MgSO4 After solvent removal the crude product was further purified by silica gel chromatography (pentane as eluent)

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

実験手順: Into a mixture of 0.22 g (9.2 mmol) Mg turnings, 1.99 g (18.3 mmol) of TMSCl and 20 ml DMF at room temperature, was added 1.1 g (4.6 mmol) bromodifluoromethyl phenyl sulfide (24). The reaction was stirred at room temperature for another 1 h. Excess TMSCl was removed under vacuum (˜10 mmHg). The residue was washed with ice water and then extracted with dichloromethane (20 mL×3). The organic phase was further washed with brine and water successively, and dried over MgSO4. After solvent removal, the crude product was further purified by silica gel chromatography (pentane as eluent) to give 905 mg (85% yield) product 21 as colorless liquid, b.p. 86˜87° C./4 Torr. 1H NMR (500 MHz, CDCl3): δ0.25 (s, 9H); 7.37 (m, 3H); 7.59 (d, 2H). 13C NMR (125 MHz, CDCl3): δ−4.2; 126.3 (t, 3JC-F=4.1 Hz); 128.8; 129.3; 134.0 (t, 1JC-F=300.1 Hz); 136.2. 19F NMR (470 MHz, CDCl3): δ−88.1 (s). 29Si NMR (99 MHz, CDCl3): 7.7 (t, 2JSi-F=31.28 Hz). IR (neat): 3064; 2965; 2904; 1884; 1585; 1475; 1441; 1414; 1307; 1255; 1076; 1025; 962; 884; 850; 825; 744; 703; 690; 631; 607; 496 cm−1. GC-MS (m/z): 232 (M+), 109 (PhS+), 73 (Me3Si+). HRMS (DEI): m/z calculated for C10H14F2SSi (M+) 232.0553, found 232.0545. Excess TMSCl was removed under vacuum (˜10 mmHg) The residue was washed with ice water extracted with dichloromethane (20 mL×3) The organic phase was further washed with brine and water successively dried over MgSO4 After solvent removal the crude product was further purified by silica gel chromatography (pentane as eluent)

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

実験手順: A solution of sulfur dioxide was prepared by bubbling sulfur dioxide (3.9 g, 61 mmol) in a solution of anhydrous acetonitrile (20 ml) at ambient temperature. This solution was added to PhSCF2SiMe3 (4.3 g, 18.4 mmol, obtained according to the procedure from example 6) and stirred at ambient temperature under an inert atmosphere. Anhydrous CsF (2.8 g, 18.5 mmol) was then added to the reaction mixture, which was stirred at ambient temperature overnight. The reaction was monitored by TLC and by 19F NMR (CDCl3) until the disappearance of PhSCF2SiMe3. F-TEDA (7.15 g, 20 mmol) was added to the mixture, at −20° C., which was then stirred for 1 h at ambient temperature. The mixture was concentrated and the solid residue washed with ethyl ether (10×50 ml). The filtrate was evaporated and the product purified by bulb-to-bulb distillation. The product difluoro(phenylsulfanyl)methanesulfonyl fluoride was obtained in the form of a colorless liquid (2.5 g, 57%). obtained was stirred at ambient temperature overnight which was then stirred for 1 h at ambient temperature The mixture was concentrated the solid residue washed with ethyl ether (10×50 ml) The filtrate was evaporated the product purified by bulb-to-bulb distillation

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

実験手順: Into a mixture of 0.22 g (9.2 mmol) Mg turnings, 1.99 g (18.3 mmol) of TMSCl and 20 ml DMF at room temperature, was added 1.1 g (4.6 mmol) bromodifluoromethyl phenyl sulfide (24). The reaction was stirred at room temperature for another 1 h. Excess TMSCl was removed under vacuum (˜10 mmHg). The residue was washed with ice water and then extracted with dichloromethane (20 mL×3). The organic phase was further washed with brine and water successively, and dried over MgSO4. After solvent removal, the crude product was further purified by silica gel chromatography (pentane as eluent) to give 905 mg (85% yield) product 21 as colorless liquid, b.p. 86˜87° C./4 Torr. 1H NMR (500 MHz, CDCl3): δ0.25 (s, 9H); 7.37 (m, 3H); 7.59 (d, 2H). 13C NMR (125 MHz, CDCl3): δ−4.2; 126.3 (t, 3JC-F=4.1 Hz); 128.8; 129.3; 134.0 (t, 1JC-F=300.1 Hz); 136.2. 19F NMR (470 MHz, CDCl3): δ−88.1 (s). 29Si NMR (99 MHz, CDCl3): 7.7 (t, 2JSi-F=31.28 Hz). IR (neat): 3064; 2965; 2904; 1884; 1585; 1475; 1441; 1414; 1307; 1255; 1076; 1025; 962; 884; 850; 825; 744; 703; 690; 631; 607; 496 cm−1. GC-MS (m/z): 232 (M+), 109 (PhS+), 73 (Me3Si+). HRMS (DEI): m/z calculated for C10H14F2SSi (M+) 232.0553, found 232.0545. Excess TMSCl was removed under vacuum (˜10 mmHg) The residue was washed with ice water extracted with dichloromethane (20 mL×3) The organic phase was further washed with brine and water successively dried over MgSO4 After solvent removal the crude product was further purified by silica gel chromatography (pentane as eluent)