Fluorine → Meconin

HRID 336813

Reaktionsgleichung

Reaktionsgleichung von HRID 336813
CN1[C@@H]([C@H:12]2[O:21][C:19](=[O:20])[C:18]3[C:17]([O:22][CH3:23])=[C:16]([O:24][CH3:25])[CH:15]=[CH:14][C:13]2=3)C2C(OC)=C3OCOC3=CC=2CC1.[F-].FF>C1COCC1>[CH3:25][O:24][C:16]1[C:17]([O:22][CH3:23])=[C:18]2[C:13]([CH2:12][O:21][C:19]2=[O:20])=[CH:14][CH:15]=1

Komponenten

5

Edukt 3

HCID 24524FluorineHCID 28179Fluoride IonHCID 275196Noscapine

Produkt 1

HCID 68437MeconinAusbeute 74 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Aromatic fluorination of noscapine was achieved by employing the fluoride form of Amberlyst-A 26, a macroreticular anion-exchange resin containing quaternary ammonium groups. The method described [33] for Hal/F exchange may also be applied to other Hal/Hal′ exchange reactions. In Br/F exchange reactions, good yields were obtained only when a large molar ratio of the resin with respect to the substrate was employed. Thus, after refluxing a solution of bromonoscapine in anhydrous THF and an excess of Amberlyst-A 26 (fluorine, polymer-supported, 10 milliequivalents of dry resin; the average capacity of the resin is 4 milliequivalents per gram) for 12 hours, the resin was filtered off and the solvent was removed in vacuo to afford the desired compound (3) in 74% yield. The resin was recovered by washing with 1 N NaOH and then rinsing thoroughly with water until neutrality to generate the hydroxy-form of the resin. It was then stirred overnight with 1 N aqueous hydrofluoric acid, washed with acetone, ether and dried in a vacuum oven at 50° C. for 12 hours to afford the regenerated Amberlyst-A 26 (fluorine, polymer-supported), which can be reused.

Aufarbeitung

  1. additiona macroreticular anion-exchange resin containing quaternary ammonium groups
  2. customIn Br/F exchange reactions, good yields
  3. customwere obtained only when a large molar ratio of the resin with respect to the substrate
  4. customfor 12 hours
  5. filtrationthe resin was filtered off
  6. customthe solvent was removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-6a98af94e77f4eb38471afa6e3153f02
Quelldatensatz
uspto-grants-2014_11
Patentnummer
US08889705B2

Verknüpfte Notizen

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