Hydroxyamine hydrochloride → 6-Bromo-2,4-difluoro-3-methoxy-benzonitrile

HRID 746772Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 746772
Cl.NO.[Br:4][C:5]1[C:10]([CH:11]=O)=[C:9]([F:13])[C:8]([O:14][CH3:15])=[C:7]([F:16])[CH:6]=1.CC[N+:19](S(N=C(OC)[O-])(=O)=O)(CC)CC>CN(C=O)C>[Br:4][C:5]1[C:10]([C:11]#[N:19])=[C:9]([F:13])[C:8]([O:14][CH3:15])=[C:7]([F:16])[CH:6]=1

Komponenten

5

Edukt 3

HCID 443297Hydroxyamine hydrochlorideHCID 2724994Methyl N-(triethylammoniosulfonyl)carbamateHCID 866131686-Bromo-2,4-difluoro-3-methoxybenzaldehyde

Produkt 1

HCID 866131696-Bromo-2,4-difluoro-3-methoxy-benzonitrile

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
150 °C

Versuchsvorschrift

Add hydroxylamine hydrochloride (608 mg, 8.8 mmol) to a solution of 6-Bromo-2,4-difluoro-3-methoxy-benzaldehyde (2.0 g, 7.96 mmol) in anhydrous DMF (4 ml). Heat the mixture to 150° C. for 2 h. Add water to the cooled mixture and extract the product with EtOAc (×2). Wash the combined organic layers with water (×3), saturated aq. sodium chloride and dry over anhydrous sodium sulfate. Filter and concentrate. Dissolve the concentrate in anhydrous THF and add 3 equivalent of the Burgess reagent ((methoxycarbonylsulfamoyl)triethylammonium hydroxide, inner salt). Heat the mixture under reflux under nitrogen atmosphere overnight. Concentrate to yield a crude residue. Purification by flash chromatography (Silica gel-hexane/EtOAc) yields the title compound.

Aufarbeitung

  1. extractionAdd water to the cooled mixture and extract the product with EtOAc (×2)
  2. washWash the combined organic layers with water (×3), saturated aq. sodium chloride
  3. dry with materialdry over anhydrous sodium sulfate
  4. filtrationFilter
  5. concentrationconcentrate
  6. dissolutionDissolve the
  7. concentrationconcentrate in anhydrous THF
  8. temperatureHeat the mixture
  9. temperatureunder reflux under nitrogen atmosphere overnight
  10. concentrationConcentrate
  11. customto yield a crude residue
  12. customPurification by flash chromatography (Silica gel-hexane/EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-374913e2d2124f568aef7b534fee3bc3
Quelldatensatz
uspto-grants-2008_07
Patentnummer
US07393868B2

Notizen zur Reaktion

Wird geladen…