Sulfur Dioxide → 3-(2,5,5-Trimethyl-1,3-dioxan-2-yl)thiophene-2-sulfonamide

HRID 2255497Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2255497
[CH3:1][C:2]1([C:10]2[CH:14]=[CH:13][S:12][CH:11]=2)[O:7][CH2:6][C:5]([CH3:9])([CH3:8])[CH2:4][O:3]1.C([Li])CCC.[S:20](=[O:22])=[O:21].O.O.O.C([O-])(=O)C.[Na+].[NH2:31]OS(O)(=O)=O>CCCCCC.O.C1COCC1>[CH3:1][C:2]1([C:10]2[CH:14]=[CH:13][S:12][C:11]=2[S:20]([NH2:31])(=[O:22])=[O:21])[O:3][CH2:4][C:5]([CH3:8])([CH3:9])[CH2:6][O:7]1

Komponenten

9

Edukt 5

HCID 1119Sulfur DioxideHCID 76284hydroxylamine-O-sulfonic acidHCID 22902024HCID 22902024, VerbindungHCID 23665404Sodium Acetate TrihydrateHCID 178418339Butyllithium

Produkt 1

HCID 229019383-(2,5,5-Trimethyl-1,3-dioxan-2-yl)thiophene-2-sulfonamide

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8058HexaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 3-(2,5,5-Trimethyl-1,3-dioxane-2-yl)thiophene (2.5 g, 11.7 mmol) in hexane (30 mL) cooled to 0° C. was added via syringe n-butyllithium in hexane (2.5 M, 10.3 mL, 25.7 mmol) over 5 min. The mixture was stirred at 0° C. for 20 min, the ice bath was removed and the stirring was continued for 30 min. At this time a white precipitate formed. The mixture was cooled to -60° C. and THF (20 mL) was added. Sulfur dioxide was then passed through the surface of the mixture for 30 min. The mixture was warmed to ambient temperature and stirred for an additional 15 min. The volatiles were evaporated and to the residue was added water (50 mL) and sodium acetate trihydrate (9.55 g, 70.2 mmol). The solution was cooled on an ice bath and hydroxylamine-O-sulfonic acid (4.62 g, 40.9 mmol) was added. The mixture was stirred at ambient temperature for 1 h, extracted with ethyl acetate (3×100 mL) and the combined extracts were washed with a sodium bicarbonate solution, brine and dried over molecular sieves. Evaporation to dryness gave a viscous liquid (4.93 g), which was chromatographed (silica, eluting with 33% ethyl acetate-hexane) to give a solid (2.47 g, 72%): mp 200°-202° C.

Aufarbeitung

  1. customthe ice bath was removed
  2. waitthe stirring was continued for 30 min
  3. customAt this time a white precipitate formed
  4. temperatureThe mixture was cooled to -60° C.
  5. temperatureThe mixture was warmed to ambient temperature
  6. stirringstirred for an additional 15 min
  7. customThe volatiles were evaporated and to the residue
  8. temperatureThe solution was cooled on an ice bath
  9. stirringThe mixture was stirred at ambient temperature for 1 h
  10. extractionextracted with ethyl acetate (3×100 mL)
  11. washthe combined extracts were washed with a sodium bicarbonate solution, brine
  12. customdried over molecular sieves
  13. customEvaporation to dryness

Quellen und Nachweise

ORD-Eintrag
ord-ace2544b85094767aae70d9b2b821194
Quelldatensatz
uspto-grants-1993_08
Patentnummer
US05240923

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