Methyl 4-bromobenzoate → Methyl 4-pyridin-3-ylbenzoate

HRID 352721

Reaktionsgleichung

Reaktionsgleichung von HRID 352721
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=1.C(B(CC)[C:15]1[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=1)C.[OH-].[K+].[Cl-].[NH4+]>O1CCCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OCC)(=O)C.O>[N:17]1[CH:18]=[CH:19][CH:20]=[C:15]([C:2]2[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][CH:3]=2)[CH:16]=1

Komponenten

10

Edukt 4

HCID 12081Methyl 4-bromobenzoateHCID 14797Potassium HydroxideHCID 25517Ammonium ChlorideHCID 6428513-(Diethylboryl)pyridine

Produkt 1

HCID 4133187Methyl 4-pyridin-3-ylbenzoateAusbeute 52,8 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

In tetrahydrofuran (100 ml), methyl 4-bromobenzoate (5.04 g) and diethyl-3-pyridylborane (Chem. Pharm. Bull., 33, 4755, 1985) (2.30 g) were dissolved, followed by the addition of tetrabutylammonium bromide (2.51 g), potassium hydroxide (2.63 g), tetrakis(triphenylphosphine)palladium (O) (1.8 g) and water (1 ml) under an argon atmosphere. The resulting mixture was heated under reflux for 2 hours. After ice cooling, an aqueous ammonium chloride solution and ethyl acetate were added to the reaction mixture. The organic layer so separated was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by chromatography on a silica gel column (hexane: ethyl acetate=1:1). The solvent was then distilled off. To the residue, methanol and IN aqueous hydrochloric acid in ethanol were added. The solvent was distilled off again. Tetrahydrofuran was added to the residue and the solid so precipitated was collected by filtration. After drying, the title compound (1.76 g, 45%) was obtained as a colorless solid.

Aufarbeitung

  1. temperatureThe resulting mixture was heated
  2. temperatureunder reflux for 2 hours
  3. customThe organic layer so separated
  4. dry with materialwas dried over anhydrous magnesium sulfate
  5. customThe residue obtained
  6. distillationby distilling off the solvent
  7. customwas purified by chromatography on a silica gel column (hexane: ethyl acetate=1:1)
  8. distillationThe solvent was then distilled off
  9. additionTo the residue, methanol and IN aqueous hydrochloric acid in ethanol were added
  10. distillationThe solvent was distilled off again
  11. additionTetrahydrofuran was added to the residue
  12. customthe solid so precipitated
  13. filtrationwas collected by filtration
  14. customAfter drying

Quellen und Nachweise

ORD-Eintrag
ord-25f2dd75016941328bf92f8e2b8329ca
Quelldatensatz
uspto-grants-2004_06
Patentnummer
US06747023B1

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