Dichloromethane → (3S,5S)-3,5-Dimethylmorpholine--hydrogen chloride (1/1)

HRID 584238Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 584238
C(OC([N:8]1[C@@H:13]([CH3:14])[CH2:12][O:11][CH2:10][C@@H:9]1[CH3:15])=O)(C)(C)C.[Cl:16]CCl>FC(F)(F)C(O)=O>[ClH:16].[CH3:15][C@H:9]1[CH2:10][O:11][CH2:12][C@H:13]([CH3:14])[NH:8]1

Komponenten

4

Edukt 2

HCID 6344DichloromethaneHCID 575471001,1-Dimethylethyl (3S,5S)-3,5-dimethyl-4-morpholinecarboxylate

Produkt 1

HCID 66876936(3S,5S)-3,5-Dimethylmorpholine--hydrogen chloride (1/1)

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6422Trifluoroacetic acidLösungsmittel

Versuchsvorschrift

A mixture of (3S)-3,5-dimethylmorpholine hydrochloride (8.3 g), di-tert-butyl dicarbonate (14.34 g) and sodium hydroxide (5.48 g) in water (30 ml) were stirred at room temperature overnight. Water (50 ml) and isopropyl ether were added to the mixture and the organic layer was separated, dried over magnesium sulfate, and evaporated in vacuo. The residue was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane (1:9) as an eluent to give (3S,5S)-4-tert-butoxycarbonyl-3,5-dimethylmorpholine (3.55 g) and meso-4-tert-butoxycarbonyl-3,5-dimethylmorpholine (2.84 g) (the former was less polar). (3S,5S)-4-tert-butoxycarbonyl-3,5-dimethylmorpholine (3.55 g) was dissolved in a mixture of dichloromethane (20 ml) and trifluoroacetic acid (20 ml) and the mixture was stirred at room temperature for 2 hours. After removal of the solvent under reduced pressure, 1N sodium hydroxide solution (20 ml) and dichoromethane were added thereto. The organic phase was separated, dried over magnesium sulfate, and was added 4N hydrogen chloride in ethyl acetate (20 ml). The mixture was evaporated in vacuo and the residue was triturated with a mixture of dichloromethane and isopropyl ether to give (3S,5S)-3,5-dimethylmorpholine hydrochloride (1.56 g) as a white solid.

Aufarbeitung

  1. customAfter removal of the solvent under reduced pressure, 1N sodium hydroxide solution (20 ml) and dichoromethane
  2. additionwere added
  3. customThe organic phase was separated
  4. dry with materialdried over magnesium sulfate
  5. additionwas added 4N hydrogen chloride in ethyl acetate (20 ml)
  6. customThe mixture was evaporated in vacuo
  7. customthe residue was triturated with a mixture of dichloromethane and isopropyl ether

Quellen und Nachweise

ORD-Eintrag
ord-23307795ccf64a48a7e84f7a9885073c
Quelldatensatz
uspto-grants-2005_08
Patentnummer
US06924278B2

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