Bromobenzene → 4-(4-Bromophenyl)-2,2-dimethyl-4-oxo-butyric Acid

HRID 9519

Reaction equation

HRID 9519 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:8][C:9]1([CH3:16])[CH2:13][C:12](=[O:14])[O:11][C:10]1=[O:15].[Al]>ClC(Cl)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:12](=[O:14])[CH2:13][C:9]([CH3:16])([CH3:8])[C:10]([OH:15])=[O:11])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 7961BromobenzeneHCID 870672,2-Dimethylsuccinic anhydrideHCID 5359268Aluminum

Product 1

HCID 219857574-(4-Bromophenyl)-2,2-dimethyl-4-oxo-butyric AcidYield 63%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

To a chilled solution (ice/water bath) of bromobenzene (7.71 g, 49.1 mmol) and 3,3-dimethyldihydro-2,5-furandione (5.99 g, 46.7 mmol) in dichloroethane (150 mL) was added aluminum trichworide (13.28 g, 99.58 mmol). The ice bath was removed and the reaction mixture was stirred at rt overnight. The mixture was again chilled in an ice/water bath, and then quenched with 1 M aqueous hydrochloric acid. Water (70 mL) was added and the layers were separated. The aqueous layer was extracted with ethyl acetate (3×50 mL). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by flash chromatography (Biotage apparatus, 17:83 ethyl acetate/hexane) to give 4-(4-bromophenyl)-2,2-dimethyl-4-oxobutanoic acid as a white solid (8.34 g, 63%). LC-MS: ret. time 2.79 min; m/z 284.8 (MH+); 1H NMR (300 MHz, CDCl3) δ 1.36 (s, 6H), 3.27 (s, 2H), 7.60 (d, 2H), 7.81 (d, 2H).

Workup

  1. customThe ice bath was removed
  2. temperatureThe mixture was again chilled in an ice/water bath
  3. customquenched with 1 M aqueous hydrochloric acid
  4. additionWater (70 mL) was added
  5. customthe layers were separated
  6. extractionThe aqueous layer was extracted with ethyl acetate (3×50 mL)
  7. dry with materialThe combined organic layers were dried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by flash chromatography (Biotage apparatus, 17:83 ethyl acetate/hexane)

Sources & evidence

ORD record
ord-df37945b51904d399bb64ad4006d4aeb
Source dataset
uspto-grants-2006_08
Patent number
US07091228B2

Linked notes

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