4-Chloro-3-methylphenol → 2-(Bromomethyl)-1-chloro-4-methoxybenzene

HRID 440538Notes

Reaction equation

HRID 440538 reaction equation
CI.[Cl:3][C:4]1[CH:9]=[CH:8][C:7](O)=[CH:6][C:5]=1[CH3:11].[C:12](=[O:15])([O-])[O-].[K+].[K+].[Br:18]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>CC(C)=O.C(Cl)(Cl)(Cl)Cl>[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([O:15][CH3:12])=[CH:6][C:5]=1[CH2:11][Br:18]

Participants

8

Reactant 5

HCID 17324-Chloro-3-methylphenolHCID 6328Methyl iodide2×HCID 7187Benzoyl PeroxideHCID 11430Potassium CarbonateHCID 67184N-bromobutanimide

Product 1

HCID 124845332-(Bromomethyl)-1-chloro-4-methoxybenzene

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

Methyl iodide (110 g was added dropwise to a stirred solution of 4-chloro-3-methylphenol (100 g) and potassium carbonate (194 g) in acetone (500 ml). The mixture was stirred for 1.5 hours. Methyl iodide (142 g) was added and the mixture stirred for a further hour. Solvent was removed by evaporation and the residue partitioned between water and ethyl acetate. The organic layer yielded an oil which was heated under reflux for 2 hours with N-bromosuccinimide (119 g) and benzoyl peroxide (1 g) in carbon tetrachloride (250 ml). The mixture was cooled, filtered and the filtrate concentrated to give a residue which was distilled under high vacuum. The fractions collected between 88° and 94° C./0.4 mbar were recrystallised from petroleum ether (b.p. 60°-80° C.) to give 2-chloro-5-methoxy benzyl bromide, m.p. 51°-52° C.

Workup

  1. stirringthe mixture stirred for a further hour
  2. customSolvent was removed by evaporation
  3. customthe residue partitioned between water and ethyl acetate
  4. customThe organic layer yielded an oil which
  5. temperaturewas heated
  6. temperatureThe mixture was cooled
  7. filtrationfiltered
  8. concentrationthe filtrate concentrated
  9. customto give a residue which
  10. distillationwas distilled under high vacuum
  11. customThe fractions collected between 88° and 94° C./0.4 mbar
  12. customwere recrystallised from petroleum ether (b.p. 60°-80° C.)

Sources & evidence

ORD record
ord-1d535b203d78433f9de20e65f2021495
Source dataset
uspto-grants-1996_05
Patent number
US05519034

Reaction notes

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