Methyl o-toluate → Methyl 2-(bromomethyl)benzoate

HRID 1662938Notes

Reaction equation

HRID 1662938 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH3:10].[Br:12]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:10][Br:12]

Participants

5

Reactant 2

HCID 33094Methyl o-toluateHCID 67184N-bromobutanimide

Product 1

HCID 2734813Methyl 2-(bromomethyl)benzoateYield 96%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

2-Methylbenzoic acid methyl ester (582 mg, 3.88 mmol), N-bromosuccinimid (NBS) (759 mg, 4.26 mmol), and benzoyl peroxide (13 mg, 0.04 mmol) in CCl4 (10 mL) was stirred at reflux for 5 h. After cooling to room temperature, the reaction mixture was extracted with CH2Cl2 (×3). The extract was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel (Hex/EtOAc=9:1) to give 2-(bromomethyl)benzoic acid methyl ester (Formula 5) as a white solid (850 mg, 96%). Rf=0.6 (Hex:EtOAc=9:1); 1H NMR (300 MHz, CDCl3): δ 7.97 (d, J=7.5 Hz, 1H), 7.48 (m, 2H), 7.38 (td, J=7.8 and 1.2 Hz, 1H), 4.96 (s, 2H), 3.95 (s, 3H). [lit.2 δ 7.97 (m, 1H), 7.40 (m, 3H), 4.96 (s, 2H), 3.95 (s, 3H).

Workup

  1. temperatureat reflux for 5 h
  2. extractionthe reaction mixture was extracted with CH2Cl2 (×3)
  3. washThe extract was washed with brine
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by flash chromatography on silica gel (Hex/EtOAc=9:1)

Sources & evidence

ORD record
ord-fbe72a6ad01647d08b56ee5e06c9a956
Source dataset
uspto-grants-2011_10
Patent number
US08034623B2

Reaction notes

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