Sodium Carbonate → 3-(Pyridin-3-yl)phenol

HRID 1269488Notes

Reaction equation

HRID 1269488 reaction equation
Br[C:2]1[CH:3]=[C:4]([OH:8])[CH:5]=[CH:6][CH:7]=1.C(B(CC)[C:12]1[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=1)C.C(=O)([O-])[O-].[Na+].[Na+]>C1COCC1.O.C(O)C.O.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>[OH:8][C:4]1[CH:3]=[C:2]([C:12]2[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=2)[CH:7]=[CH:6][CH:5]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 115633-BromophenolHCID 6428513-(Diethylboryl)pyridine

Product 1

HCID 129379483-(Pyridin-3-yl)phenolYield 88%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 18504229Ethanol tetrahydrofuran waterSolvent

Procedure

3-bromophenol (49.42 g, 285.66 mmol) and diethyl-(3-pyridyl)borane (40.00 g, 272.05 mmol) were dissolved in 945 mL of a 4:2:1 mixture of THF/H2O/ethanol in a 2 L round bottom flask equipped with a magnetic stirrer. Sodium carbonate (57.7 g, 544.11 mmol) and tetrakis(triphenylphosphine)palladium(0) (3.14 g, 2.72 mmol) was added and the mixture was heated at reflux for 2 h then cooled to ambient temperature and stirred an additional 18 h. The mixture was diluted with 400 mL water and extracted with ethyl acetate (3×500 mL). The organic phases were combined and dried over anhydrous sodium sulfate, filtered and concentrated to a volume of 1 L. The organic solution was diluted with 500 mL water and made acidic with 12N HCl. The layers were separated and the organic phase extracted with water (2×300 mL). The acidic extractions were combined and made basic with 5N aqueous sodium hydroxide. This basic layer was extracted with diethyl ether (3×500 mL) and the extracts were combined, washed with 500 mL brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to yield 40.91 g (88%) of 3-(3-hydroxyphenyl)pyridine as a pale yellow oil which crystallized on standing.

Workup

  1. customequipped with a magnetic stirrer
  2. temperaturethe mixture was heated
  3. temperatureat reflux for 2 h
  4. extractionextracted with ethyl acetate (3×500 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated to a volume of 1 L
  8. additionThe organic solution was diluted with 500 mL water
  9. customThe layers were separated
  10. extractionthe organic phase extracted with water (2×300 mL)
  11. extractionThe acidic extractions
  12. extractionThis basic layer was extracted with diethyl ether (3×500 mL)
  13. washwashed with 500 mL brine
  14. dry with materialdried over anhydrous sodium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-03879ce676344ff4aab44700f172afcd
Source dataset
uspto-grants-2007_04
Patent number
US07199243B2

Reaction notes

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