Methanol → HCID 87870770, compound

HRID 1351065Notes

Reaction equation

HRID 1351065 reaction equation
[F:1][C:2]([F:8])(F)[S:3]([O-:6])(=[O:5])=[O:4].[CH3:9][S:10][C:11]1[CH:16]=[CH:15][C:14]([S+:17]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:13][CH:12]=1.[F:30][C:31]([F:37])(F)S([O-])(=O)=O.ClCl.[CH3:40]O>>[CH:24]12[CH2:40][CH:27]([CH2:26][CH2:25]1)[CH2:28][CH:29]2[C:31]([F:37])([F:30])[C:2]([F:8])([F:1])[S:3]([O-:6])(=[O:5])=[O:4].[CH:9]1([S:10][C:11]2[CH:12]=[CH:13][C:14]([S+:17]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[CH:15][CH:16]=2)[CH2:15][CH2:16][CH2:11][CH2:12][CH2:13]1

Participants

5

Reactant 4

HCID 887MethanolHCID 24526ChlorineHCID 2758875TrifluoromethanesulfonateHCID 23133064HCID 23133064, compound

Product 1

HCID 87870770HCID 87870770, compound

Procedure

19.2 g of the resulting 4-methanethiophenyl diphenylsulfonium trifluoromethane sulfonate was dissolved in 100 g of methanol in a reaction flask. The mixture was fed into an ion-exchange chromatography (an ion-exchange resin: Shephadex R-QAE A25, packing amount: 60 g, manufactured by Aldrich Corporation) to replace trifluoromethanesulfonate anions with chlorine ions. After evaporating methanol using an evaporator, the resulting residue was dissolved in 100 g of dichloromethane. 15 g of 30 wt % 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethane sodium sulfonate aqueous solution was added. The mixture was stirred for one hour at room temperature and transferred to a separatory funnel, shaken, and allowed to stand still. The water layer was removed. 100 ml of distilled water was added and the mixture was shaken again and allowed to stand still. The water layer was removed. The resulting dichloromethane solution was dried with anhydrous magnesium sulfate and filtered. After evaporating dichloromethane from the dried solution, the residual liquid was dried under reduced pressure to obtain 20.1 g of 4-cyclohexylthiophenyl diphenylsulfonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate. 20.1 g of the resulting 4-methanethiophenyl diphenylsulfonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate was dissolved in 300 ml of methanol in a reaction flask. 18 g of 30 wt % hydrogen peroxide solution and 10.5 g of sodium tangstate dihydride were added. The mixture was stirred for 30 minutes at room temperature. The resulting methanol solution was condensed under reduced pressure and the residue was dissolved in 300 g of dichloromethane. The mixture was transferred to a separatory funnel, shaken, and allowed to stand still. The water layer was removed. 100 ml of distilled water was added and the mixture was shaken again and allowed to stand still. The water layer was removed. The resulting dichloromethane solution was dried with anhydrous magnesium sulfate and filtered. After evaporating dichloromethane from the dried solution, the residual liquid was dried under reduced pressure to obtain 15.5 g of 4-methanesulfonylphenyl diphenylsulfonium 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate. This compound is indicated as “acid generator (A-17)”.

Workup

  1. customAfter evaporating methanol using
  2. customan evaporator
  3. dissolutionthe resulting residue was dissolved in 100 g of dichloromethane
  4. addition15 g of 30 wt % 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethane sodium sulfonate aqueous solution was added
  5. customtransferred to a separatory funnel
  6. stirringshaken
  7. customThe water layer was removed
  8. addition100 ml of distilled water was added
  9. stirringthe mixture was shaken again
  10. customThe water layer was removed
  11. dry with materialThe resulting dichloromethane solution was dried with anhydrous magnesium sulfate
  12. filtrationfiltered
  13. customAfter evaporating dichloromethane from the dried solution
  14. customthe residual liquid was dried under reduced pressure

Sources & evidence

ORD record
ord-92b657e17386482b8ead3d034e8ae4d7
Source dataset
uspto-grants-2007_05
Patent number
US07217492B2

Reaction notes

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