Phenol → 2-Hydroxybenzonitrile

HRID 623243Notes

Reaction equation

HRID 623243 reaction equation
B(Cl)(Cl)Cl.[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 25135Boron TrichlorideHCID 6451240Aluminum(III) Chloride2×

Product 1

HCID 119072-HydroxybenzonitrileYield 84%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent2×

Procedure

To 6 ml of a solution of 2.02M of boron trichloride in 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 is poured into 33 ml of 4N aqueous sodium hydroxide and stirred at 75°-80° C. for 30 min. on an oil bath. The aqueous layer was washed with methylene chloride, acidified with 25 ml of 6N HCl and extracted with ether. Then, the ether layer was washed with 2N aqueous sodium carbonate, dried over anhydrous magnesium sulfate and concentrated to recover 39 mg of phenol. On the other hand, the sodium carbonate layer was acidified with 6N HCl and extracted with ether. The ether layer was dried over anhydrous magnesium sulfate and evaporated to remove the solvent. The crystalline residue (1.13 g) was recrystallized from methylene chloride-petroleum ether, whereby 1.002 g of 2-cyanophenol was obtained as colorless 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. washThe aqueous layer was washed with methylene chloride
  6. extractionextracted with ether
  7. washThen, the ether layer was washed with 2N aqueous sodium carbonate
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated
  10. customto recover 39 mg of phenol
  11. extractionextracted with ether
  12. dry with materialThe ether layer was dried over anhydrous magnesium sulfate
  13. customevaporated
  14. customto remove the solvent
  15. customThe crystalline residue (1.13 g) was recrystallized from methylene chloride-petroleum ether

Sources & evidence

ORD record
ord-6de94f7954d244f89f4bd14e0060f1a4
Source dataset
uspto-grants-1988_09
Patent number
US04774331

Reaction notes

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