Water → (+)-Nootkatone

HRID 2217056

Reaktionsgleichung

Reaktionsgleichung von HRID 2217056
O.O.O.C([O-])(=O)C.[Na+].[CH3:9][C@H:10]1[C@@:19]2([CH3:20])[C:14]([CH2:15][CH2:16][C@@H:17]([C:21](Cl)([CH3:23])[CH3:22])[CH2:18]2)=[CH:13][C:12](=[O:25])[CH2:11]1.O>C(O)(=O)C>[CH3:9][C@H:10]1[C@:19]2([CH3:20])[CH2:18][C@H:17]([C:21]([CH3:23])=[CH2:22])[CH2:16][CH2:15][C:14]2=[CH:13][C:12](=[O:25])[CH2:11]1

Komponenten

5

Edukt 3

HCID 962WaterHCID 17747870(4R,4aS,6R)-4,4a,5,6,7,8-hexahydro-4,4a-dimethyl-6-(1-chloro-1-methylethyl)-2(3H)-naphthalenoneHCID 23665404Sodium Acetate Trihydrate

Produkt 1

HCID 1268142(+)-NootkatoneAusbeute 93 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

Sodium acetate trihydrate (0.22 g, 1.6 mmol) was added to a single-neck round bottom flask that had been fitted with a reflux condenser. A solution of the chloroenone Compound 8 (0.14 g, 0.54 mmol) in glacial acetic acid (4 mL) was injected into the flask, and the mixture was heated to 100° C. and held at that temperature for 2 hours. The reaction mixture was then cooled to room temperature, poured into cold water, and extracted with chloroform. The organic layer was then washed with successive portions of 2% aqueous KOH, 2 N HCl, NaHCO3, and brine, and then dried over MgSO4. The excess solvent was removed via rotary evaporator to provide nootkatone as a yellow oil (93%). The overall yield from β-pinene to nootkatone was 23% using path b, and 25% using path a, both of which are relatively high overall yields. Because the Oxy-Cope reaction and the methylation both provided the desired enantiomeric product, the enantiomeric purity of the final nootkatone product was little changed from that of the β-pinene starting product. Qualitatively, the fragrance of the synthesized nootkatone was identical to the fragrance of nootkatone derived from other sources. NMR data matched that previously reported for nootkatone: 1H NMR: (250 MHz, CDCl3), δ 5.77 (s, 1H), 4.75–4.72 (m, 2H), 2.62–2.43 (m, 1H), 2.41–2.22 (m, 4H), 2.09–1.87 (M, 3H), 1.46–1.38 (m, 1H), 1.12–1.10 (m, 4H), 0.98 (d, 3H).

Aufarbeitung

  1. customhad been fitted with a reflux condenser
  2. temperatureThe reaction mixture was then cooled to room temperature
  3. extractionextracted with chloroform
  4. washThe organic layer was then washed with successive portions of 2% aqueous KOH, 2 N HCl, NaHCO3, and brine
  5. dry with materialdried over MgSO4
  6. customThe excess solvent was removed via rotary evaporator

Quellen und Nachweise

ORD-Eintrag
ord-8a9883a3c79041128940c7ff4219b34d
Quelldatensatz
uspto-grants-2006_09
Patentnummer
US07112700B1

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