Diphenyl Ether → 2-Benzylphenol

HRID 1158268Notes

Reaction equation

HRID 1158268 reaction equation
[CH:1](=[C:8]1[CH2:13][CH2:12][CH2:11][CH2:10][C:9]1=[O:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(OC2C=CC=CC=2)C=CC=CC=1>[C].[Pd].C1(C)C=CC=CC=1>[CH2:1]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[OH:14])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 7583Diphenyl EtherHCID 989262-Benzylidenecyclohexanone

Product 1

HCID 242162-BenzylphenolYield 97%

Reagents, catalysts & solvents 2

HCID 178418390HCID 178418390, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
245 °C

Procedure

In a 100-ml, four-necked flask equipped with a magnetic stirrer, a reflux condenser and a thermometer were placed 18.6 g (0.1 mole) of the 2-benzylidenecyclohexanone produced in Example 1 and 40 ml of diphenyl ether in this order. The flask inside was purged with nitrogen. Thereto was added 1.9 g (10 wt. %, 0.89 mmole as palladium) of 5% palladium carbon (a product of Wako Pure Chemical Industries, Ltd.). The system was made vacuum using an aspirator and then was returned to ordinary pressure using nitrogen; this operation was repeated three times. Then, the system was stirred at 240 to 250° C. for 8 hours and cooled to room temperature. 50 ml of toluene was added to the system. Filtration was conducted to remove the palladium carbon. The filtrate was extracted with 50 ml of a 10% aqueous sodium hydroxide solution, and this operation was repeated twice. The aqueous layer was washed with 50 ml of toluene. To the resulting aqueous layer was added 35% hydrochloric acid until the aqueous layer became acidic, after which the aqueous layer was extracted with 50 ml of ethyl acetate twice. The ethyl acetate layer was washed with water and a saturated aqueous sodium chloride solution in this order. The ethyl acetate layer was dried over anhydrous sodium sulfate and then subjected to vacuum distillation to remove ethyl acetate, to obtain 17.8 g of an oil. Yield: 97% The purity of the intended product in the oil was 95% as measured by gas chromatography.

Workup

  1. customIn a 100-ml, four-necked flask equipped with a magnetic stirrer, a reflux condenser
  2. customThe flask inside was purged with nitrogen
  3. temperaturecooled to room temperature
  4. filtrationFiltration
  5. customto remove the palladium carbon
  6. extractionThe filtrate was extracted with 50 ml of a 10% aqueous sodium hydroxide solution
  7. washThe aqueous layer was washed with 50 ml of toluene
  8. additionTo the resulting aqueous layer was added 35% hydrochloric acid until the aqueous layer
  9. extractionafter which the aqueous layer was extracted with 50 ml of ethyl acetate twice
  10. washThe ethyl acetate layer was washed with water
  11. dry with materialThe ethyl acetate layer was dried over anhydrous sodium sulfate
  12. distillationsubjected to vacuum distillation
  13. customto remove ethyl acetate

Sources & evidence

ORD record
ord-b853e5b5728743d4aa106ac5f6702004
Source dataset
uspto-grants-2010_10
Patent number
US07807856B2

Reaction notes

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