Diethyl Maleate → Benzyl-p-cresol

HRID 1158273Notes

Reaction equation

HRID 1158273 reaction equation
[CH:1](=[C:8]1[CH2:13][CH:12]([CH3:14])[CH2:11][CH2:10][C:9]1=[O:15])[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]=[C:12]([CH3:14])[CH:11]=[CH:10][C:9]=1[OH:15])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 5271566Diethyl MaleateHCID 545605944-Methyl-2-(phenylmethylene)cyclohexanone

Product 1

HCID 104342Benzyl-p-cresolYield 50%

Reagents, catalysts & solvents 2

HCID 178418390HCID 178418390, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
200 °C

Procedure

In a 100-ml, four-necked flask equipped with a magnetic stirrer, a reflux condenser and a thermometer were placed 20.0 g (0.1 mole) of the 2-benzylidene-4-methylcyclohexanone produced in Example 10 and 51.7 g (0.3 mole) of diethyl maleate in this order. The flask inside was purged with nitrogen. Thereto was added 1.0 g (5 wt. %, 0.47 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 180° C. for 2 hours and at 200° C. for 2 hours, and then cooled to room temperature. 100 ml of toluene was added to the system. Filtration was conducted to remove the palladium carbon. The filtrate was subjected to vacuum distillation to remove the solvent including toluene and diethyl maleate. To the residue was added 100 ml of toluene, followed by extraction with 100 ml of a 10% aqueous sodium hydroxide solution; and this operation was repeated twice. To the aqueous layer was added 35% hydrochloric acid until the aqueous layer became acidic, after which the aqueous layer was extracted with 100 ml of ethyl acetate. 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 9.8 g of a brown oil. Yield: 50% The purity of the intended product in the oil was 91% 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. distillationThe filtrate was subjected to vacuum distillation
  7. customto remove the solvent
  8. additionTo the residue was added 100 ml of toluene
  9. extractionfollowed by extraction with 100 ml of a 10% aqueous sodium hydroxide solution
  10. additionTo the aqueous layer was added 35% hydrochloric acid until the aqueous layer
  11. extractionafter which the aqueous layer was extracted with 100 ml of ethyl acetate
  12. washThe ethyl acetate layer was washed with water
  13. dry with materialThe ethyl acetate layer was dried over anhydrous sodium sulfate
  14. distillationsubjected to vacuum distillation
  15. customto remove ethyl acetate

Sources & evidence

ORD record
ord-4db767b1e7bb446993f3cb237451ed54
Source dataset
uspto-grants-2010_10
Patent number
US07807856B2

Reaction notes

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