pentafluoro(phenyl)-lambda6-sulfane

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1-(pentafluorosulfanyl)benzene (495.9 mg, 2.263 mmol) in CH2Cl2 (10 mL) was added dropwise to BF3.OEt2 (493.3 mg, 3.476 mmol) in a flask cooled with an ice-water bath. tert-Butyl nitrite (300.1 mg, 2.910 mmol) in 2 mL of CH2Cl2 was added dropwise and stirred at 0° C. for 1 h. The precipitated colorless crystals were isolated by filtration. The crystals was dissolve in CH3CN (0.4 mL) and precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether. Removal of the solvent under vacuum afforded the title compound as pale yellow crystals (605.1 mg, 84%): IR (ATR): {tilde over (v)}=2924, 2852, 2309, 1574, 1418, 1304, 1053, 768 cm−1. 1H NMR (500 MHz, CD3CN): δ=8.72 (d, J=9.2 Hz, 2H), 8.40 (d, J=9.2 Hz, 2H) ppm. 13C NMR (125 MHz, CD3COCD3): δ=160.4, (C), 134.4 (2CH), 129.5 (2CH), 120.4 (C) ppm. 19F NMR (470 MHz, CD3CN): δ=77.7 (quint, J=151 Hz, 1 F), 60.9 (d, J=151 Hz, 4 F), −151.5 (s, 4 F) ppm. cooled with an ice-water bath The precipitated colorless crystals were isolated by filtration precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether Removal of the solvent under vacuum

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1-(pentafluorosulfanyl)benzene (495.9 mg, 2.263 mmol) in CH2Cl2 (10 mL) was added dropwise to BF3.OEt2 (493.3 mg, 3.476 mmol) in a flask cooled with an ice-water bath. tert-Butyl nitrite (300.1 mg, 2.910 mmol) in 2 mL of CH2Cl2 was added dropwise and stirred at 0° C. for 1 h. The precipitated colorless crystals were isolated by filtration. The crystals was dissolve in CH3CN (0.4 mL) and precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether. Removal of the solvent under vacuum afforded the title compound as pale yellow crystals (605.1 mg, 84%): IR (ATR): {tilde over (v)}=2924, 2852, 2309, 1574, 1418, 1304, 1053, 768 cm−1. 1H NMR (500 MHz, CD3CN): δ=8.72 (d, J=9.2 Hz, 2H), 8.40 (d, J=9.2 Hz, 2H) ppm. 13C NMR (125 MHz, CD3COCD3): δ=160.4, (C), 134.4 (2CH), 129.5 (2CH), 120.4 (C) ppm. 19F NMR (470 MHz, CD3CN): δ=77.7 (quint, J=151 Hz, 1 F), 60.9 (d, J=151 Hz, 4 F), −151.5 (s, 4 F) ppm. cooled with an ice-water bath The precipitated colorless crystals were isolated by filtration precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether Removal of the solvent under vacuum

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

実験手順: Diazonium salt 1 reacted slowly in MeOH at room temperature to give Ph-SF5 as a major product along with p-SF5—C6H4OH and p-SF5—C6H4OMe as minor products. The rate of dediazoniation was found to increase in warm MeOH; the reaction was nearly complete after 90 min. The observed product distribution, seen in FIG. 9, is consistent with homolytic dediazoniation as the predominant mechanistic pathway (Zollinger, in: Diazo Chemistry I, VCH Verlagsgesellschaft, Weinheim, Germany, 1994, chapter 8).

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1-(pentafluorosulfanyl)benzene (495.9 mg, 2.263 mmol) in CH2Cl2 (10 mL) was added dropwise to BF3.OEt2 (493.3 mg, 3.476 mmol) in a flask cooled with an ice-water bath. tert-Butyl nitrite (300.1 mg, 2.910 mmol) in 2 mL of CH2Cl2 was added dropwise and stirred at 0° C. for 1 h. The precipitated colorless crystals were isolated by filtration. The crystals was dissolve in CH3CN (0.4 mL) and precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether. Removal of the solvent under vacuum afforded the title compound as pale yellow crystals (605.1 mg, 84%): IR (ATR): {tilde over (v)}=2924, 2852, 2309, 1574, 1418, 1304, 1053, 768 cm−1. 1H NMR (500 MHz, CD3CN): δ=8.72 (d, J=9.2 Hz, 2H), 8.40 (d, J=9.2 Hz, 2H) ppm. 13C NMR (125 MHz, CD3COCD3): δ=160.4, (C), 134.4 (2CH), 129.5 (2CH), 120.4 (C) ppm. 19F NMR (470 MHz, CD3CN): δ=77.7 (quint, J=151 Hz, 1 F), 60.9 (d, J=151 Hz, 4 F), −151.5 (s, 4 F) ppm. cooled with an ice-water bath The precipitated colorless crystals were isolated by filtration precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether Removal of the solvent under vacuum

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1-(pentafluorosulfanyl)benzene (495.9 mg, 2.263 mmol) in CH2Cl2 (10 mL) was added dropwise to BF3.OEt2 (493.3 mg, 3.476 mmol) in a flask cooled with an ice-water bath. tert-Butyl nitrite (300.1 mg, 2.910 mmol) in 2 mL of CH2Cl2 was added dropwise and stirred at 0° C. for 1 h. The precipitated colorless crystals were isolated by filtration. The crystals was dissolve in CH3CN (0.4 mL) and precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether. Removal of the solvent under vacuum afforded the title compound as pale yellow crystals (605.1 mg, 84%): IR (ATR): {tilde over (v)}=2924, 2852, 2309, 1574, 1418, 1304, 1053, 768 cm−1. 1H NMR (500 MHz, CD3CN): δ=8.72 (d, J=9.2 Hz, 2H), 8.40 (d, J=9.2 Hz, 2H) ppm. 13C NMR (125 MHz, CD3COCD3): δ=160.4, (C), 134.4 (2CH), 129.5 (2CH), 120.4 (C) ppm. 19F NMR (470 MHz, CD3CN): δ=77.7 (quint, J=151 Hz, 1 F), 60.9 (d, J=151 Hz, 4 F), −151.5 (s, 4 F) ppm. cooled with an ice-water bath The precipitated colorless crystals were isolated by filtration precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether Removal of the solvent under vacuum

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

実験手順: Diazonium salt 1 reacted slowly in MeOH at room temperature to give Ph-SF5 as a major product along with p-SF5—C6H4OH and p-SF5—C6H4OMe as minor products. The rate of dediazoniation was found to increase in warm MeOH; the reaction was nearly complete after 90 min. The observed product distribution, seen in FIG. 9, is consistent with homolytic dediazoniation as the predominant mechanistic pathway (Zollinger, in: Diazo Chemistry I, VCH Verlagsgesellschaft, Weinheim, Germany, 1994, chapter 8).

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A dried 125 mL fluoropolymer (FEP) vessel was flowed with N2 gas and charged with 48.0 g (2.40 mmol) of liquid anhydrous hydrogen fluoride which was cooled at −20° C. The vessel was set with a condenser (made of fluoropolymer) and a thermometer, and cooled in a bath of −20° C. A coolant (−15° C.) was flowed through the condenser. Into the vessel, 8.6 g (0.11 mol) of KF.HF was added. While the mixture was warmed to +15° C., 22.1 g (96.2 mmol) (purity 96 wt % and the other was phenylsulfur trifluoride) of phenylsulfur chlorotetrafluoride was added to the mixture over 1 hour through a syringe. The temperature of the reaction mixture was 3.4° C. and 13.6° C. at the starting point and completing point of the addition, respectively. After the addition, the reaction mixture was stirred at 15° C. for 18 h. After that, the reaction mixture was warmed to 25° C. and hydrogen fluoride was removed under atmospheric pressure. The residue was neutralized with about 15% aqueous KOH and extracted with dichloromethane. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure. The resulting residue was distilled under reduced pressure to give 14.4 g (yield 73%) of phenylsulfur pentafluoride (boiling point 57.5° C./35 mmHg). The purity of the product was determined to be 100% by GC analysis. The product was identified by spectral comparison with an authentic reference sample. The vessel was set with a condenser A coolant (−15° C.) HF was added While the mixture was warmed to +15° C. was added to the mixture over 1 hour through a syringe was 3.4° C. and 13.6° C. at the starting point point of the addition After the addition After that, the reaction mixture was warmed to 25° C. hydrogen fluoride was removed under atmospheric pressure extracted with dichloromethane The organic layer was separated dried over anhydrous magnesium sulfate filtered The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure The resulting residue was distilled under reduced pressure

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A dried 125 mL fluoropolymer (FEP) vessel was flowed with N2 gas and charged with 48.0 g (2.40 mmol) of liquid anhydrous hydrogen fluoride which was cooled at −20° C. The vessel was set with a condenser (made of fluoropolymer) and a thermometer, and cooled in a bath of −20° C. A coolant (−15° C.) was flowed through the condenser. Into the vessel, 8.6 g (0.11 mol) of KF.HF was added. While the mixture was warmed to +15° C., 22.1 g (96.2 mmol) (purity 96 wt % and the other was phenylsulfur trifluoride) of phenylsulfur chlorotetrafluoride was added to the mixture over 1 hour through a syringe. The temperature of the reaction mixture was 3.4° C. and 13.6° C. at the starting point and completing point of the addition, respectively. After the addition, the reaction mixture was stirred at 15° C. for 18 h. After that, the reaction mixture was warmed to 25° C. and hydrogen fluoride was removed under atmospheric pressure. The residue was neutralized with about 15% aqueous KOH and extracted with dichloromethane. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure. The resulting residue was distilled under reduced pressure to give 14.4 g (yield 73%) of phenylsulfur pentafluoride (boiling point 57.5° C./35 mmHg). The purity of the product was determined to be 100% by GC analysis. The product was identified by spectral comparison with an authentic reference sample. The vessel was set with a condenser A coolant (−15° C.) HF was added While the mixture was warmed to +15° C. was added to the mixture over 1 hour through a syringe was 3.4° C. and 13.6° C. at the starting point point of the addition After the addition After that, the reaction mixture was warmed to 25° C. hydrogen fluoride was removed under atmospheric pressure extracted with dichloromethane The organic layer was separated dried over anhydrous magnesium sulfate filtered The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure The resulting residue was distilled under reduced pressure

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A dried 125 mL fluoropolymer (FEP) vessel was flowed with N2 gas and charged with 48.0 g (2.40 mmol) of liquid anhydrous hydrogen fluoride which was cooled at −20° C. The vessel was set with a condenser (made of fluoropolymer) and a thermometer, and cooled in a bath of −20° C. A coolant (−15° C.) was flowed through the condenser. Into the vessel, 8.6 g (0.11 mol) of KF.HF was added. While the mixture was warmed to +15° C., 22.1 g (96.2 mmol) (purity 96 wt % and the other was phenylsulfur trifluoride) of phenylsulfur chlorotetrafluoride was added to the mixture over 1 hour through a syringe. The temperature of the reaction mixture was 3.4° C. and 13.6° C. at the starting point and completing point of the addition, respectively. After the addition, the reaction mixture was stirred at 15° C. for 18 h. After that, the reaction mixture was warmed to 25° C. and hydrogen fluoride was removed under atmospheric pressure. The residue was neutralized with about 15% aqueous KOH and extracted with dichloromethane. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure. The resulting residue was distilled under reduced pressure to give 14.4 g (yield 73%) of phenylsulfur pentafluoride (boiling point 57.5° C./35 mmHg). The purity of the product was determined to be 100% by GC analysis. The product was identified by spectral comparison with an authentic reference sample. The vessel was set with a condenser A coolant (−15° C.) HF was added While the mixture was warmed to +15° C. was added to the mixture over 1 hour through a syringe was 3.4° C. and 13.6° C. at the starting point point of the addition After the addition After that, the reaction mixture was warmed to 25° C. hydrogen fluoride was removed under atmospheric pressure extracted with dichloromethane The organic layer was separated dried over anhydrous magnesium sulfate filtered The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure The resulting residue was distilled under reduced pressure

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A dried 125 mL fluoropolymer (FEP) vessel was flowed with N2 gas and charged with 48.0 g (2.40 mmol) of liquid anhydrous hydrogen fluoride which was cooled at −20° C. The vessel was set with a condenser (made of fluoropolymer) and a thermometer, and cooled in a bath of −20° C. A coolant (−15° C.) was flowed through the condenser. Into the vessel, 8.6 g (0.11 mol) of KF.HF was added. While the mixture was warmed to +15° C., 22.1 g (96.2 mmol) (purity 96 wt % and the other was phenylsulfur trifluoride) of phenylsulfur chlorotetrafluoride was added to the mixture over 1 hour through a syringe. The temperature of the reaction mixture was 3.4° C. and 13.6° C. at the starting point and completing point of the addition, respectively. After the addition, the reaction mixture was stirred at 15° C. for 18 h. After that, the reaction mixture was warmed to 25° C. and hydrogen fluoride was removed under atmospheric pressure. The residue was neutralized with about 15% aqueous KOH and extracted with dichloromethane. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure. The resulting residue was distilled under reduced pressure to give 14.4 g (yield 73%) of phenylsulfur pentafluoride (boiling point 57.5° C./35 mmHg). The purity of the product was determined to be 100% by GC analysis. The product was identified by spectral comparison with an authentic reference sample. The vessel was set with a condenser A coolant (−15° C.) HF was added While the mixture was warmed to +15° C. was added to the mixture over 1 hour through a syringe was 3.4° C. and 13.6° C. at the starting point point of the addition After the addition After that, the reaction mixture was warmed to 25° C. hydrogen fluoride was removed under atmospheric pressure extracted with dichloromethane The organic layer was separated dried over anhydrous magnesium sulfate filtered The filtrate was concentrated by distilling the solvent at 70° C. under atmospheric pressure The resulting residue was distilled under reduced pressure

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 1-(pentafluorosulfanyl)benzene (495.9 mg, 2.263 mmol) in CH2Cl2 (10 mL) was added dropwise to BF3.OEt2 (493.3 mg, 3.476 mmol) in a flask cooled with an ice-water bath. tert-Butyl nitrite (300.1 mg, 2.910 mmol) in 2 mL of CH2Cl2 was added dropwise and stirred at 0° C. for 1 h. The precipitated colorless crystals were isolated by filtration. The crystals was dissolve in CH3CN (0.4 mL) and precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether. Removal of the solvent under vacuum afforded the title compound as pale yellow crystals (605.1 mg, 84%): IR (ATR): {tilde over (v)}=2924, 2852, 2309, 1574, 1418, 1304, 1053, 768 cm−1. 1H NMR (500 MHz, CD3CN): δ=8.72 (d, J=9.2 Hz, 2H), 8.40 (d, J=9.2 Hz, 2H) ppm. 13C NMR (125 MHz, CD3COCD3): δ=160.4, (C), 134.4 (2CH), 129.5 (2CH), 120.4 (C) ppm. 19F NMR (470 MHz, CD3CN): δ=77.7 (quint, J=151 Hz, 1 F), 60.9 (d, J=151 Hz, 4 F), −151.5 (s, 4 F) ppm. cooled with an ice-water bath The precipitated colorless crystals were isolated by filtration precipitated by addition of ether to give pale yellow solid crystals, which were washed with diethyl ether Removal of the solvent under vacuum

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

実験手順: Diazonium salt 1 reacted slowly in MeOH at room temperature to give Ph-SF5 as a major product along with p-SF5—C6H4OH and p-SF5—C6H4OMe as minor products. The rate of dediazoniation was found to increase in warm MeOH; the reaction was nearly complete after 90 min. The observed product distribution, seen in FIG. 9, is consistent with homolytic dediazoniation as the predominant mechanistic pathway (Zollinger, in: Diazo Chemistry I, VCH Verlagsgesellschaft, Weinheim, Germany, 1994, chapter 8).