Dimethylformamide → 4-Acetyl-2-chloro-5-hydroxybenzonitrile

HRID 626833Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 626833
Br[C:2]1[C:7]([Cl:8])=[CH:6][C:5]([C:9](=[O:11])[CH3:10])=[C:4]([OH:12])[CH:3]=1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:55][N:56](C)C=O>[C-]#N.[Zn+2].[C-]#N.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:9]([C:5]1[C:4]([OH:12])=[CH:3][C:2]([C:55]#[N:56])=[C:7]([Cl:8])[CH:6]=1)(=[O:11])[CH3:10]

Komponenten

6

Edukt 3

HCID 6228DimethylformamideHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 595641771-(4-Bromo-5-chloro-2-hydroxyphenyl)ethanone

Produkt 1

HCID 866975254-Acetyl-2-chloro-5-hydroxybenzonitrileAusbeute 72 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysator

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

1-(4-bromo-5-chloro-2-hydroxyphenyl)ethanone (6.2 g, 25 mmol) was combined with zinc cyanide (4.4 g, 37 mmol) in N,N-dimethylformamide (40 mL) degassed with nitrogen and tris(dibenzylideneacetone)dipalladium(0) (0.38 g, 0.42 mmol) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (0.57 g, 0.99 mmol) were added. The reaction was degassed with nitrogen and heated to 120° C. and monitored by LC/MS. After heating for 2 hrs, the reaction was allowed to cool to room temperature, diluted with ethyl acetate, and filtered to remove the solids. The organic layer was washed with water, brine, dried over magnesium sulfate and concentrated in vacuo to give the crude product. The product was purified by FCC on silica gel eluting hexane:ethyl acetate gradient to give 4-acetyl-2-chloro-5-hydroxybenzonitrile as a yellow crystalline solid (3.5 g, 72%).

Aufarbeitung

  1. additionwere added
  2. customThe reaction was degassed with nitrogen
  3. temperatureAfter heating for 2 hrs
  4. temperatureto cool to room temperature
  5. additiondiluted with ethyl acetate
  6. filtrationfiltered
  7. customto remove the solids
  8. washThe organic layer was washed with water, brine
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated in vacuo
  11. customto give the crude product
  12. customThe product was purified by FCC on silica gel
  13. washeluting hexane

Quellen und Nachweise

ORD-Eintrag
ord-888e931804f44f959a9cc959d6523252
Quelldatensatz
uspto-grants-2016_04
Patentnummer
US09309251B2

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