N-bromobutanimide → Methyl 4-(bromomethyl)-2-hydroxybenzoate

HRID 1600399Notes

Reaction equation

HRID 1600399 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([OH:12])[C:5](=[CH:10][CH:11]=1)[C:6]([O:8][CH3:9])=[O:7].[Br:13]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.BrN1C(=O)CCC1=O>[CH3:9][O:8][C:6](=[O:7])[C:5]1[C:4](=[CH:3][C:2]([CH2:1][Br:13])=[CH:11][CH:10]=1)[OH:12]

Participants

6

Reactant 2

HCID 67184N-bromobutanimideHCID 78400Benzoic acid, 2-hydroxy-4-methyl-, methyl ester

Product 1

HCID 22556059Methyl 4-(bromomethyl)-2-hydroxybenzoateYield 58%

Reagents, catalysts & solvents 3

HCID 7187Benzoyl PeroxideCatalystHCID 67184N-bromobutanimideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

Methyl 4-methylsalicylate (98.1 g 590 mmoles) was dissolved in carbon tetrachloride (600 ml), and N-bromosuccinimide (105.0 g, 590 mmoles) and benzoyl peroxide (0.7 g, 3 mmoles) were added. The mixture was refluxed under nitrogen. After 2 hours, an additional portion (0.7 g) of N-bromosuccinimide was added. Reflux was continued for 16 hours. The reaction mixture was cooled to room temperature and the solid removed by filtration. The yellow filtrate was evaporated to dryness to afford a thick yellow syrup that solidified on standing. Hexanes (500 mL) was addedto the solid, and the mixture was boiled until almost all solids dissolved.The hot hexanes solution was filtered and concentrated until a solid just began to precipitate. The mixture was heated to dissolve the solid, and the solution was allowed to cool slowly to room temperature. Pale yellow crystals formed slowly. The mixture was then chilled in ice for 2 hours tocomplete crystallization. Finally, the solid was filtered, washed with coldhexanes (100 mL), and dried in vacuo to afford 83.5 g (58% yield) of methyl4-bromomethyl-salicylate (m.p. 73°-75° C., open capillary, uncorrected).

Workup

  1. temperatureThe mixture was refluxed under nitrogen
  2. temperatureReflux
  3. waitwas continued for 16 hours
  4. customthe solid removed by filtration
  5. customThe yellow filtrate was evaporated to dryness
  6. customto afford a thick yellow syrup that solidified
  7. filtrationwas filtered
  8. concentrationconcentrated until a solid
  9. customto precipitate
  10. temperatureThe mixture was heated
  11. dissolutionto dissolve the solid
  12. temperatureto cool slowly to room temperature
  13. customPale yellow crystals formed slowly
  14. temperatureThe mixture was then chilled in ice for 2 hours
  15. customtocomplete crystallization
  16. filtrationFinally, the solid was filtered
  17. washwashed with coldhexanes (100 mL)
  18. customdried in vacuo

Sources & evidence

ORD record
ord-612b26b5a9544e989f356888b8da04a5
Source dataset
uspto-grants-1998_04
Patent number
US05744627

Reaction notes

Loading…