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

HRID 643773Notes

Reaction equation

HRID 643773 reaction equation
[C:1]1([CH3:11])[C:2]([C:7]([O:9][CH3:10])=[O:8])=[CH:3][CH:4]=[CH:5][CH:6]=1.C1C(=O)N([Br:19])C(=O)C1>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH3:10][O:9][C:7](=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=1[CH2:11][Br:19]

Participants

5

Reactant 2

HCID 33094Methyl o-toluateHCID 67184N-bromobutanimide

Product 1

HCID 2734813Methyl 2-(bromomethyl)benzoateYield 37.4%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

A mixture of methyl o-toluate (13.5 g, 89.9 mmol), NBS (17.6 g, 98.9 mmol), and benzoyl peroxide (50 mg, 0.2 mmol) in carbon tetrachloride (250 mL) was heated at reflux over the weekend. The reaction mixture was allowed to cool, and it was then filtered. The solvents were evaporated under reduced pressure and the residue was purified by chromatography, eluting with 3% ethyl acetate/hexanes to give 2-bromomethyl-benzoic acid methyl ester (7.7 g, 37%) as a white solid. 1HNMR (CDCl3): δ 7.97 (dd, J=1.5 Hz, 8.0 Hz, 1H) 7.49 (m, 2H), 7.38 (dt, J=1.5 Hz, 8.0 Hz, 1H), 4.96 (s, 2H), 3.94 (s, 3H). MS (APCI+): 231 (100), 229 (93).

Workup

  1. temperaturewas heated
  2. temperatureat reflux over the weekend
  3. temperatureto cool
  4. filtrationit was then filtered
  5. customThe solvents were evaporated under reduced pressure
  6. customthe residue was purified by chromatography
  7. washeluting with 3% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-93af325017294a3991d94e7563deb157
Source dataset
uspto-grants-2010_04
Patent number
US07700632B2

Reaction notes

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