Bromine → 3-(2-Bromo-acetyl)-4-methoxy-benzoic acid methyl ester

HRID 2405231Notes

Reaction equation

HRID 2405231 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[C:6]([C:12](=[O:14])[CH3:13])[CH:5]=1.[Br:16]Br>C(O)(=O)C.Br>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[C:6]([C:12](=[O:14])[CH2:13][Br:16])[CH:5]=1

Participants

5

Reactant 2

HCID 24408BromineHCID 10798398HCID 10798398, compound

Product 1

HCID 866547993-(2-Bromo-acetyl)-4-methoxy-benzoic acid methyl esterYield 68.5%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 260Hydrogen BromideSolvent

Procedure

3-Acetyl-4-methoxy-benzoic acid methyl ester (T. Nagano et al., J. Am. Chem. Soc. 75 (1953), 6237-6238) (1.25 g) was dissolved in a mixture of acetic acid (7 ml) and hydrobromic acid (3 ml), the solution was cooled in an ice bath, and bromine (0.961 g) added. The mixture was allowed to slowly warm to room temperature and react for 2 h. Then the mixture was evaporated to dryness in vacuo, the residue was partitioned between EA and a saturated aqueous sodium hydrogencarbonate solution, the aqueous phase extracted with EA, and the combined organic extracts were dried over sodium sulfate, filtered and evaporated to dryness. Upon stirring with a mixture of EA and HEP, part of the title compound crystallized and was filtered off. The filtrate was evaporated to dryness and the residue purified by preparative RP HPLC (water/ACN gradient). Altogether, 1.18 g of the title compound were obtained.

Workup

  1. temperaturethe solution was cooled in an ice bath
  2. customreact for 2 h
  3. customThen the mixture was evaporated to dryness in vacuo
  4. customthe residue was partitioned between EA
  5. extractiona saturated aqueous sodium hydrogencarbonate solution, the aqueous phase extracted with EA
  6. dry with materialthe combined organic extracts were dried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated to dryness
  9. customcrystallized
  10. filtrationwas filtered off
  11. customThe filtrate was evaporated to dryness
  12. customthe residue purified by preparative RP HPLC (water/ACN gradient)

Sources & evidence

ORD record
ord-4ed98a498a7f45c2a1a3e7c6fdcaf98b
Source dataset
uspto-grants-2014_08
Patent number
US08802720B2

Reaction notes

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