Toluene → 5-Methyl-2-phenylpyridine

HRID 1522706

Reaktionsgleichung

Reaktionsgleichung von HRID 1522706
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N:3]=1.[C:9]1(B(O)O)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].C1(C)C=CC=CC=1>[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.O>[C:9]1([C:2]2[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N:3]=2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Komponenten

8

Edukt 4

HCID 1140TolueneHCID 62657Potassium Phosphate, TribasicHCID 66827Phenylboronic AcidHCID 5642162-Bromo-5-methylpyridine

Produkt 1

HCID 474675-Methyl-2-phenylpyridineAusbeute 92 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9832798Tris(dibenzylideneacetone) dipalladiumKatalysatorHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylKatalysatorHCID 962WaterLösungsmittel

Versuchsvorschrift

2-bromo-5-methylpyridine (11.25 g, 65.39 mmol), phenylboronic acid (9.5 g, 78.47 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (1.0 g, 2.61 mmol), and potassium phosphate tribasic (45 g, 196.17 mmol), 250 mL of toluene and 25 mL of water were placed in a 500 mL round-bottom flask. Nitrogen was bubbled directly into the mixture for 30 min after which tris(dibenzylideneacetone) dipalladium(0) (598 mg, 0.653 mmol) was added. Nitrogen was bubbled for another 15 min then the reaction mixture was heated to reflux for 16 h under nitrogen. The mixture was cooled and the organic layer was separated from the aqueous layer. The organic layers are washed with saturated brine solution, dried over magnesium sulfate, filtered, and the solvent removed under vacuum to give an off-white solid as the crude. The crude was purified by column chromatography using silica gel as the stationary phase and 5%-10% ethyl acetate in hexanes as the mobile phase. 10.11 g of desired product was obtained after purification (92% yield).

Aufarbeitung

  1. additionwas added
  2. customNitrogen was bubbled for another 15 min
  3. temperaturethe reaction mixture was heated
  4. temperatureto reflux for 16 h under nitrogen
  5. temperatureThe mixture was cooled
  6. customthe organic layer was separated from the aqueous layer
  7. washThe organic layers are washed with saturated brine solution
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customthe solvent removed under vacuum
  11. customto give an off-white solid as the crude
  12. customThe crude was purified by column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-c839b2803eb649b180725a3fe95a315a
Quelldatensatz
uspto-grants-2015_07
Patentnummer
US09076973B2

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