Methyl morpholine oxide → Ethyl 1-(p-chlorophenyl)-beta-oxocyclopropanepropionate

HRID 1741431Notes

Reaction equation

HRID 1741431 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([CH:11]([OH:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.C[N+]1([O-])CCOCC1>C(#N)C.C(OCC)C.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2([C:11](=[O:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH2:10][CH2:9]2)=[CH:6][CH:7]=1

Participants

6

Reactant 2

HCID 82029Methyl morpholine oxideHCID 21835801Ethyl 1-(p-chlorophenyl)-beta-hydroxy-cyclopropanepropionate

Product 1

HCID 21835800Ethyl 1-(p-chlorophenyl)-beta-oxocyclopropanepropionateYield 55%

Reagents, catalysts & solvents 3

HCID 178419074HCID 178419074, compoundCatalystHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Procedure

A solution of ethyl 1-(p-chlorophenyl)-β-hydroxy-cyclopropanepropionate (7.9 g, 29.4 mmol) and 4-methyl-morpholine N-oxide (14.0 g, 120 mmol) in acetonitrile containing 30 4 Å molecular sieves is stirred at room temperature for 20 minutes, treated with tetrapropyl-ammonium perruthenate (0.8 g, 2.3 mmol), stirred for two hours while maintaining the reaction mixture temperature at room temperature with an ice-water bath, diluted with diethyl ether, filtered through diatomaceous earth, and concentrated in vacuo to obtain a residue. A solution of the residue in diethyl ether is washed sequentially with water, 5% sulfuric acid, water and brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to obtain a dark oil. Chromatography of the oil using silica gel and a 1:19 to 3:17 ethyl acetate/hexanes gradient gives the title product as a pale yellow oil (4.3 g, 55%) which is identified by NMR spectral analyses.

Workup

  1. filtrationfiltered through diatomaceous earth
  2. concentrationconcentrated in vacuo
  3. customto obtain a residue
  4. washA solution of the residue in diethyl ether is washed sequentially with water, 5% sulfuric acid, water and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customto obtain a dark oil

Sources & evidence

ORD record
ord-f97e9bc5afca420a8c2ec6ed565db699
Source dataset
uspto-grants-1999_10
Patent number
US05973190

Reaction notes

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