[溴(二氟)甲基]硫基苯

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a three-necked round-bottomed flask placed under a nitrogen atmosphere, topped with a dry-ice condenser and a dropping funnel, thiophenol (10.2 ml, 100 mmol) was added dropwise, over 40 min at 0° C., to a suspension of NaH (6 g, 150 mmol) in anhydrous DMF (100 ml). The mixture was then stirred at 0° C. for 30 min then cooled to −50° C. Dibromodifluoromethane (27 ml, 300 mmol) was then added at −50° C. The mixture was then stirred for 3 h at this temperature, then 30 min at ambient temperature. Water (100 ml) was added to the reaction mixture, then the product was extracted with ethyl ether (3×100 ml). The organic phases were washed with water (3×100 ml) and dried over MgSO4. After evaporation of the solvent, the residue was purified by distillation under reduced pressure (97° C./34 mmHg) to give the product [(bromodifluoromethyl)sulfanyl]benzene in the form of a colorless liquid (15.3 g, 60%). In a three-necked round-bottomed flask placed under a nitrogen atmosphere topped with a dry-ice condenser and a dropping funnel then cooled to −50° C The mixture was then stirred for 3 h at this temperature 30 min at ambient temperature the product was extracted with ethyl ether (3×100 ml) The organic phases were washed with water (3×100 ml) dried over MgSO4 After evaporation of the solvent the residue was purified by distillation under reduced pressure (97° C./34 mmHg)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a three-necked round-bottomed flask placed under a nitrogen atmosphere, topped with a dry-ice condenser and a dropping funnel, thiophenol (10.2 ml, 100 mmol) was added dropwise, over 40 min at 0° C., to a suspension of NaH (6 g, 150 mmol) in anhydrous DMF (100 ml). The mixture was then stirred at 0° C. for 30 min then cooled to −50° C. Dibromodifluoromethane (27 ml, 300 mmol) was then added at −50° C. The mixture was then stirred for 3 h at this temperature, then 30 min at ambient temperature. Water (100 ml) was added to the reaction mixture, then the product was extracted with ethyl ether (3×100 ml). The organic phases were washed with water (3×100 ml) and dried over MgSO4. After evaporation of the solvent, the residue was purified by distillation under reduced pressure (97° C./34 mmHg) to give the product [(bromodifluoromethyl)sulfanyl]benzene in the form of a colorless liquid (15.3 g, 60%). In a three-necked round-bottomed flask placed under a nitrogen atmosphere topped with a dry-ice condenser and a dropping funnel then cooled to −50° C The mixture was then stirred for 3 h at this temperature 30 min at ambient temperature the product was extracted with ethyl ether (3×100 ml) The organic phases were washed with water (3×100 ml) dried over MgSO4 After evaporation of the solvent the residue was purified by distillation under reduced pressure (97° C./34 mmHg)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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)