Methanol → Methyl 4-(2-bromophenyl)-2,4-dioxobutanoate

HRID 1712933Notes

Reaction equation

HRID 1712933 reaction equation
[Na].CO.[C:4]([O:10][CH3:11])(=[O:9])[C:5]([O:7]C)=O.[Br:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19](=[O:21])[CH3:20]>CCOCC>[Br:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19](=[O:21])[CH2:20][C:5](=[O:7])[C:4]([O:10][CH3:11])=[O:9]

Participants

6

Reactant 4

HCID 887MethanolHCID 11120Dimethyl oxalateHCID 750602'-BromoacetophenoneHCID 5360545Sodium

Product 1

HCID 43119003Methyl 4-(2-bromophenyl)-2,4-dioxobutanoateYield 90.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Sodium (120 mg, 0.0051 mol) was added slowly to MeOH (2.5 mL, 0.062 mol) at −5° C. To this solution were added dimethyl oxalate (500 mg, 0.0042 mol) and 1-(2-bromophenyl)ethanone (840 mg, 0.0042 mol) in Et2O (5 mL). The reaction mixture was allowed to stir for 12 h and then concentrated and partitioned between Et2O and water. The aqueous solution was separated and cooled in an ice bath. AcOH was added followed by 1N HCl until the solution was acidic. The mixture was extracted with Et2O, and organic solution was dried over Na2SO4, filtered and concentrated to afford methyl 4-(2-bromophenyl)-2,4-dioxobutanoate (1.08 g, 89%) which was used without purification in the next step. LCMS: (FA) ES+ 287.0

Workup

  1. concentrationconcentrated
  2. custompartitioned between Et2O and water
  3. customThe aqueous solution was separated
  4. temperaturecooled in an ice bath
  5. additionAcOH was added
  6. extractionThe mixture was extracted with Et2O, and organic solution
  7. dry with materialwas dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-cea7d65805fb4405b58d4db9a95c412a
Source dataset
uspto-grants-2010_09
Patent number
US07795249B2

Reaction notes

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