Cesium fluoride → HCID 66604498, Verbindung

HRID 2410674Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2410674
[NH2:1][C:2]1[C:9](Br)=[CH:8][C:7](Br)=[CH:6][C:3]=1[C:4]#[N:5].[CH3:12][O:13][C:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.[F-].[Cs+]>[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>[NH2:1][C:2]1[C:3]([C:4]#[N:5])=[CH:6][C:7]([C:17]2[CH:18]=[CH:19][C:14]([O:13][CH3:12])=[CH:15][CH:16]=2)=[CH:8][C:9]=1[C:17]1[CH:18]=[CH:19][C:14]([O:13][CH3:12])=[CH:15][CH:16]=1

Komponenten

5

Edukt 3

HCID 25953Cesium fluorideHCID 201262(4-Methoxyphenyl)boronic acidHCID 27340822-Amino-3,5-dibromobenzonitrile

Produkt 1

HCID 66604498HCID 66604498, VerbindungAusbeute 89,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysator

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A mixture of 2-amino-3,5-dibromobenzonitrile (250 mg, 0.906 mmol), 4-methoxyphenylboronic acid (330 mg, 2.17 mmol), tetrakis(triphenylphosphine)-palladium(0) (52 mg, 0.045 mmol) and cesium fluoride (661 mg, 4.35 mmol) was placed in a vial and flushed with nitrogen. Dimethoxyethane (4.5 mL) was added and the reaction was heated at 80° C. for 7 hr. After cooling to room temperature, the reaction was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution. The organic phase was separated, washed with saturated aqueous sodium bicarbonate solution, brine, and then dried with sodium sulfate. Removal of the solvent followed by silica gel radial chromatography (step gradient elution with hexane containing 0 to 20% ethyl acetate) afforded 4′-amino-4,4″-dimethoxy-[1,1′:3′,1″-terphenyl]-5′-carbonitrile (267 mg, 89% yield) as an oil. MS (ESI) m/z 331.1 (M+H). 1H NMR (CDCl3) δ ppm 7.54 (1H, d, J=2.14 Hz), 7.46 (1H, d, J=2.14 Hz), 7.42 (2H, d, J=8.55 Hz), 7.36 (2H, d, J=8.55 Hz), 7.01 (2H, d, J=8.55 Hz), 6.94 (2H, d, J=8.55 Hz), 4.50 (2H, s), 3.86 (3H, s), 3.83 (3H, s).

Aufarbeitung

  1. customflushed with nitrogen
  2. additionDimethoxyethane (4.5 mL) was added
  3. temperatureAfter cooling to room temperature
  4. customthe reaction was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution
  5. customThe organic phase was separated
  6. washwashed with saturated aqueous sodium bicarbonate solution, brine
  7. dry with materialdried with sodium sulfate
  8. customRemoval of the solvent
  9. washfollowed by silica gel radial chromatography (step gradient elution with hexane containing 0 to 20% ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-8ec90faea3934ca786b932d17d3a980d
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08815840B2

Notizen zur Reaktion

Wird geladen…