Dimethylformamide → 4-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzonitrile

HRID 62065

Reaktionsgleichung

Reaktionsgleichung von HRID 62065
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]=[CH:11][N:10]([C:13]3[CH:18]=[CH:17][C:16]([O:19][C:20]([F:23])([F:22])[F:21])=[CH:15][CH:14]=3)[N:9]=2)=[CH:4][CH:3]=1.[CH3:24][N:25](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:21][C:20]([F:23])([F:22])[O:19][C:16]1[CH:17]=[CH:18][C:13]([N:10]2[CH:11]=[N:12][C:8]([C:5]3[CH:6]=[CH:7][C:2]([C:24]#[N:25])=[CH:3][CH:4]=3)=[N:9]2)=[CH:14][CH:15]=1

Komponenten

6

Edukt 2

HCID 6228DimethylformamideHCID 904040773-(4-bromophenyl)-1-(4-(trifluoromethoxy)phenyl)-1 H-1,2,4-triazole

Produkt 1

HCID 669571074-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzonitrileAusbeute 94 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

In a 250 mL flask, 3-(4-bromophenyl)-1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole (4.00 g, 10.4 mmol) was dissolved in N,N-dimethylformamide (30 mL) under nitrogen atmosphere. Zinc cyanide (1.46 g, 12.4 mmol) and tetrakis(triphenylphosphine) palladium(0) (0.601 g, 0.0500 mmol) were added and the reaction mixture was heated to 110° C. for 16 hours. The reaction mixture was cooled to room temperature, diluted with ethyl acetate and washed with water. The aqueous layer was further extracted with ethyl acetate. The combined organics were washed with water and brine, dried over magnesium sulfate and concentrated. Purification by flash column chromatography eluting with 30% ethyl acetate/hexanes gave the title compound as off-white solid (3.40 g, 94%): mp 172-176° C.; 1H NMR (400 MHz, CDCl3): δ 8.60 (s, 1H), 8.31 (d, J=8.8 Hz, 2H), 7.81 (d, J=8.8 Hz, 2H), 7.77 (d, J=8.8 Hz, 2H), 7.41 (d, J=8.8 Hz, 2H); ES+API m/z 331 ([M+H]+).

Aufarbeitung

  1. temperatureThe reaction mixture was cooled to room temperature
  2. washwashed with water
  3. extractionThe aqueous layer was further extracted with ethyl acetate
  4. washThe combined organics were washed with water and brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. customPurification by flash column chromatography
  8. washeluting with 30% ethyl acetate/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-6923f5cd857b4c6c972bc13a2d4e7a77
Quelldatensatz
uspto-grants-2016_09
Patentnummer
US09445594B2

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