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

HRID 907656

Reaction equation

HRID 907656 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].[Cl-].[Cl-].[Cl-].[Al+3]>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 6451240Aluminum(III) Chloride

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 trichloride (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-75447bba3b514e409f443015d7bfb054
Source dataset
uspto-grants-2011_09
Patent number
US08013166B2

Linked notes

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