Bromobenzene → Triphenylsulfonium Tetrafluoroborate

HRID 743943Notes

Reaction equation

HRID 743943 reaction equation
[Mg].Br[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[C:9]1([S:15]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=O)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[F:23][B-:24]([F:27])([F:26])[F:25].[H+]>C(OCC)C.C1C=CC=CC=1>[F:23][B-:24]([F:27])([F:26])[F:25].[C:3]1([S+:15]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

7

Reactant 4

HCID 7961BromobenzeneHCID 13679Diphenyl sulfoxideHCID 28118Tetrafluoroboric acidHCID 5462224Magnesium

Product 1

HCID 2760877Triphenylsulfonium Tetrafluoroborate

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of magnesium turning (12 g) in ethyl ether (500 ml), bromobenzene (83.5 g, 0.54 mole) was added dropwise under reflux with stirring and continued to stir for 1 hour under reflux. to this Grignard reagent, benzene (500 ml) was added and concentrated until 500 ml. To this resultant mixture, a solution of diphenylsulfoxide (30 g, 0.15 mole) in benzene (200 ml) was added and reacted with stirring for 40 hours under reflux. After the reaction mixture was cooled to 0° C., 40% tetrafluoroboric acid (50 ml) was added dropwise at 0°-5° C. and reacted with stirring for 5 hours at the same temperature. After standing at room temperature overnight, the aqueous layer separated was extracted with methylene chloride (100 ml×3), the organic layer was washed with H2O, dried over anhydrous sodium sulfate and dried. The residual crude solid was recrystallized from chloroform/ethyl ether to give 28 g of triphenylsulfonium tetrafluoroborate as white crystals. m.p. 291°-292° C.

Workup

  1. additionwas added dropwise
  2. temperatureunder reflux
  3. stirringto stir for 1 hour
  4. temperatureunder reflux
  5. concentrationconcentrated until 500 ml
  6. customreacted
  7. stirringwith stirring for 40 hours
  8. temperatureunder reflux
  9. customreacted
  10. stirringwith stirring for 5 hours at the same temperature
  11. customthe aqueous layer separated
  12. extractionwas extracted with methylene chloride (100 ml×3)
  13. washthe organic layer was washed with H2O
  14. dry with materialdried over anhydrous sodium sulfate
  15. customdried
  16. customThe residual crude solid was recrystallized from chloroform/ethyl ether

Sources & evidence

ORD record
ord-45cc512aded3406ab97ae1606aaa7cc1
Source dataset
uspto-grants-1996_09
Patent number
US05558976

Reaction notes

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