Sodium Acetate → (4R,5R)-3-Methoxyamino-4,5-dimethyl-(Z)-oct-2-enoic Acid Ethyl Ester

HRID 132666

Reaktionsgleichung

Reaktionsgleichung von HRID 132666
[CH2:1]([O:3][C:4](=[O:15])[CH2:5][C:6](=O)[C@H:7]([CH3:13])[C@H:8]([CH3:12])[CH2:9][CH2:10][CH3:11])[CH3:2].Cl.[O:17]([NH2:19])[CH3:18].C([O-])(=O)C.[Na+]>CCO>[CH2:1]([O:3][C:4](=[O:15])/[CH:5]=[C:6](\[NH:19][O:17][CH3:18])/[C@H:7]([CH3:13])[C@H:8]([CH3:12])[CH2:9][CH2:10][CH3:11])[CH3:2]

Komponenten

5

Edukt 3

HCID 517045Sodium AcetateHCID 521874O-Methylhydroxylamine hydrochlorideHCID 25232467(4R,5R)-4,5-Dimethyl-3-oxo-octanoic Acid Ethyl Ester

Produkt 1

HCID 86597973(4R,5R)-3-Methoxyamino-4,5-dimethyl-(Z)-oct-2-enoic Acid Ethyl EsterAusbeute 99,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Versuchsvorschrift

A 2 L 3-necked round bottom flask, equipped with magnetic stirring and nitrogen inlet, was charged with 153 g (0.71 mol) of (4R,5R)-4,5-dimethyl-3-oxo-octanoic acid ethyl ester and 600 mL of anhydrous EtOH. The solution was cooled to 0° C.-5° C. with an ice bath and 65.6 g (0.79 mol) of methoxylamine hydrochloride was added, followed by 58.6 g (0.71 mol) of sodium acetate. This flask contents were slowly warmed to room temperature (about 2 hours) and the reaction mixture was stirred at room temperature for another 24 hours. The solvent (EtOH) was removed under reduced pressure and the mixture was charged with CH2Cl2 (2×300 mL), which was subsequently removed. The mixture was cooled to RT, diluted with CH2Cl2 (300 mL), stirred at room temperature for 0.5 hours, and filtered under 5 psig of nitrogen. The filter cake was washed with CH2Cl2 (150 mL). The filtrate was concentrated under vacuum (50° C.) to give 172 g (99% yield) of the titled compound as a light yellow oil: 1H NMR (400 MHz, CHLOROFORM-D) 0.87 (t, J=3.5 Hz, 5H), 0.89 (d, J=7.2 Hz, 3H), 1.08 (d, J=7.0 Hz, 3H), 1.24 (t, J=7.2 Hz, 4H), 1.3-1.55 (m, 2H), 2.25 (m, 1H), 3.15 (q, J=19.5 Hz, 2H) 3.81 (s, 3H), 4.14 (q, J=7.0 Hz, 2H).

Aufarbeitung

  1. customA 2 L 3-necked round bottom flask, equipped
  2. temperatureThe solution was cooled to 0° C.-5° C. with an ice bath
  3. stirringthe reaction mixture was stirred at room temperature for another 24 hours
  4. customThe solvent (EtOH) was removed under reduced pressure
  5. additionthe mixture was charged with CH2Cl2 (2×300 mL), which
  6. customwas subsequently removed
  7. temperatureThe mixture was cooled to RT
  8. additiondiluted with CH2Cl2 (300 mL)
  9. stirringstirred at room temperature for 0.5 hours
  10. filtrationfiltered under 5 psig of nitrogen
  11. washThe filter cake was washed with CH2Cl2 (150 mL)
  12. concentrationThe filtrate was concentrated under vacuum (50° C.)

Quellen und Nachweise

ORD-Eintrag
ord-d6c54c25d39f4d3f903dd6134749592d
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07388023B2

Verknüpfte Notizen

Wird geladen…