Dimethylformamide → Methyl 3-cyano-1H-indazole-5-carboxylate

HRID 2064253Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2064253
Br[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][N:6]=[C:5]2[C:11]#[N:12].[C:13]([O-:16])(=[O:15])C.[Na+].[CH3:18]N(C)C=O>CO.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].[Pd](Cl)Cl>[C:11]([C:5]1[C:4]2[C:8](=[CH:9][CH:10]=[C:2]([C:13]([O:16][CH3:18])=[O:15])[CH:3]=2)[NH:7][N:6]=1)#[N:12]

Komponenten

6

Edukt 3

HCID 6228DimethylformamideHCID 517045Sodium AcetateHCID 247289115-bromo-1H-indazole-3-carbonitrile

Produkt 1

HCID 44632177Methyl 3-cyano-1H-indazole-5-carboxylateAusbeute 68 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 887MethanolLösungsmittel

Versuchsvorschrift

A suspension of 5-bromo-3-cyanoindazole (3 g, 13.51 mmol), palladium dichloride 1,1′-bis(diphenylphosphino)ferrocene (1.76 g, 2.16 mmol), sodium acetate (3.32 g, 40.5 mmol), dimethylformamide (1 mL) in methanol (100 mL) was degassed, and kept under carbon monoxide (80 psi) pressure at 80° C. in a autoclave for 16 hours. The mixture was diluted with water (50 mL), filtered through Celite® bed and the filtrate was concentrated. The obtained residue was acidified with 10% citric acid solution and extracted with ethyl acetate (2×100 mL). The combined organic layers were washed with brine (50 mL), dried over anhydrous sodium sulfate and concentrated. The obtained crude product was purified by column chromatography (100-200 mesh silica gel) using 10% ethyl acetate in chloroform as eluent to afford methyl 3-cyano-1H-indazole-5-carboxylate (1.8 g, 68%) as a solid. 1HNMR (CDCl3) δ ppm 10.8 (s, 1H), 8.7 (s, 1H), 8.22 (d, 1H), 7.64 (d, 1H), 4.0 (s, 3H).

Aufarbeitung

  1. customwas degassed
  2. customat 80° C.
  3. customfor 16 hours
  4. additionThe mixture was diluted with water (50 mL)
  5. filtrationfiltered through Celite® bed
  6. concentrationthe filtrate was concentrated
  7. extractionextracted with ethyl acetate (2×100 mL)
  8. washThe combined organic layers were washed with brine (50 mL)
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated
  11. customThe obtained crude product
  12. customwas purified by column chromatography (100-200 mesh silica gel)

Quellen und Nachweise

ORD-Eintrag
ord-3c948cdbc25c41698c64af4ef581f4d3
Quelldatensatz
uspto-grants-2012_10
Patentnummer
US08288405B2

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