Dimethylformamide → Methyl 2-chloro-4-cyano-5-fluorobenzoate

HRID 219858

Reaktionsgleichung

Reaktionsgleichung von HRID 219858
Br[C:2]1[C:11]([F:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([Cl:13])[CH:3]=1.[CH3:14][N:15](C=O)C>[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].[Zn].C([O-])(=O)C.[Zn+2].C([O-])(=O)C>[Cl:13][C:4]1[CH:3]=[C:2]([C:14]#[N:15])[C:11]([F:12])=[CH:10][C:5]=1[C:6]([O:8][CH3:9])=[O:7]

Komponenten

8

Edukt 2

HCID 6228DimethylformamideHCID 44203099Methyl 4-bromo-2-chloro-5-fluorobenzoate

Produkt 1

HCID 67528656Methyl 2-chloro-4-cyano-5-fluorobenzoate

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 11192Zinc AcetateKatalysatorHCID 23994ZincKatalysatorHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysator

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

Methyl 4-bromo-2-chloro-5-fluorobenzoate (1.80 g; 6.73 mmol; 1 eq.), zinc cyanide (474.13 mg; 4.04 mmol; 0.60 eq.), tris(dibenzylideneacetone)dipalladium(0) (49.30 mg; 0.05 mmol; 0.01 eq.), 1,1′-bis(diphenylphosphino)ferrocene (59.69 mg; 0.11 mmol; 0.02 eq.), zinc (17.60 mg; 0.27 mmol; 0.04 eq.) and zinc acetate (49.39 mg; 0.27 mmol; 0.04 eq.) were put in dry DMF (18 mL). The reaction mixture was purged with N2 and then heated to 90° C. for 12 hours. The reaction mixture was cooled to RT, filtered over a pad of celite and washed with EtOAc. The organic phase was washed with water, brine, dried over MgSO4 and concentrated affording a brown solid. It was purified by washing with EtOH affording the title compound as a beige solid. 1H NMR (DMSO-d6, 300 MHz) δ 8.37-8.35 (d, J=5.86 Hz, 1H), 8-7.97 (d, J=9.18 Hz, 1H), 3.91 (s, 3H).

Aufarbeitung

  1. customThe reaction mixture was purged with N2
  2. temperatureThe reaction mixture was cooled to RT
  3. filtrationfiltered over a pad of celite
  4. washwashed with EtOAc
  5. washThe organic phase was washed with water, brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customaffording a brown solid
  9. customIt was purified
  10. washby washing with EtOH affording the title compound as a beige solid

Quellen und Nachweise

ORD-Eintrag
ord-3dacc5ce7094418cb5217eb62f884e7a
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08202865B2

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