Tetramethylene sulfoxide → 4-(2,2,2-Trifluoroethoxy)-1-naphthyl-tetrahydrothiophenium 1,1,3,3,3-pentafluoro-2-(3,7,12-trioxocholanoyloxy)-1-propanesulfonate

HRID 1907086Notes

Reaction equation

HRID 1907086 reaction equation
[F:1][C:2]([F:16])([F:15])[CH2:3][O:4][C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:8]=[CH:7][CH:6]=1.[CH2:17]1[S:21](=O)[CH2:20][CH2:19][CH2:18]1.C(OC(C)C)(C)C.[F:30][C:31]([F:70])([S:66]([O-:69])(=[O:68])=[O:67])[CH:32]([O:37][C:38](=[O:65])[CH2:39][CH2:40][C@H:41]([C@@H:43]1[C@:60]2([CH3:61])[C@H:46]([C@H:47]3[C@H:57]([CH2:58][C:59]2=[O:62])[C@:55]2([CH3:56])[CH:50]([CH2:51][C:52](=[O:63])[CH2:53][CH2:54]2)[CH2:49][C:48]3=[O:64])[CH2:45][CH2:44]1)[CH3:42])[C:33]([F:36])([F:35])[F:34].C([N+](C)(C)C)C1C=CC=CC=1>CS(O)(=O)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.O>[F:70][C:31]([F:30])([S:66]([O-:69])(=[O:67])=[O:68])[CH:32]([O:37][C:38](=[O:65])[CH2:39][CH2:40][C@H:41]([C@@H:43]1[C@:60]2([CH3:61])[C@H:46]([C@H:47]3[C@H:57]([CH2:58][C:59]2=[O:62])[C@:55]2([CH3:56])[CH:50]([CH2:51][C:52](=[O:63])[CH2:53][CH2:54]2)[CH2:49][C:48]3=[O:64])[CH2:45][CH2:44]1)[CH3:42])[C:33]([F:34])([F:36])[F:35].[F:1][C:2]([F:15])([F:16])[CH2:3][O:4][C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]([S+:21]2[CH2:17][CH2:18][CH2:19][CH2:20]2)=[CH:7][CH:6]=1

Participants

7

Reactant 4

HCID 1128Tetramethylene sulfoxideHCID 7914Diisopropyl EtherHCID 134430561-(2,2,2-Trifluoroethoxy)naphthaleneHCID 86664299Benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2-(3,7,12-trioxocholanoyloxy)-1-propanesulfonate

Product 1

HCID 866642984-(2,2,2-Trifluoroethoxy)-1-naphthyl-tetrahydrothiophenium 1,1,3,3,3-pentafluoro-2-(3,7,12-trioxocholanoyloxy)-1-propanesulfonateYield 67%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 86584057Phosphorus Pentoxide-Methanesulfonic AcidSolvent

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%.

Workup

  1. customin Synthesis Example 1-3
  2. customwas separated
  3. washThe water layer was again washed with 30 g of diisopropyl ether
  4. extractionafter which extraction
  5. washThe organic layer was washed with water
  6. distillationdistilled in vacuum
  7. customto remove the solvent
  8. custompurified by silica gel column chromatography (elute, dichloromethane/methanol)
  9. dissolutionThe product was dissolved in methyl isobutyl ketone
  10. washwashed with water
  11. distillationdistilled in vacuum
  12. customto remove the solvent
  13. customdried in vacuum
  14. additionThe product was poured into isopropyl ether for crystallization
  15. filtrationfiltered
  16. customdried
  17. customobtaining the target compound

Sources & evidence

ORD record
ord-b008e0e4ee0041508306f9518781d2e0
Source dataset
uspto-grants-2013_12
Patent number
US08597869B2

Reaction notes

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