Iodine → 2-Bromo-6-iodobenzoic acid

HRID 1519651Notes

Reaction equation

HRID 1519651 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].C(O)(=O)C.C(O)(=O)C.[I:19]C1C=CC=CC=1.II>CN(C)C=O.COC(C)(C)C.Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Br:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([I:19])[C:3]=1[C:4]([OH:6])=[O:5]

Participants

8

Reactant 3

HCID 807IodineHCID 69402-Bromobenzoic acidHCID 12217721Iodo benzene diacetate

Product 1

HCID 534243762-Bromo-6-iodobenzoic acidYield 74.3%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 313Hydrochloric AcidSolventHCID 6228DimethylformamideSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
100 °C

Procedure

2-bromobenzoic acid (20.1 g, 100 mmol), palladium(II) acetate (1.12 mg, 5 mmol), iodobenzene diacetate (38.64 g, 120 mmol) and elemental iodine (30.48 g, 120 mmol) were dissolved in N,N-dimethylformamide (240 mL) and stirred overnight at 100° C. The reaction mixture was cooled to room temperature, diluted with methyl-tert-butylether and 2M hydrochloric acid and washed with 10% aqueous solution of sodium metabisulphite. Organic phase was extracted with 2M sodium hydroxide and the resulting basic aqueous phase was acidified with concentrated aqueous hydrochloric acid and re-extracted with methyl-tert-butylether. The solvent was removed under reduced pressure affording 2-bromo-6-iodobenzoic acid (24.3 g, 74% yield), which was used in the next step without further purification.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. washwashed with 10% aqueous solution of sodium metabisulphite
  3. extractionOrganic phase was extracted with 2M sodium hydroxide
  4. extractionre-extracted with methyl-tert-butylether
  5. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-5cdbea2c0992452e8167d84dcd139286
Source dataset
uspto-grants-2015_07
Patent number
US09073893B2

Reaction notes

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