Hydrochloric Acid → 4-Fluorophenyldiphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate

HRID 1625643Notes

Reaction equation

HRID 1625643 reaction equation
[F:1][C:2]([F:19])([S:15]([O-:18])(=[O:17])=[O:16])[CH:3]([O:8]C(=O)C(C)(C)C)[C:4]([F:7])([F:6])[F:5].[F:20][C:21]1[CH:26]=[CH:25][C:24]([S+:27]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[CH:23][CH:22]=1.[OH-].[Na+].Cl.FF.FC(F)(S([O-])(=O)=O)C(O)C(F)(F)F.COC1C=CC([S+](C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>CO.O.FC1C=CC([S+](C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:19][C:2]([F:1])([S:15]([O-:18])(=[O:16])=[O:17])[CH:3]([OH:8])[C:4]([F:5])([F:7])[F:6].[F:20][C:21]1[CH:26]=[CH:25][C:24]([S+:27]([C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[CH:23][CH:22]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 24524FluorineHCID 866653594-Fluorophenyldiphenylsulfonium 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane-1-sulfonateHCID 866653604-Methoxyphenyldiphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonate

Product 1

HCID 866496594-Fluorophenyldiphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 34976544-FluorophenyldiphenylsulfoniumSolvent

Procedure

In 139 g of methanol was dissolved 59.4 g (0.1 mole) of 4-fluorophenyldiphenylsulfonium 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane-1-sulfonate in Comparative Synthesis Example 1. The solution was stirred under ice cooling, to which a solution of 8.0 g (0.2 mole) of sodium hydroxide in 24 g of water was added dropwise at a temperature below 20° C. The solution was stirred overnight at room temperature, after which 21 g of conc. hydrochloric acid and 60 g of water were added to quench the reaction. Methanol was removed in vacuum from the reaction solution, dichloromethane and water were added to the residue, and the organic layer was separated and concentrated again. Diisopropyl ether was added to the residue for crystallization. Filtration and drying gave white crystals. On 19F-NMR analysis of the crystal, however, the peak assigned to fluorine in 4-fluorophenyldiphenylsulfonium cation and observed near −104 ppm extinguished. The product was identified as 4-methoxyphenyldiphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonate (PAG-3). The 1H-NMR and 19F-NMR spectra of PAG-3 are shown in FIGS. 5 and 6, respectively.

Workup

  1. customin Comparative Synthesis Example 1
  2. additionwas added dropwise at a temperature below 20° C
  3. customto quench
  4. customthe reaction
  5. customMethanol was removed in vacuum from the reaction solution, dichloromethane and water
  6. additionwere added to the residue
  7. customthe organic layer was separated
  8. concentrationconcentrated again
  9. additionDiisopropyl ether was added to the residue for crystallization
  10. filtrationFiltration
  11. customdrying
  12. customgave white crystals

Sources & evidence

ORD record
ord-7a6c7ad8052c4bf4a4c6761c3908f74e
Source dataset
uspto-grants-2014_07
Patent number
US08785105B2

Reaction notes

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