Tetramethylene sulfoxide → 4-(2,2,2-Trifluoroethoxy)-1-naphthyl-tetrahydrothiophenium 2-(adamantane-1-carbonyloxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate

HRID 1907083Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1907083
[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.[C:30]12([C:40]([O:42][CH:43]([C:51]([F:54])([F:53])[F:52])[C:44]([F:50])([F:49])[S:45]([O-:48])(=[O:47])=[O:46])=[O:41])[CH2:39][CH:34]3[CH2:35][CH:36]([CH2:38][CH:32]([CH2:33]3)[CH2:31]1)[CH2:37]2.C([N+](C)(C)C)C1C=CC=CC=1>CS(O)(=O)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.O>[C:30]12([C:40]([O:42][CH:43]([C:51]([F:54])([F:52])[F:53])[C:44]([F:49])([F:50])[S:45]([O-:48])(=[O:46])=[O:47])=[O:41])[CH2:31][CH:32]3[CH2:38][CH:36]([CH2:35][CH:34]([CH2:33]3)[CH2:39]1)[CH2:37]2.[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

Komponenten

7

Edukt 4

HCID 1128Tetramethylene sulfoxideHCID 7914Diisopropyl EtherHCID 134430561-(2,2,2-Trifluoroethoxy)naphthaleneHCID 86662332Benzyltrimethylammonium 1,1,3,3,3-pentafluoro-2-(adamantane-1-carbonyloxy)propanesulfonate

Produkt 1

HCID 866642934-(2,2,2-Trifluoroethoxy)-1-naphthyl-tetrahydrothiophenium 2-(adamantane-1-carbonyloxy)-1,1,3,3,3-pentafluoropropane-1-sulfonateAusbeute 78 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittel2×HCID 86584057Phosphorus Pentoxide-Methanesulfonic AcidLösungsmittel

Versuchsvorschrift

In 6 g of Eaton's reagent (Aldrich, diphosphorus pentoxide/methanesulfonic acid solution) was dispersed 3 g (0.0127 mol) of 1-(2,2,2-trifluoroethoxy)naphthalene in Synthesis Example 1-3. With stirring, 2.6 g (0.0253 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 5.5 g (0.0101 mol) of benzyltrimethylammonium 2-(adamantane-1-carbonyloxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate in Synthesis Example 1-2, after which extraction was effected twice with 50 g of dichloromethane. The organic layer was washed with water, and the solvent was distilled off in vacuum. The residue was purified by silica gel column chromatography (elute, dichloromethane/methanol). It was dissolved in methyl isobutyl ketone and washed with water, followed by solvent removal and vacuum drying. The product was poured into isopropyl ether for crystallization, filtered and dried, obtaining the target compound. White crystal, 5.6 g, yield 78%.

Aufarbeitung

  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. distillationthe solvent was distilled off in vacuum
  7. customThe residue was purified by silica gel column chromatography (elute, dichloromethane/methanol)
  8. dissolutionIt was dissolved in methyl isobutyl ketone
  9. washwashed with water
  10. customfollowed by solvent removal and vacuum
  11. customdrying
  12. additionThe product was poured into isopropyl ether for crystallization
  13. filtrationfiltered
  14. customdried
  15. customobtaining the target compound

Quellen und Nachweise

ORD-Eintrag
ord-149ac466e23e484aa4f9f5503c5ceae6
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08597869B2

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