Thionyl Chloride → Tris(4-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate

HRID 725284Notes

Reaction equation

HRID 725284 reaction equation
[Mg].[C:2]([O:6][C:7]1[CH:12]=[CH:11][C:10](Cl)=[CH:9][CH:8]=1)([CH3:5])([CH3:4])[CH3:3].S(Cl)(Cl)=O.C[Si]([O:22][S:23]([C:26]([F:29])([F:28])[F:27])(=[O:25])=[O:24])(C)C.[Cl-].[NH4+]>C1COCC1>[F:27][C:26]([F:29])([F:28])[S:23]([O-:25])(=[O:24])=[O:22].[C:2]([O:6][C:7]1[CH:12]=[CH:11][C:10]([S+:23]([C:26]2[CH:11]=[CH:12][C:7]([O:6][C:2]([CH3:5])([CH3:4])[CH3:3])=[CH:8][CH:9]=2)[C:10]2[CH:11]=[CH:12][C:7]([O:6][C:2]([CH3:5])([CH3:3])[CH3:4])=[CH:8][CH:9]=2)=[CH:9][CH:8]=1)([CH3:5])([CH3:4])[CH3:3]

Participants

7

Reactant 5

HCID 24386Thionyl ChlorideHCID 25517Ammonium ChlorideHCID 65367Trimethylsilyl triflateHCID 1404581-Chloro-4-tert-butoxybenzeneHCID 5462224Magnesium

Product 1

HCID 11814213Tris(4-tert-butoxyphenyl)sulfonium trifluoromethanesulfonateYield 45%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A Grignard reagent was conventionally prepared using 60.7 g (2.5 mol) of magnesium, 461 g (2.5 mol) of 4-tert-butoxyphenyl chloride, and 700 g of THF. The Grignard reagent solution was cooled in an ice water bath whereupon 59.5 g (0.5 mol) of thionyl chloride diluted with 100 g of THF was added dropwise at less 30° C. Reaction mixture was ripened for about 30 minutes. Thereafter, 277.8 g (1.25 mol) of trimethylsilyltrifluoromethane sulfonate was added dropwise at less 20° C. Reaction mixture was further ripened for 1 hour and thereafter, the reaction solution was allowed to stand overnight at room temperature. After the reaction solution was again cooled in an ice water bath, 1,800 g of 16.7% ammonium chloride aqueous solution (NH4Cl 300 g+H2O 1,500 g) was added thereto at a temperature not in excess of 30° C. After separation, 1,000 g of chloroform was added to the organic layer, which was washed three times using 1,000 g of water. Thereafter, the solvent was distilled off under reduced pressure by means of a rotary evaporator and the resulting oily residue was recrystallized, isolating tris(4-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate of 99% purity in an amount of 141 g (yield 45%).

Workup

  1. additionwas added dropwise at less 30° C
  2. customReaction mixture
  3. customReaction mixture
  4. waitwas further ripened for 1 hour
  5. waitto stand overnight at room temperature
  6. temperatureAfter the reaction solution was again cooled in an ice water bath
  7. customexcess of 30° C
  8. customAfter separation, 1,000 g of chloroform
  9. additionwas added to the organic layer, which
  10. washwas washed three times
  11. distillationThereafter, the solvent was distilled off under reduced pressure by means of a rotary evaporator
  12. customthe resulting oily residue was recrystallized

Sources & evidence

ORD record
ord-d40fa7740303486b978211610b1e1984
Source dataset
uspto-grants-1998_01
Patent number
US05705702

Reaction notes

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