Hydrochloric Acid → Methyl 2-bromo-5-methoxybenzoate

HRID 1925087Notes

Reaction equation

HRID 1925087 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][C:8]([O:11][CH3:12])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].Cl.[CH3:14]O>>[Br:1][C:2]1[CH:10]=[CH:9][C:8]([O:11][CH3:12])=[CH:7][C:3]=1[C:4]([O:6][CH3:14])=[O:5]

Participants

4

Reactant 3

HCID 313Hydrochloric AcidHCID 887MethanolHCID 899062-Bromo-5-methoxybenzoic acid

Product 1

HCID 2776849Methyl 2-bromo-5-methoxybenzoateYield 85%

Procedure

To a stirred solution of 2-bromo-5-methoxybenzoic acid (Aldrich 384003; 5.0 g, 21.6 mmol) in methanol (80 mL) was added concentrated hydrochloric acid (2 mL) and the mixture was heated under reflux for 18 hours. The resulting solution was cooled, the solvent was removed in vacuo, water (100 mL) was added and the mixture was extracted with ethyl acetate (2×100 mL). The combined extracts were washed with saturated aqueous sodium hydrogen carbonate, dried over MgSO4, filtered and evaporated to obtain methyl 2-bromo-5-methoxybenzoate as a light brown oil (4.50 g, 85%); NMR Spectrum δH (300 MHz, CDCl3) 7.53 (1H, d, J 8.8 Hz, 3-H), 7.32 (1H, d, J 3.0 Hz, 6-H), 6.89 (1H, dd, J 3.0, 8.8 Hz, 4-H), 3.94 (3H, s, Ar OCH3) and 3.82 (3H, s, CO2CH3) (data in accordance with published values, see Barhate, N. B.; Gajare, A. S.; Wakharkar, R. D.; Bedekar, A. V. Tetrahedron 1999, 55, 11127-11142); νmax/cm−1 (thin film) 2951, 1732 (C═O), 1592, 1472, 1433, 1289, 1250, 1227, 1099, 1017, 975, 823, 792 (data in accordance with published values, see Barhate, N. B.; Gajare, A. S.; Wakharkar, R. D.; Bedekar, A. V. Tetrahedron 1999, 55, 11127-11142); Rf (hexane-ethyl acetate 5:1) 0.58.

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 18 hours
  3. temperatureThe resulting solution was cooled
  4. customthe solvent was removed in vacuo, water (100 mL)
  5. additionwas added
  6. extractionthe mixture was extracted with ethyl acetate (2×100 mL)
  7. washThe combined extracts were washed with saturated aqueous sodium hydrogen carbonate
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-0353252efe1b405db5927fa9d88a3c95
Source dataset
uspto-grants-2012_05
Patent number
US08178578B2

Reaction notes

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