Benzoyl Peroxide → Methyl 4-bromo-2-(bromomethyl)benzoate

HRID 894179Notes

Reaction equation

HRID 894179 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=1.[Br:13]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Br:13][CH2:8][C:6]1[C:5]([C:9]([O:11][CH3:12])=[O:10])=[CH:4][CH:3]=[C:2]([Br:1])[CH:7]=1

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 22031226Methyl 4-bromo-2-methylbenzoate

Product 1

HCID 22031079Methyl 4-bromo-2-(bromomethyl)benzoate

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

Treat a solution of 15.0 gm. (0.0655 mole) of methyl 5-bromo-o-toluate in 75 ml. of carbon tetrachloride portionwise during 30 minutes with a mixture of 12.83 gm. (0.0721 mole) of N-bromosuccinimide and 130 mg. of benzoyl peroxide. Heat the resulting mixture under reflux for 3 hours. Cool to room temperature and separate the succinimide by filtration. Remove the solvent under vacuum to obtain methyl α,5-dibromo-o-toluate as a yellow residual oil. Heat a mixture of 9.05 gm. (0.0655 mole) of 3,4-methylenedioxyphenol, 75 ml. of dimethylformamide, 27.16 gm. (0.1965 mole) of potassium carbonate and the methyl α,5-dibromo-o-toluate obtained above at 55°-60° C. for 2 hours. Cool the mixture and pour into 350 ml. of water. Extract the resulting oil into ether, wash with water and dry over anhydrous magnesium sulfate. Remove the solvent under vacuum to obtain the title product as a waxy solid (yield 23.92 gm.). Recrystallize from cyclohexane to obtain pure product as yellow needles [yield 16.12 gm. m.p. 93°-98° C., pmr (CDCl3) 3.88 (3H,s, CH3O--), 5.30 (2H,s,CH2O--), 5.85 (2H, s,OCH2O--)].

Workup

  1. additionTreat a solution of 15.0 gm
  2. temperatureHeat the resulting mixture
  3. temperatureunder reflux for 3 hours
  4. customseparate the succinimide
  5. filtrationby filtration
  6. customRemove the solvent under vacuum

Sources & evidence

ORD record
ord-a357942396c2447aa53c59fa4f3d4b12
Source dataset
uspto-grants-1981_08
Patent number
US04282365

Reaction notes

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