Ethyl 8-methyl-1,4-dioxaspiro[4.5]decane-8-carboxylate → Ethyl 1-methyl-4-oxocyclohexanecarboxylate

HRID 1913268Notes

Reaction equation

HRID 1913268 reaction equation
[CH3:1][C:2]1([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:11][CH2:10][C:5]2(OCC[O:6]2)[CH2:4][CH2:3]1.[N+]([O-])([O-])=O.[Ce].[NH4+]>C(#N)C.O>[CH3:1][C:2]1([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:3][CH2:4][C:5](=[O:6])[CH2:10][CH2:11]1

Participants

5

Reactant 2

HCID 19004805Ethyl 8-methyl-1,4-dioxaspiro[4.5]decane-8-carboxylateHCID 57418452Ammonium cerium-nitrate

Product 1

HCID 21911973Ethyl 1-methyl-4-oxocyclohexanecarboxylateYield 101.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 6342AcetonitrileSolvent

Conditions

Temperature
70 °C

Procedure

Ethyl 8-methyl-1,4-dioxaspiro[4.5]decane-8-carboxylate (Int-18b, 2.09 g, 9.17 mmol) was dissolved in acetonitrile (100 mL) and water (50 mL). Ammonium cerium nitrate (503 mg, 0.92 mmol) in water (50 mL) was added and the resulting mixture was heated up to 70° C. and stirred for 1 h. After being cooled down to room temperature, water (100 mL) was added and the mixture was extracted with ether (100 mL×3). The combined organics were washed with water, brine and dried. After concentration, the residue was purified on a column (silica gel, 0-30% ethyl acetate in hexane) which gave ethyl 1-methyl-4-oxocyclohexanecarboxylate (Int-18c) (1.72 g) as an oil.

Workup

  1. temperatureAfter being cooled down to room temperature
  2. extractionthe mixture was extracted with ether (100 mL×3)
  3. washThe combined organics were washed with water, brine
  4. customdried
  5. concentrationAfter concentration
  6. customthe residue was purified on a column (silica gel, 0-30% ethyl acetate in hexane) which

Sources & evidence

ORD record
ord-05e4d28d91c34094b81f567dce02b417
Source dataset
uspto-grants-2013_12
Patent number
US08609675B2

Reaction notes

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