Dimethylacetamide → 5-Chloro-3-methylpyridine-2-carbonitrile

HRID 930446Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 930446
Br[C:2]1[C:7]([CH3:8])=[CH:6][C:5]([Cl:9])=[CH:4][N:3]=1.C[C:11]([N:13](C)C)=O>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].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[Cl:9][C:5]1[CH:6]=[C:7]([CH3:8])[C:2]([C:11]#[N:13])=[N:3][CH:4]=1

Komponenten

7

Edukt 2

HCID 31374DimethylacetamideHCID 126309852-Bromo-5-chloro-3-methylpyridine

Produkt 1

HCID 218645635-Chloro-3-methylpyridine-2-carbonitrileAusbeute 76 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

A mixture of 2-bromo-5-chloro-3-methylpyridine (45 g, 218 mmol), zinc cyanide (8.30 mL, 131 mmol), tris(dibenzylideneacetone)dipalladium (0) (4.99 g, 5.45 mmol), and 1,1′-bis(diphenylphosphino)ferrocene (6.04 g, 10.90 mmol) in dimethylacetamide (40 mL) was heated to 110° C. for 4 hours. The reaction mixture was cooled to RT, diluted with water and extracted with ethyl acetate. The organic phase obtained was concentrated under reduced pressure and residue purified by chromatography on silica gel using ISCO eluting with 0-60% EtOAc/hex to afford the title compound 5-chloro-3-methylpicolinonitrile (25.4 g, 166 mmol, 76% yield). LC/MS (ESI+) m/z=153.1 (M+H).

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to RT
  2. extractionextracted with ethyl acetate
  3. customThe organic phase obtained
  4. concentrationwas concentrated under reduced pressure and residue
  5. custompurified by chromatography on silica gel using ISCO
  6. washeluting with 0-60% EtOAc/hex

Quellen und Nachweise

ORD-Eintrag
ord-c17d09739ac04ffdb721c3842a77efd7
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09296734B2

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