trifluoromethylsulfinylbenzene

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (485 mg, 2.5 mmol) in dry 1,3-difluorobenzene (7.4 mL, 75 mmol) was added (CF3SO2)2O (2.10 mL, 12.5 mmol) at 0° C. The reaction mixture was stirred for 2 h at 0° C., and then at rt for another 20 h. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent. The product was obtained as a white crystal (770 mg, 70%), m. p. 78-9° C. (recrystallized from ethyl acetate/hexanes). IR (nujol): 3099 (s), 1600 (s), 1479 (s), 1450 (s), 1200 (s) (cm−1); 1H NMR (CDCl3): 8.26 (d, J2′3′=8.1 Hz, J4′3′=8.1 Hz, 3H), 7.90 (bd, J657.5 Hz, 1H), 7.75 (dd, J3′2′=7.8 Hz, J3′4′=7.8 Hz, 2H), 7.45 (dd, J56=8.1 Hz, J54F=7.8 Hz, 1H), 7.25 (dd, J32F=9.0 Hz, J34F=9.0 Hz, 1H); 19F NMR (CDCl3): −47.6 (s, 3F), −78.3 (s, 3F), −91.7 (s, 1F), −98.2 (s, 1F); 13C NMR (CDCl3): 168 (d, J=261 Hz), 163 (d, J=262), 138, 137, 133, 132, 126 (q, J=262), 123 (q, J=262 Hz), 120, 117, 115, 108 ppm; FAB+-MS [m/e (species, intensity)]: 291 ((C13H8F5S)+, 100), 222 ((C13H8F5S)+-CF3, 80.6), 145 ((C13H8F5S)+-C6H5-CF3, 15.0) ); Chemical analysis: Calculated for C14H8F8O3S2: C, 38.18; H, 1.83; F, 34.52. Found: C, 37.97; H, 1.88; F, 34.90. at rt for another 20 h The solvent was evaporated under reduced pressure the residue was purified by column chromatography on silica gel

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (582 mg, 3.0 mmol) in dry 1-fluorobenzene (8.4 mL, 30 mmol) was added (CF3SO2)2O (2.5 mL, 15 mmol) at 0° C. The reaction mixture was stirred for 10 h at 0° C., and then at rt for another 2 h. Removal of the solvent left a crude residue that was subjected to column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes). IR (nujol): 3108 (m), 1719 (w), 1589 (m), 1494 (m), 1255 (s), 1171 (s), 640 (s) cm−1; 1H NMR (CDCl3): 8.35 (dd, J23=6.0 Hz, J2F=4.0 Hz, 2H), 8.19 (bd, J2′3′=6.0 Hz, 2H), 7.83 (m, 3H), 7.51 (dd, J32=6.0 Hz, J3F=9.0 Hz, 2H); 19F NMR (CDCl3): −50.7 (s, 3F), −78.7 (s, 3F), −95.5 (s, 1F); 13C NMR (CDCl3): 170 (d, J=261 Hz), 139, 137, 135, 135, 127 (q, J=265 Hz), 126 (q, J=263 Hz), 121, 116 ppm; FAB+-MS [m/e (species, intensity)]: 273 ((Cl3H9F4S)+, 100), 272 ((C13H8F4S)+, 14.2), 254 ((C13H9F3S)+, 5.9), 204 ((C13H9F4S)+-CF3, 98.0), 196 ((C13H9F4S)+-C6H5, 5.3), 178 ((C13H9F4S)+-C6H4F, 3.4), 127 ((C6H4FS)+, 13.0), 109 ((C6H5S)+, 20.1) ); Chemical analysis: Calculated for C14H9F7O3S2: C, 39.81; H, 2.15. Found: C, 39.45; H, 2.17. at rt for another 2 h Removal of the solvent left a crude residue that to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes)

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

Procedure: Phenyl trifluoromethyl sulfoxide (0.4 g, 2.1 mmol) and then benzene (4.9 g, 64 mmol) are introduced, under an inert atmosphere and at approximately 0° C. (lower limit below which benzene crystallizes), into a Schlenck tube purged beforehand with argon. Five equivalents of triflic anhydride (2.82 g, 10 mmol) are gradually added. The mixture is stirred for 1 h at 0° C. and then for 24 h at ambient temperature. The medium is evaporated and the residue is purified by chromatography with the CH3CN/CH2Cl2 (1/4) mixture as eluent. White crystals, having a melting point of 69-70° C., are obtained with a yield of 40%. (lower limit below which benzene crystallizes) into a Schlenck tube purged beforehand with argon for 24 h at ambient temperature The medium is evaporated the residue is purified by chromatography with the CH3CN/CH2Cl2 (1/4) mixture as eluent are obtained with a yield of 40%

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (485 mg, 2.5 mmol) in dry 1,3-difluorobenzene (7.4 mL, 75 mmol) was added (CF3SO2)2O (2.10 mL, 12.5 mmol) at 0° C. The reaction mixture was stirred for 2 h at 0° C., and then at rt for another 20 h. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent. The product was obtained as a white crystal (770 mg, 70%), m. p. 78-9° C. (recrystallized from ethyl acetate/hexanes). IR (nujol): 3099 (s), 1600 (s), 1479 (s), 1450 (s), 1200 (s) (cm−1); 1H NMR (CDCl3): 8.26 (d, J2′3′=8.1 Hz, J4′3′=8.1 Hz, 3H), 7.90 (bd, J657.5 Hz, 1H), 7.75 (dd, J3′2′=7.8 Hz, J3′4′=7.8 Hz, 2H), 7.45 (dd, J56=8.1 Hz, J54F=7.8 Hz, 1H), 7.25 (dd, J32F=9.0 Hz, J34F=9.0 Hz, 1H); 19F NMR (CDCl3): −47.6 (s, 3F), −78.3 (s, 3F), −91.7 (s, 1F), −98.2 (s, 1F); 13C NMR (CDCl3): 168 (d, J=261 Hz), 163 (d, J=262), 138, 137, 133, 132, 126 (q, J=262), 123 (q, J=262 Hz), 120, 117, 115, 108 ppm; FAB+-MS [m/e (species, intensity)]: 291 ((C13H8F5S)+, 100), 222 ((C13H8F5S)+-CF3, 80.6), 145 ((C13H8F5S)+-C6H5-CF3, 15.0) ); Chemical analysis: Calculated for C14H8F8O3S2: C, 38.18; H, 1.83; F, 34.52. Found: C, 37.97; H, 1.88; F, 34.90. at rt for another 20 h The solvent was evaporated under reduced pressure the residue was purified by column chromatography on silica gel

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (485 mg, 2.5 mmol) in dry 1,3-difluorobenzene (7.4 mL, 75 mmol) was added (CF3SO2)2O (2.10 mL, 12.5 mmol) at 0° C. The reaction mixture was stirred for 2 h at 0° C., and then at rt for another 20 h. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent. The product was obtained as a white crystal (770 mg, 70%), m. p. 78-9° C. (recrystallized from ethyl acetate/hexanes). IR (nujol): 3099 (s), 1600 (s), 1479 (s), 1450 (s), 1200 (s) (cm−1); 1H NMR (CDCl3): 8.26 (d, J2′3′=8.1 Hz, J4′3′=8.1 Hz, 3H), 7.90 (bd, J657.5 Hz, 1H), 7.75 (dd, J3′2′=7.8 Hz, J3′4′=7.8 Hz, 2H), 7.45 (dd, J56=8.1 Hz, J54F=7.8 Hz, 1H), 7.25 (dd, J32F=9.0 Hz, J34F=9.0 Hz, 1H); 19F NMR (CDCl3): −47.6 (s, 3F), −78.3 (s, 3F), −91.7 (s, 1F), −98.2 (s, 1F); 13C NMR (CDCl3): 168 (d, J=261 Hz), 163 (d, J=262), 138, 137, 133, 132, 126 (q, J=262), 123 (q, J=262 Hz), 120, 117, 115, 108 ppm; FAB+-MS [m/e (species, intensity)]: 291 ((C13H8F5S)+, 100), 222 ((C13H8F5S)+-CF3, 80.6), 145 ((C13H8F5S)+-C6H5-CF3, 15.0) ); Chemical analysis: Calculated for C14H8F8O3S2: C, 38.18; H, 1.83; F, 34.52. Found: C, 37.97; H, 1.88; F, 34.90. at rt for another 20 h The solvent was evaporated under reduced pressure the residue was purified by column chromatography on silica gel

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (582 mg, 3.0 mmol) in dry 1-fluorobenzene (8.4 mL, 30 mmol) was added (CF3SO2)2O (2.5 mL, 15 mmol) at 0° C. The reaction mixture was stirred for 10 h at 0° C., and then at rt for another 2 h. Removal of the solvent left a crude residue that was subjected to column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes). IR (nujol): 3108 (m), 1719 (w), 1589 (m), 1494 (m), 1255 (s), 1171 (s), 640 (s) cm−1; 1H NMR (CDCl3): 8.35 (dd, J23=6.0 Hz, J2F=4.0 Hz, 2H), 8.19 (bd, J2′3′=6.0 Hz, 2H), 7.83 (m, 3H), 7.51 (dd, J32=6.0 Hz, J3F=9.0 Hz, 2H); 19F NMR (CDCl3): −50.7 (s, 3F), −78.7 (s, 3F), −95.5 (s, 1F); 13C NMR (CDCl3): 170 (d, J=261 Hz), 139, 137, 135, 135, 127 (q, J=265 Hz), 126 (q, J=263 Hz), 121, 116 ppm; FAB+-MS [m/e (species, intensity)]: 273 ((Cl3H9F4S)+, 100), 272 ((C13H8F4S)+, 14.2), 254 ((C13H9F3S)+, 5.9), 204 ((C13H9F4S)+-CF3, 98.0), 196 ((C13H9F4S)+-C6H5, 5.3), 178 ((C13H9F4S)+-C6H4F, 3.4), 127 ((C6H4FS)+, 13.0), 109 ((C6H5S)+, 20.1) ); Chemical analysis: Calculated for C14H9F7O3S2: C, 39.81; H, 2.15. Found: C, 39.45; H, 2.17. at rt for another 2 h Removal of the solvent left a crude residue that to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes)

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (582 mg, 3.0 mmol) in dry 1-fluorobenzene (8.4 mL, 30 mmol) was added (CF3SO2)2O (2.5 mL, 15 mmol) at 0° C. The reaction mixture was stirred for 10 h at 0° C., and then at rt for another 2 h. Removal of the solvent left a crude residue that was subjected to column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes). IR (nujol): 3108 (m), 1719 (w), 1589 (m), 1494 (m), 1255 (s), 1171 (s), 640 (s) cm−1; 1H NMR (CDCl3): 8.35 (dd, J23=6.0 Hz, J2F=4.0 Hz, 2H), 8.19 (bd, J2′3′=6.0 Hz, 2H), 7.83 (m, 3H), 7.51 (dd, J32=6.0 Hz, J3F=9.0 Hz, 2H); 19F NMR (CDCl3): −50.7 (s, 3F), −78.7 (s, 3F), −95.5 (s, 1F); 13C NMR (CDCl3): 170 (d, J=261 Hz), 139, 137, 135, 135, 127 (q, J=265 Hz), 126 (q, J=263 Hz), 121, 116 ppm; FAB+-MS [m/e (species, intensity)]: 273 ((Cl3H9F4S)+, 100), 272 ((C13H8F4S)+, 14.2), 254 ((C13H9F3S)+, 5.9), 204 ((C13H9F4S)+-CF3, 98.0), 196 ((C13H9F4S)+-C6H5, 5.3), 178 ((C13H9F4S)+-C6H4F, 3.4), 127 ((C6H4FS)+, 13.0), 109 ((C6H5S)+, 20.1) ); Chemical analysis: Calculated for C14H9F7O3S2: C, 39.81; H, 2.15. Found: C, 39.45; H, 2.17. at rt for another 2 h Removal of the solvent left a crude residue that to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes)

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

Procedure: Phenyl trifluoromethyl sulfoxide (0.4 g, 2.1 mmol) and then benzene (4.9 g, 64 mmol) are introduced, under an inert atmosphere and at approximately 0° C. (lower limit below which benzene crystallizes), into a Schlenck tube purged beforehand with argon. Five equivalents of triflic anhydride (2.82 g, 10 mmol) are gradually added. The mixture is stirred for 1 h at 0° C. and then for 24 h at ambient temperature. The medium is evaporated and the residue is purified by chromatography with the CH3CN/CH2Cl2 (1/4) mixture as eluent. White crystals, having a melting point of 69-70° C., are obtained with a yield of 40%. (lower limit below which benzene crystallizes) into a Schlenck tube purged beforehand with argon for 24 h at ambient temperature The medium is evaporated the residue is purified by chromatography with the CH3CN/CH2Cl2 (1/4) mixture as eluent are obtained with a yield of 40%

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (485 mg, 2.5 mmol) in dry 1,3-difluorobenzene (7.4 mL, 75 mmol) was added (CF3SO2)2O (2.10 mL, 12.5 mmol) at 0° C. The reaction mixture was stirred for 2 h at 0° C., and then at rt for another 20 h. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent. The product was obtained as a white crystal (770 mg, 70%), m. p. 78-9° C. (recrystallized from ethyl acetate/hexanes). IR (nujol): 3099 (s), 1600 (s), 1479 (s), 1450 (s), 1200 (s) (cm−1); 1H NMR (CDCl3): 8.26 (d, J2′3′=8.1 Hz, J4′3′=8.1 Hz, 3H), 7.90 (bd, J657.5 Hz, 1H), 7.75 (dd, J3′2′=7.8 Hz, J3′4′=7.8 Hz, 2H), 7.45 (dd, J56=8.1 Hz, J54F=7.8 Hz, 1H), 7.25 (dd, J32F=9.0 Hz, J34F=9.0 Hz, 1H); 19F NMR (CDCl3): −47.6 (s, 3F), −78.3 (s, 3F), −91.7 (s, 1F), −98.2 (s, 1F); 13C NMR (CDCl3): 168 (d, J=261 Hz), 163 (d, J=262), 138, 137, 133, 132, 126 (q, J=262), 123 (q, J=262 Hz), 120, 117, 115, 108 ppm; FAB+-MS [m/e (species, intensity)]: 291 ((C13H8F5S)+, 100), 222 ((C13H8F5S)+-CF3, 80.6), 145 ((C13H8F5S)+-C6H5-CF3, 15.0) ); Chemical analysis: Calculated for C14H8F8O3S2: C, 38.18; H, 1.83; F, 34.52. Found: C, 37.97; H, 1.88; F, 34.90. at rt for another 20 h The solvent was evaporated under reduced pressure the residue was purified by column chromatography on silica gel

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

Procedure: Synthetic details: To a solution of phenyl trifluoromethyl sulfoxide (5) (582 mg, 3.0 mmol) in dry 1-fluorobenzene (8.4 mL, 30 mmol) was added (CF3SO2)2O (2.5 mL, 15 mmol) at 0° C. The reaction mixture was stirred for 10 h at 0° C., and then at rt for another 2 h. Removal of the solvent left a crude residue that was subjected to column chromatography on silica gel using CH3CN—CH2Cl2 (1:4) as eluent to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes). IR (nujol): 3108 (m), 1719 (w), 1589 (m), 1494 (m), 1255 (s), 1171 (s), 640 (s) cm−1; 1H NMR (CDCl3): 8.35 (dd, J23=6.0 Hz, J2F=4.0 Hz, 2H), 8.19 (bd, J2′3′=6.0 Hz, 2H), 7.83 (m, 3H), 7.51 (dd, J32=6.0 Hz, J3F=9.0 Hz, 2H); 19F NMR (CDCl3): −50.7 (s, 3F), −78.7 (s, 3F), −95.5 (s, 1F); 13C NMR (CDCl3): 170 (d, J=261 Hz), 139, 137, 135, 135, 127 (q, J=265 Hz), 126 (q, J=263 Hz), 121, 116 ppm; FAB+-MS [m/e (species, intensity)]: 273 ((Cl3H9F4S)+, 100), 272 ((C13H8F4S)+, 14.2), 254 ((C13H9F3S)+, 5.9), 204 ((C13H9F4S)+-CF3, 98.0), 196 ((C13H9F4S)+-C6H5, 5.3), 178 ((C13H9F4S)+-C6H4F, 3.4), 127 ((C6H4FS)+, 13.0), 109 ((C6H5S)+, 20.1) ); Chemical analysis: Calculated for C14H9F7O3S2: C, 39.81; H, 2.15. Found: C, 39.45; H, 2.17. at rt for another 2 h Removal of the solvent left a crude residue that to give the product as white crystals (886 mg, 70%), mp 80-1 C (recrystallized from ethyl acetate/hexanes)