Bromine → Methyl 4-(bromomethyl)-2-hydroxybenzoate

HRID 884439Notes

Reaction equation

HRID 884439 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[C:5](=[CH:7][C:8]([CH3:11])=[CH:9][CH:10]=1)[OH:6].[Br:13]Br>C(Cl)(Cl)(Cl)Cl>[CH3:1][O:2][C:3](=[O:12])[C:4]1[C:5](=[CH:7][C:8]([CH2:11][Br:13])=[CH:9][CH:10]=1)[OH:6]

Participants

4

Reactant 2

HCID 24408BromineHCID 78400Benzoic acid, 2-hydroxy-4-methyl-, methyl ester

Product 1

HCID 22556059Methyl 4-(bromomethyl)-2-hydroxybenzoate

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent2×

Procedure

A refluxing solution of 4-methylsalicylic acid methyl ester (5.1 g, 31.3 mmol) in carbon tetrachloride (50 mL) was treated dropwise with a solution of bromine (1.6 mL, 31.3 mmol) in carbon tetrachloride (5 mL) while under illumination by a 200 W incandescent light bulb. The reaction mixture was stirred for an additional 30 min at reflux and concentrated in vacuo. The residue was dissolved in EtOAc (50 mL) and washed with aqueous sodium thiosulfate (5%, 50 mL), water (50 mL), and brine (50 mL). The organic layer was dried over Na2SO4, concentrated, and the product 4-bromomethylsalicylic acid methyl ester was isolated by recrystallization from heptane (1.6 g, 21%).

Workup

  1. temperatureat reflux
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in EtOAc (50 mL)
  4. washwashed with aqueous sodium thiosulfate (5%, 50 mL), water (50 mL), and brine (50 mL)
  5. dry with materialThe organic layer was dried over Na2SO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-4288fd434a91404191e1d4f368ec1d60
Source dataset
uspto-grants-2012_08
Patent number
US08242115B2

Reaction notes

Loading…