Hydrogen Peroxide → 1-(Cyclohexyloxy)-4-methoxy-2,2,6,6-tetramethylpiperidine

HRID 133633Notes

Reaction equation

HRID 133633 reaction equation
CS(O)(=O)=O.[OH:6][N:7]1[C:12]([CH3:14])([CH3:13])[CH2:11][CH:10]([O:15][CH3:16])[CH2:9][C:8]1([CH3:18])[CH3:17].OO.S([O-])([O-])=O.[Na+].[Na+].C(O[CH2:31][CH3:32])(=O)C>O.C1CCCCC1.C(#N)C>[CH:32]1([O:6][N:7]2[C:12]([CH3:13])([CH3:14])[CH2:11][CH:10]([O:15][CH3:16])[CH2:9][C:8]2([CH3:18])[CH3:17])[CH2:31][CH2:10][CH2:9][CH2:8][CH2:17]1

Participants

9

Reactant 5

HCID 784Hydrogen PeroxideHCID 6395Methanesulfonic AcidHCID 8857Ethyl AcetateHCID 24437Sodium SulfiteHCID 4125777HCID 4125777, compound

Product 1

HCID 498514451-(Cyclohexyloxy)-4-methoxy-2,2,6,6-tetramethylpiperidineYield 59%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8078CyclohexaneSolvent

Conditions

Temperature
52 °C

Procedure

A solution of 0.246 g (0.885 mmol) of ferrous sulfate heptahydrate and 0.246 g (2.6 mmol) of methanesulfonic acid in 2 ml of water is added to a mixture of 4.85 g (26.0 mmol) of 1-oxyl-4-methoxy-2,2,6,6-tetramethylpiperidine, 35 ml of acetonitrile, and 22 ml of cyclohexane. The reaction mixture is heated to 52° C. A solution of 5.68 g (83 mmol) of 50% aqueous hydrogen peroxide is added dropwise to the reaction mixture over 2.5 hours while the reaction temperature is brought to and maintained at reflux (62° C). After the peroxide is added, the reaction mixture is stirred at reflux for 1.75 hours, and then allowed to cool slowly to 33° C. Peroxide is decomposed by the addition of aqueous sodium sulfite solution. The reaction mixture is diluted with ethyl acetate, and the organic layer is washed with water and then concentrated. Purification by flash chromatography with 20:1 heptane-ethyl acetate affords 4.11 g (59% yield) of the title compound, a colorless liquid. Structure is verified by NMR analysis.

Workup

  1. temperaturemaintained
  2. temperatureat reflux (62° C)
  3. temperatureat reflux for 1.75 hours
  4. temperatureto cool slowly to 33° C
  5. washthe organic layer is washed with water
  6. concentrationconcentrated
  7. customPurification by flash chromatography with 20:1 heptane-ethyl acetate

Sources & evidence

ORD record
ord-91e8d80d63d945e8ac0a92ead8bc9728
Source dataset
uspto-grants-2008_06
Patent number
US07390904B2

Reaction notes

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