Phenol → HCID 66712812, compound

HRID 523741Notes

Reaction equation

HRID 523741 reaction equation
[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][C:6]=1[CH3:12])[CH3:2].[C:14]1([OH:20])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C([O-])([O-])=O.[Cs+].[Cs+].C(OCC)(=O)C>C1(C)C=CC=CC=1>[CH2:1]([O:3][C:4](=[O:13])[C:5]1[CH:10]=[CH:9][C:8]([O:20][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:7][C:6]=1[CH3:12])[CH3:2]

Participants

6

Reactant 4

HCID 996PhenolHCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 22616358Ethyl 4-bromo-2-methylbenzoate

Product 1

HCID 66712812HCID 66712812, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

27.5 g of 4-bromo-2-methyl-benzoic acid ethyl ester was dissolved in 120 mL of anhydrous toluene. To the solution was added 21.3 g of phenol, 73.6 g of Cs2CO3, 551 μL of ethyl acetate, 22 g of activated 4 A molecular sieves, and 5.68 g of 90% copper(I) trifluoromethanesulfonate benzene complex. The reaction was placed under a nitrogen atmosphere and heated at reflux temperature for 48 h. The resultant mixture was partitioned between water and ethyl acetate, and the mixture filtered through a fine sintered glass filter to remove insoluble material. The organic fraction was washed three times with 1.0N NaOH, once with brine, dried over anhydrous sodium sulfate, and concentrated to 18.2 g of a pale tan liquid: 1H NMR (200 MHz, CDCl3) δ 7.93-7.88 (dd, J=1.3, 7.8 Hz, 1H) 7.39-7.30 (m, 2H), 7.19-7.10 (tt, J=1.2, 7.4 Hz, 1H), 7.06-7.7.0 (m, 2H), 6.80-6.75 (m, 2H), 4.37-4.26 (q, J=7.0 Hz, 2H), 2.56 (s, 3H), 1.40-1.33 (t, J=7.0 Hz, 3H).

Workup

  1. temperatureheated
  2. temperatureat reflux temperature for 48 h
  3. customThe resultant mixture was partitioned between water and ethyl acetate
  4. filtrationthe mixture filtered through a fine sintered glass
  5. filtrationfilter
  6. customto remove insoluble material
  7. washThe organic fraction was washed three times with 1.0N NaOH
  8. dry with materialonce with brine, dried over anhydrous sodium sulfate
  9. concentrationconcentrated to 18.2 g of a pale tan liquid

Sources & evidence

ORD record
ord-d0ca7ef5f21d4d1e9458da61b37c3abd
Source dataset
uspto-grants-2016_05
Patent number
US09339527B2

Reaction notes

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