2-Benzylidenecyclohexanone → 2-Benzylphenol

HRID 1158267Notes

Reaction equation

HRID 1158267 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.C(OCC)(=O)/C=C\C(OCC)=O>[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 989262-BenzylidenecyclohexanoneHCID 5271566Diethyl Maleate

Product 1

HCID 242162-BenzylphenolYield 58.1%

Reagents, catalysts & solvents 2

HCID 178418390HCID 178418390, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
185 °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 51.7 g (0.3 mole) of diethyl maleate 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 returned to ordinary pressure using nitrogen; this operation was repeated three times. Then, the system was stirred at 185° C. for 3 hours and cooled to room temperature. 100 ml of toluene was added to the system. Filtration was conducted to remove the palladium carbon. The filtrate was extracted with 100 ml of a 10% aqueous sodium hydroxide solution, and this operation was repeated four times. The aqueous layer was washed with 30 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 100 ml of toluene. The toluene layer was washed with water and a saturated aqueous sodium chloride solution in this order. The toluene layer was dried over anhydrous sodium sulfate and then subjected to vacuum distillation to remove toluene, to obtain 10.7 g of an oil. This oil was subjected to Kugel Rohr distillation to obtain 9.0 of a colorless oil. Yield: 49% The purity of the intended product in the oil was >99.9% 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 100 ml of a 10% aqueous sodium hydroxide solution
  7. washThe aqueous layer was washed with 30 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 100 ml of toluene
  10. washThe toluene layer was washed with water
  11. dry with materialThe toluene layer was dried over anhydrous sodium sulfate
  12. distillationsubjected to vacuum distillation
  13. customto remove toluene

Sources & evidence

ORD record
ord-da664eb427fc4f6b9a97408a5ca85c88
Source dataset
uspto-grants-2010_10
Patent number
US07807856B2

Reaction notes

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