Fluorine → Meconin

HRID 336813ノート

反応式

HRID 336813 の反応式
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

参加物

5

反応物 3

HCID 24524FluorineHCID 28179Fluoride IonHCID 275196Noscapine

生成物 1

HCID 68437Meconin収率 74%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-6a98af94e77f4eb38471afa6e3153f02
出典データセット
uspto-grants-2014_11
特許番号
US08889705B2

反応ノート

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