Phenol → HCID 66712812, compound

HRID 908774Notes

Reaction equation

HRID 908774 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 1.0 N 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 1.0 N 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-2e784ad511f44600ba4e4044f3224168
Source dataset
uspto-grants-2011_09
Patent number
US08017625B2

Reaction notes

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