N-bromobutanimide → Benzoic acid, 4-(bromomethyl)-2,5-difluoro-, methyl ester

HRID 508436Notes

Reaction equation

HRID 508436 reaction equation
[F:1][C:2]1[CH:11]=[C:10]([CH3:12])[C:9]([F:13])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[Br:14]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[Br:14][CH2:12][C:10]1[C:9]([F:13])=[CH:8][C:3]([C:4]([O:6][CH3:7])=[O:5])=[C:2]([F:1])[CH:11]=1

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 22955958Methyl 2,5-difluoro-4-methylbenzoate

Product 1

HCID 66666576Benzoic acid, 4-(bromomethyl)-2,5-difluoro-, methyl esterYield 37.1%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
88 °C

Procedure

To methyl 2,5-difluoro-4-methylbenzoate (Preparation 26, 55 g, 0.29 mol) in carbon tetrachloride (0.4 L) was added N-bromosuccinimide (52.6 g, 0.29 mol) and dibenzoyl peroxide (1 g, 3.5 mmol) and heated at 88° C. for 5 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and allowed to stand for 18 hours, then washed with water (400 mL), brine (100 mL), dried over sodium sulphate and concentrated in vacuo. The resulting solid was triturated with n-heptane (120 mL) and recrystallised from hot n-heptane (50 mL) to yield the title compound as a pale yellow solid (28.5 g, 36%).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. washwashed with water (400 mL), brine (100 mL)
  3. dry with materialdried over sodium sulphate
  4. concentrationconcentrated in vacuo
  5. customThe resulting solid was triturated with n-heptane (120 mL)
  6. customrecrystallised from hot n-heptane (50 mL)

Sources & evidence

ORD record
ord-5f8be42c46924cbc9c397217469f2b72
Source dataset
uspto-grants-2015_08
Patent number
US09096500B2

Reaction notes

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