Reaction #1994268

ord-b008e0e4ee0041508306f9518781d2e0

Reaction equation

C[C@H](CCC(=O)OC(C(F)(F)F)C(F)(F)S(=O)(=O)[O-])[C@H]1CC[C@H]2[C@@H]3C(=O)CC4CC(=O)CC[C@]4(C)[C@H]3CC(=O)[C@]12C.C[N+](C)(C)Cc1ccccc1
benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2-(3,7,12-trioxocholanoyloxy)-1-propanesulfonate
FC(F)(F)COc1cccc2ccccc12
1-(2,2,2-trifluoroethoxy)naphthalene
O=S1CCCC1
tetramethylene sulfoxide
CC(C)OC(C)C
diisopropyl ether
→
C[C@H](CCC(=O)OC(C(F)(F)F)C(F)(F)S(=O)(=O)[O-])[C@H]1CC[C@H]2[C@@H]3C(=O)CC4CC(=O)CC[C@]4(C)[C@H]3CC(=O)[C@]12C.FC(F)(F)COc1ccc([S+]2CCCC2)c2ccccc12
4-(2,2,2-trifluoroethoxy)-1-naphthyl-tetrahydrothiophenium 1,1,3,3,3-pentafluoro-2-(3,7,12-trioxocholanoyloxy)-1-propanesulfonate
Yield 67.0%

Reactants

C[C@H](CCC(=O)OC(C(F)(F)F)C(F)(F)S(=O)(=O)[O-])[C@H]1CC[C@H]2[C@@H]3C(=O)CC4CC(=O)CC[C@]4(C)[C@H]3CC(=O)[C@]12C.C[N+](C)(C)Cc1ccccc1
benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2-(3,7,12-trioxocholanoyloxy)-1-propanesulfonate
FC(F)(F)COc1cccc2ccccc12
1-(2,2,2-trifluoroethoxy)naphthalene
O=S1CCCC1
tetramethylene sulfoxide
CC(C)OC(C)C
diisopropyl ether

Reagents

None

Solvents

O
water
CS(=O)(=O)O.O=P12OP3(=O)OP(=O)(O1)OP(=O)(O2)O3
Eaton's reagent
O
water

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    Otherin Synthesis Example 1-3
  2. 2
    Otherwas separated
  3. 3
    WashThe water layer was again washed with 30 g of diisopropyl ether
  4. 4
    Extractionafter which extraction
  5. 5
    WashThe organic layer was washed with water
  6. 6
    workup.DISTILLATIONdistilled in vacuum
  7. 7
    Otherto remove the solvent
  8. 8
    Otherpurified by silica gel column chromatography (elute, dichloromethane/methanol)
  9. 9
    workup.DISSOLUTIONThe product was dissolved in methyl isobutyl ketone
  10. 10
    Washwashed with water
  11. 11
    workup.DISTILLATIONdistilled in vacuum
  12. 12
    Otherto remove the solvent
  13. 13
    Otherdried in vacuum
  14. 14
    workup.ADDITIONThe product was poured into isopropyl ether for crystallization
  15. 15
    Filtrationfiltered
  16. 16
    Otherdried
  17. 17
    Otherobtaining the target compound

Procedure

In 6 g of Eaton's reagent (Aldrich, diphosphorus pentoxide/methanesulfonic acid solution) was dispersed 3.4 g (0.0150 mol) of 1-(2,2,2-trifluoroethoxy)naphthalene in Synthesis Example 1-3. With stirring, 3.2 g (0.0300 mol) of tetramethylene sulfoxide was added dropwise to the dispersion. The solution was matured overnight at room temperature and combined with 30 g of water and 30 g of diisopropyl ether, from which a water layer was separated. The water layer was again washed with 30 g of diisopropyl ether. This aqueous solution was combined with 3.4 g (0.0100 mol) of benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2-(3,7,12-trioxocholanoyloxy)-1-propanesulfonate in Synthesis Example 1-7, after which extraction was effected twice with 50 g of dichloromethane. The organic layer was washed with water, distilled in vacuum to remove the solvent, and purified by silica gel column chromatography (elute, dichloromethane/methanol). The product was dissolved in methyl isobutyl ketone, washed with water, distilled in vacuum to remove the solvent, and dried in vacuum. The product was poured into isopropyl ether for crystallization, filtered and dried, obtaining the target compound. White crystals, 6.2 g, yield 67%.

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08597869B2uspto-grants-2013_12