Benzoic acid, 4-(4-methoxybenzoyl)-, methyl ester → Methyl 4-(4-hydroxybenzoyl)benzoate

HRID 2100041Notes

Reaction equation

HRID 2100041 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].C[O:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]([C:15]2[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][CH:16]=2)=[O:14])=[CH:9][CH:8]=1>C1(C)C=CC=CC=1>[OH:6][C:7]1[CH:8]=[CH:9][C:10]([C:13]([C:15]2[CH:16]=[CH:17][C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:23][CH:24]=2)=[O:14])=[CH:11][CH:12]=1

Participants

4

Reactant 2

HCID 257913Benzoic acid, 4-(4-methoxybenzoyl)-, methyl esterHCID 6451240Aluminum(III) Chloride

Product 1

HCID 10038024Methyl 4-(4-hydroxybenzoyl)benzoateYield 93%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a 3-necked round-bottomed flask was added AlCl3 (32 g, 0.24 mol.) followed by anhydrous toluene (250 mL). The flask was equipped with a reflux condenser and nitrogen inlet and the suspension was stirred at RT under a nitrogen atmosphere. To the stirred suspension was added methyl 4-{[4-(methyloxy)phenyl]carbonyl}benzoate (23) (16.0 g, 0.059 mol.) portionwise at RT under a nitrogen atmosphere. The reaction mixture was heated at 85° C. with stirring under a nitrogen atmosphere. After 2 h, the oil bath was removed and the reaction mixture was allowed to cool at RT. The reaction mixture was cooled in an ice-water bath and ice was added very slowly portionwise (Note: significant HCl evolved upon addition of ice to the reaction mixture.) followed by the slow addition of ice-water. The reaction mixture was partitioned between EtOAc and water. The organic phase washed with brine, dried over MgSO4, filtered, and the filtrate was concentrated to give the crude product as a red-brown solid. The crude product was triturated with hot hexanes and the brown solid was filtered to give 14.0 g (93%) of compound 24. 1H NMR (400 MHz, DMSO-d6): δ 3.88 (s, 3 H), 6.88 (d, J=8.6 Hz, 2 H), 7.65 (d, J=8.7 Hz, 2 H), 7.74 (d, J=8.2 Hz, 2 H), 8.07 (d, J=8.2 Hz, 2 H), 10.51 (s, 1 H).

Workup

  1. customThe flask was equipped with a reflux condenser and nitrogen inlet
  2. temperatureThe reaction mixture was heated at 85° C.
  3. stirringwith stirring under a nitrogen atmosphere
  4. customthe oil bath was removed
  5. temperatureto cool at RT
  6. temperatureThe reaction mixture was cooled in an ice-water bath
  7. additionice was added very slowly portionwise (
  8. additionsignificant HCl evolved upon addition of ice to the reaction mixture
  9. addition) followed by the slow addition of ice-water
  10. customThe reaction mixture was partitioned between EtOAc and water
  11. washThe organic phase washed with brine
  12. dry with materialdried over MgSO4
  13. filtrationfiltered
  14. concentrationthe filtrate was concentrated
  15. customto give the crude product as a red-brown solid
  16. customThe crude product was triturated with hot hexanes
  17. filtrationthe brown solid was filtered

Sources & evidence

ORD record
ord-f38eeccda18a4548902657d4c08e89e5
Source dataset
uspto-grants-2009_08
Patent number
US07569601B2

Reaction notes

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