Hydrochloric Acid → Benzoic acid, 4-(4-methoxybenzoyl)-, methyl ester

HRID 2100040Notes

Reaction equation

HRID 2100040 reaction equation
[C:1]1([O:7][CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl-].[CH3:10][O:11][C:12](=[O:22])[C:13]1[CH:21]=[CH:20][C:16]([C:17](O)=[O:18])=[CH:15][CH:14]=1.[Al+3].[Cl-].[Cl-].[Cl-].Cl>>[CH3:8][O:7][C:1]1[CH:6]=[CH:5][C:4]([C:17]([C:16]2[CH:20]=[CH:21][C:13]([C:12]([O:11][CH3:10])=[O:22])=[CH:14][CH:15]=2)=[O:18])=[CH:3][CH:2]=1

Participants

5

Reactant 4

HCID 313Hydrochloric AcidHCID 7519AnisoleHCID 6451240Aluminum(III) Chloride2×HCID 53442854Terephthalic acid monomethylester chloride

Product 1

HCID 257913Benzoic acid, 4-(4-methoxybenzoyl)-, methyl esterYield 60%

Procedure

To a 3-necked round-bottomed flask equipped with a magnetic stir bar were added anisole (31 mL, 30.8 g, 0.285 mol.) and terephthalic acid monomethyl ester chloride (19.6 g, 0.099 mol.). The flask was equipped with a powder addition funnel and nitrogen inlet. The powder addition funnel was charged with AlCl3 (40.2 g, 0.301 mol.). The reaction mixture was cooled in an ice-water bath and the AlCl3 was added slowly, portionwise with stirring, under a nitrogen atmosphere. The ice-water bath was removed and the stirred reaction mixture was allowed to warm to room temperature for 3.5 h. The viscous reaction mixture was cooled in an ice-water bath and ice was added very slowly portionwise (Note: significant HCl was released upon addition of ice) followed by the slow addition of ice-water. The reaction mixture solidified upon quenching. The solid was filtered, washed with water, and allowed to stand overnight at RT. The solid washed with water and triturated with hexanes (2×) to give a pink solid. The crude product was recrystallized from EtOAc to give a white solid. The solid was dried to give 16.0 g (60%) of compound 23 as a white solid. 1H NMR (400 MHz, DMSO-d6): δ 3.84 (s, 3 H), 3.88 (s, 3 H), 7.08 (d, J=8.8 Hz, 2 H), 7.74 (d, J=8.8 Hz, 2 H), 7.77 (d, J=8.3 Hz, 2 H), 8.08 (d, J=8.3 Hz, 2 H).

Workup

  1. customTo a 3-necked round-bottomed flask equipped with a magnetic stir bar
  2. customThe flask was equipped with a powder addition funnel and nitrogen inlet
  3. additionThe powder addition funnel
  4. temperatureThe reaction mixture was cooled in an ice-water bath
  5. customThe ice-water bath was removed
  6. customthe stirred reaction mixture
  7. temperatureThe viscous reaction mixture was cooled in an ice-water bath
  8. additionice was added very slowly portionwise
  9. customupon quenching
  10. filtrationThe solid was filtered
  11. washwashed with water
  12. washThe solid washed with water
  13. customtriturated with hexanes (2×)
  14. customto give a pink solid
  15. customThe crude product was recrystallized from EtOAc
  16. customto give a white solid
  17. customThe solid was dried

Sources & evidence

ORD record
ord-3acba4a7dc7a45769fe67d9346944434
Source dataset
uspto-grants-2009_08
Patent number
US07569601B2

Reaction notes

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