Bromine → Methyl 6-bromo-3-hydroxy-2-methylbenzoate

HRID 577547Notes

Reaction equation

HRID 577547 reaction equation
[OH:1][C:2]1[C:3]([CH3:12])=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[Br:13]Br.[O-]S([O-])(=S)=O.[Na+].[Na+]>ClCCl>[Br:13][C:9]1[C:4]([C:5]([O:7][CH3:8])=[O:6])=[C:3]([CH3:12])[C:2]([OH:1])=[CH:11][CH:10]=1

Participants

5

Reactant 3

HCID 24408BromineHCID 24477Sodium ThiosulfateHCID 12488879Methyl 3-hydroxy-2-methylbenzoate

Product 1

HCID 77058981Methyl 6-bromo-3-hydroxy-2-methylbenzoateYield 92%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of methyl 3-hydroxy-2-methylbenzoate (114a, 3.557 g, 21.40 mmol) in dichloromethane (100 mL) in a dry ice/acetonitrile bath (˜−45° C.) was added bromine (1.15 mL, 22.5 mmol) dropwise. The reaction was stirred at −45° C. for 2 hours before Na2S2O3 (sat. aq., 2 mL) was added. The reaction mixture was allowed to warm to room temperature. The reaction mixture was diluted with dichloromethane and washed with water. The dichloromethane layer was concentrated under vacuum, and the resulting crude product was purified by column chromatography (0-40% ethyl acetate/heptane) to give methyl 6-bromo-3-hydroxy-2-methylbenzoate (114b, 4.8 g, 92% yield) as a white solid.

Workup

  1. additionwas added
  2. washwashed with water
  3. concentrationThe dichloromethane layer was concentrated under vacuum
  4. customthe resulting crude product was purified by column chromatography (0-40% ethyl acetate/heptane)

Sources & evidence

ORD record
ord-df2ba9b3fe8045e9b14c73f71d8c0c4d
Source dataset
uspto-grants-2015_05
Patent number
US09040515B2

Reaction notes

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