Benzoyl Peroxide → Methyl 2-(bromomethyl)-4-methoxybenzoate

HRID 1715158Notes

Reaction equation

HRID 1715158 reaction equation
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[CH:6][C:5]=1[CH3:12].[Br:14]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH3:11])=[CH:6][C:5]=1[CH2:12][Br:14]

Participants

6

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimide2×HCID 13257269Methyl 4-methoxy-2-methylbenzoate

Product 1

HCID 139928Methyl 2-(bromomethyl)-4-methoxybenzoateYield 68%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 4-methoxy-2-methyl-benzoic acid methyl ester (1.47 g, 8.16 mmol, 1.0 equiv; commercially available) in CCl4 (15 mL) was added N-bromosuccinimide (1.60 g, 8.97 mmol, 1.1 equiv) and dibenzoyl peroxide (0.198 g, 0.45 mmol, 0.05 equiv). The mixture was heated to reflux for 1.5 h, when TLC indicated that still some starling material was left. Therefore, additional N-bromosuccinimide (0.16 g, 0.90 mmol, 0.11 equiv) and dibenzoyl peroxide (0.080 g, 0.41 mmol, 0.18 equiv) was added and heating continued for 1 h. The reaction mixture was cooled down, poured on crashed ice, extracted with ethyl acetate, the combined organic phases washed with a sat. solution of NaCl, dried over Na2SO4 and concentrated by evaporation under reduced pressure. The crude material was purified with silica column chromatography eluting with hexane/ethyl acetate (95:5) affording 1.43 g (68%) of the title compound as yellow crystals. 1H NMR (300 MHz, CDCl3): δ 3.87 (s, 3H), 3.91 (s, 3H), 4.97 (s, 2H), 6.86 (dd, J=8.7 Hz, J=2.7 Hz, 1H), 6.97 (d, J=2.7 Hz, 1H), 7.99 (d, J=8.7 Hz, 1H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 1.5 h
  3. waitwas left
  4. temperatureheating
  5. temperatureThe reaction mixture was cooled down
  6. additionpoured
  7. extractionextracted with ethyl acetate
  8. washthe combined organic phases washed with a sat. solution of NaCl
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated by evaporation under reduced pressure
  11. customThe crude material was purified with silica column chromatography
  12. washeluting with hexane/ethyl acetate (95:5)

Sources & evidence

ORD record
ord-c180be12d2c248f98df9704dd411fbb5
Source dataset
uspto-grants-2010_09
Patent number
US07799806B2

Reaction notes

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