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Tetramethylene sulfoxide → 4-(2-Methoxyethoxy)naphthalene 1-tetrahydrothiophenium 2-(adamantane-1-carbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate

HRID 2367905
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[CH3:1][O:2][CH2:3][CH2:4][O:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1.[CH2:16]1[S:20](=O)[CH2:19][CH2:18][CH2:17]1.C(OC(C)C)(C)C.[F:29][C:30]([F:53])([S:49]([O-:52])(=[O:51])=[O:50])[CH:31]([O:36][C:37]([C:39]12[CH2:48][CH:43]3[CH2:44][CH:45]([CH2:47][CH:41]([CH2:42]3)[CH2:40]1)[CH2:46]2)=[O:38])[C:32]([F:35])([F:34])[F:33].[Na+]>CS(O)(=O)=O.O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.O>[CH3:1][O:2][CH2:3][CH2:4][O:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1.[C:39]12([C:37]([O:36][CH:31]([C:32]([F:35])([F:33])[F:34])[C:30]([F:29])([F:53])[S:49]([O-:52])(=[O:50])=[O:51])=[O:38])[CH2:40][CH:41]3[CH2:47][CH:45]([CH2:44][CH:43]([CH2:42]3)[CH2:48]1)[CH2:46]2.[SH+:20]1[CH2:16][CH2:17][CH2:18][CH2:19]1
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Komponenten

7

Edukt 4

HCID 1128Tetramethylene sulfoxideHCID 7914Diisopropyl EtherHCID 206591711-(2-Methoxyethoxy)naphthaleneHCID 86662327Sodium 1,1,3,3,3-pentafluoro-2-(adamantane-1-carbonyloxy)propanesulfonate

Produkt 1

HCID 866623284-(2-Methoxyethoxy)naphthalene 1-tetrahydrothiophenium 2-(adamantane-1-carbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittel2×HCID 86584057Phosphorus Pentoxide-Methanesulfonic AcidLösungsmittel

Versuchsvorschrift

In 100 g of ethanol were dissolved 50.0 g (0.0347 mol) of 1-naphthol, 34.4 g (0.0364 mol) of 2-methoxyethyl chloride, 14.6 g (0.0364 mol) of sodium hydroxide, and 2.6 g (0.017 mol) of sodium iodide. The solution was heated and stirred at 80° C. for 8 hours. After cooling, the solution was combined with 100 g of water and 200 g of toluene, from which an organic layer was separated. It was washed 5 times with 100 g of 5 wt % sodium hydroxide aqueous solution and then 4 times with 100 g of water. The organic layer was concentrated, obtaining 45 g of oily matter. On vacuum distillation at 110° C. and 13 Pa, 41 g of 1-(2-methoxyethoxy)naphthalene was obtained (yield 58%). Next 5.0 g (0.024 mol) of 1-(2-methoxyethoxy)naphthalene was dispersed in 10 g of Eaton's Reagent (Aldrich, diphosphorus pentoxide/methanesulfonic acid solution), to which 5.1 g (0.049 mol) of tetramethylene sulfoxide was added dropwise and mixed. 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 an aqueous solution (corresponding to 0.007 mol) of sodium 1,1,3,3,3-pentafluoro-2-(adamantane-1-carbonyloxy)propanesulfonate which was synthesized according to the formulation described in JP-A 2007-145797, 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 poured into isopropyl ether for crystallization. Subsequent filtration and drying gave the target compound. White crystal, 7.9 g, yield 94%.

Aufarbeitung

  1. additionwas added dropwise
  2. additionmixed
  3. customwas separated
  4. washThe water layer was again washed with 30 g of diisopropyl ether
  5. customwas synthesized
  6. extractionafter which extraction
  7. washThe organic layer was washed with water
  8. distillationthe solvent was distilled off in vacuum
  9. additionThe residue was poured into isopropyl ether for crystallization
  10. filtrationSubsequent filtration
  11. customdrying
  12. customgave the target compound

Quellen und Nachweise

ORD-Eintrag
ord-9f11a6dac0cf45d985f0a3b29daea606
Quelldatensatz
uspto-grants-2014_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08703384B2

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