Citric Acid → 2-Bromo-1-[3-methoxy-5-(1-methylethyl)phenyl]ethanone

HRID 657936Notes

Reaction equation

HRID 657936 reaction equation
[CH:1]([C:4]1[CH:5]=[C:6]([C:12](=[O:14])[CH3:13])[CH:7]=[C:8]([O:10][CH3:11])[CH:9]=1)([CH3:3])[CH3:2].[Br-:15].[Br-].[Br-].C1([N+](C)(C)C)C=CC=CC=1.C1([N+](C)(C)C)C=CC=CC=1.C1([N+](C)(C)C)C=CC=CC=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O.O>CO.C1COCC1.CC(=O)OCC>[Br:15][CH2:13][C:12]([C:6]1[CH:7]=[C:8]([O:10][CH3:11])[CH:9]=[C:4]([CH:1]([CH3:3])[CH3:2])[CH:5]=1)=[O:14]

Participants

7

Reactant 4

HCID 311Citric AcidHCID 962WaterHCID 17977687Phenyltrimethylammonium bromide dibromideHCID 58136851HCID 58136851, compound

Product 1

HCID 581368132-Bromo-1-[3-methoxy-5-(1-methylethyl)phenyl]ethanoneYield 149.6%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

1-(3-Isopropyl-5-methoxyphenyl)ethanone (O2.030; 425 mg) was dissolved in methanol/THF (15 ml/15 ml) and admixed while stirring with phenyltrimethylammonium tribromide (831 mg). After stirring at RT for 3 h, the reaction mixture was added to 50 ml of 20% citric acid and stirred for 1 h. After adding water and EA, the EA phase was removed, dried and concentrated. The residue was dissolved in acetonitrile (50 ml), and 2 N sulfuric acid (15 ml) was added to the solution. After standing at RT for 2 h, the mixture was admixed with water and extracted with EA. The EA phase was washed with saturated sodium hydrogencarbonate solution, dried and concentrated. The residue was purified using silica gel (40 g cartridge, n-heptane/EA gradient of 0-50% within 30 min). 520 mg of the title compound were obtained.

Workup

  1. stirringstirred for 1 h
  2. customthe EA phase was removed
  3. customdried
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in acetonitrile (50 ml)
  6. addition2 N sulfuric acid (15 ml) was added to the solution
  7. waitAfter standing at RT for 2 h
  8. extractionextracted with EA
  9. washThe EA phase was washed with saturated sodium hydrogencarbonate solution
  10. customdried
  11. concentrationconcentrated
  12. customThe residue was purified
  13. customsilica gel (40 g cartridge, n-heptane/EA gradient of 0-50% within 30 min)

Sources & evidence

ORD record
ord-1cd31229d89441bc9bd8ab8fae93e998
Source dataset
uspto-grants-2011_12
Patent number
US08076336B2

Reaction notes

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