Cesium carbonate → Ethyl 2-(4-acetyl-2-methylphenoxy)-2-methylpropanoate

HRID 9626

Reaction equation

HRID 9626 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][C:3]=1[CH3:11].C(=O)([O-])[O-].[Cs+].[Cs+].Br[C:19]([CH3:26])([CH3:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21]>C(#N)C.C(OCC)(=O)C>[C:8]([C:5]1[CH:6]=[CH:7][C:2]([O:1][C:19]([CH3:26])([CH3:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[C:3]([CH3:11])[CH:4]=1)(=[O:10])[CH3:9]

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl ester2×HCID 701354'-Hydroxy-3'-methylacetophenone

Product 1

HCID 16756777Ethyl 2-(4-acetyl-2-methylphenoxy)-2-methylpropanoate

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A suspension of 1-(4-hydroxy-3-methylphenyl)ethanone (20.1 g) in acetonitrile (200 ml) was added to a suspension of cesium carbonate (86.6 g) in acetonitrile (400 ml) and the mixture stirred under nitrogen at room temperature for 2 minutes. ethyl 2-bromo-2-methylpropanoate (33 g) was added and the mixture stirred for 25 hours, further ethyl 2-bromo-2-methylpropanoate (33 g) was added and the mixture stirred for a further 16 hours. The mixture was filtered and the filtrate concentrated to give an orange oil, the oil was dissolved in ethyl acetate and the solution washed thrice with 1M sodium hydroxide and brine. The organic layer was separated, dried over sodium sulfate, filtered and the filtrate concentrated; the resulting oil was purified by Biotage® chromatography eluting with cyclohexane:ethyl acetate (9:1) to give the title compound as a clear oil.

Workup

  1. stirringthe mixture stirred for 25 hours
  2. stirringthe mixture stirred for a further 16 hours
  3. filtrationThe mixture was filtered
  4. concentrationthe filtrate concentrated
  5. customto give an orange oil
  6. washthe solution washed thrice with 1M sodium hydroxide and brine
  7. customThe organic layer was separated
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationthe filtrate concentrated
  11. customthe resulting oil was purified by Biotage® chromatography
  12. washeluting with cyclohexane:ethyl acetate (9:1)

Sources & evidence

ORD record
ord-e9e3abe3037745ca9722783f856fcc9a
Source dataset
uspto-grants-2006_08
Patent number
US07091237B2

Linked notes

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