2,5-Dichloropyridine → 5-Chloro-2-phenylpyridine

HRID 1801712Notes

Reaction equation

HRID 1801712 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[CH:4][N:3]=1.[C:9]1(B(O)O)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>C1C=CC(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[N:3][CH:4]=1

Participants

4

Reactant 2

HCID 276852,5-DichloropyridineHCID 66827Phenylboronic Acid

Product 1

HCID 27628665-Chloro-2-phenylpyridineYield 75%

Reagents, catalysts & solvents 1

HCID 10974057(Butane-1,4-diyl)bis(diphenylphosphane)--dichloropalladium (1/1)Catalyst

Procedure

A 100-mL, round-bottomed flask, fitted with a reflux condenser was charged with 2,5-dichloropyridine (1.00 g, 6.76 mmol), phenylboronic acid (1.07 g, 8.78 mmol), [1,4-bis(diphenylphosphino)butane]palladium(II) dichloride (0.204 g, 0.338 mmol), argon-degassed toluene/ethanol (4:1, 17 mL) and argon-degassed aqueous 1 N sodium carbonate (6.6 mL). The mixture was heated to reflux for 3 h, cooled to room temperature and diluted with water (15 mL) and EtOAc (100 mL). The layers separated and the aqueous phase was extracted with EtOAc (100 mL). The combine organic extracts were dried over Na2SO4, filtered and concentrated. Purification by flash column chromatography (silica gel, 50:50 hexanes/CH2Cl2) provided 5-chloro-2-phenylpyridine (0.959 g, 75%) as a white solid.

Workup

  1. customA 100-mL, round-bottomed flask, fitted with a reflux condenser
  2. customdegassed toluene/ethanol (4:1, 17 mL) and argon-
  3. customdegassed aqueous 1 N sodium carbonate (6.6 mL)
  4. temperatureThe mixture was heated
  5. temperatureto reflux for 3 h
  6. additiondiluted with water (15 mL) and EtOAc (100 mL)
  7. customThe layers separated
  8. extractionthe aqueous phase was extracted with EtOAc (100 mL)
  9. dry with materialThe combine organic extracts were dried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by flash column chromatography (silica gel, 50:50 hexanes/CH2Cl2)

Sources & evidence

ORD record
ord-73874e108c404f19b702db5f595f3c2e
Source dataset
uspto-grants-2013_01
Patent number
US08349858B2

Reaction notes

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