Phenol → 2-Hydroxybenzonitrile

HRID 623244Notes

Reaction equation

HRID 623244 reaction equation
B(Br)(Br)Br.[C:5]1([OH:11])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[Cl-].[Al+3].[Cl-].[Cl-].[OH-].[Na+].CS[C:20]#[N:21]>ClCCCl>[C:20]([C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=1[OH:11])#[N:21]

Participants

7

Reactant 5

HCID 996PhenolHCID 11168Methyl thiocyanateHCID 14798Sodium HydroxideHCID 25134Boron tribromideHCID 6451240Aluminum(III) Chloride2×

Product 1

HCID 119072-HydroxybenzonitrileYield 79%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent2×

Procedure

To a solution of 1.13 ml of boron tribromide in 6 ml of 1,2-dichloroethane were added a solution of 941 mg of phenol in 10 ml of 1,2-dichloroethane, 0.82 ml of methyl thiocyanate and 1.33 g of aluminium chloride under ice-cooling. After dissolving aluminium chloride with stirring at room temperature, the mixture was heated at 80° C. on an oil bath for 3 hr. After cooling, the reaction solution was poured into 33 ml of 4N aqueous sodium hydroxide and stirred at 75°-80° C. for 30 min. on an oil bath. After washing with methylene chloride, the aqueous layer was acidified with 25 ml of 6N HCl and extracted with ether. The ether layer was extracted with 2N aqueous sodium carbonate, dried over anhydrous magnesium sulfate and concentrated to recover 147 mg of phenol. On the other hand, the sodium carbonate layer was acidified with 6N HCl, extracted with ether, and the ether layer was dried over anhydrous magnesium sulfate and concentrated. The residue was recrystallized from methylene chloride-petroleum ether to give 943 mg of 2-cyanophenol as white crystals melting at 97°-98° C.

Workup

  1. temperaturecooling
  2. temperaturethe mixture was heated at 80° C. on an oil bath for 3 hr
  3. temperatureAfter cooling
  4. stirringstirred at 75°-80° C. for 30 min. on an oil bath
  5. washAfter washing with methylene chloride
  6. extractionextracted with ether
  7. extractionThe ether layer was extracted with 2N aqueous sodium carbonate
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated
  10. customto recover 147 mg of phenol
  11. extractionextracted with ether
  12. dry with materialthe ether layer was dried over anhydrous magnesium sulfate
  13. concentrationconcentrated
  14. customThe residue was recrystallized from methylene chloride-petroleum ether

Sources & evidence

ORD record
ord-6b4679c14b18449e9da12a94c16dc722
Source dataset
uspto-grants-1988_09
Patent number
US04774331

Reaction notes

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