Dimethylformamide → 3-Chloro-5-hydroxypicolinonitrile

HRID 221798Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 221798
[Cl:1][C:2]1[CH:3]=[C:4]([O:9]C(=O)C)[CH:5]=[N:6][C:7]=1Cl.[CH3:13][N:14](C=O)C>CC(OC)(C)C.O.[Ar].[Zn].[C-]#N.[C-]#N.[Zn+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].Cl[Pd]Cl>[Cl:1][C:2]1[C:7]([C:13]#[N:14])=[N:6][CH:5]=[C:4]([OH:9])[CH:3]=1

Komponenten

8

Edukt 2

HCID 6228DimethylformamideHCID 145952225,6-Dichloropyridin-3-yl acetate

Produkt 1

HCID 666654733-Chloro-5-hydroxypicolinonitrile

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 85978949argon ZnKatalysatorHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 962WaterLösungsmittelHCID 15413tert-Butyl methyl etherLösungsmittel

Reaktionsbedingungen

Temperatur
150 °C

Versuchsvorschrift

To a solution of acetic acid 5,6-dichloro-pyridin-3-yl ester (CA 110861-18-2, Synthesis, 1990, 499) (4.88 g, 23.6 mmol) in anhydrous DMF (45 ml) was added after degasing with argon Zn-dust (70 mg, 1.07 mmol), Zn(CN)2 (1.28 g, 10.9 mmol) and DPPF PdCl2 (966 mg, 1.18 mmol) and the reaction mixture was heated for 6 h at 130° C. and 18 h at 150° C. The reaction mixture was diluted with TBME and H2O, filtered over Celite, and the product was extracted with TBME. Combined extracts were washed with water and brine, dried over MgSO4, filtered and concentrated. The title compound was obtained as a beige solid after crystallization from EtOAc-hexane: TLC(CH2Cl2-MeOH 19:1): Rf=0.22;

Aufarbeitung

  1. filtrationfiltered over Celite
  2. extractionthe product was extracted with TBME
  3. washCombined extracts were washed with water and brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-73c6c07de58346f880298eee000aa0f6
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08207164B2

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