Hydrogen Peroxide → 1-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

HRID 133657Notes

Reaction equation

HRID 133657 reaction equation
[C:1](#N)[CH3:2].[OH:4][N:5]1[C:10]([CH3:12])([CH3:11])[CH2:9][CH:8]([O:13][C:14](=[O:21])[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH2:7][C:6]1([CH3:23])[CH3:22].OO.S([O-])([O-])=O.[Na+].[Na+]>O.C(OCC)(=O)C.C1CCCCC1>[CH:2]1([O:4][N:5]2[C:10]([CH3:12])([CH3:11])[CH2:9][CH:8]([O:13][C:14](=[O:21])[C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH2:7][C:6]2([CH3:23])[CH3:22])[CH2:1][CH2:8][CH2:7][CH2:6][CH2:22]1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 6342Acetonitrile2×HCID 24437Sodium SulfiteHCID 6881781-Hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

Product 1

HCID 233720981-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidineYield 74%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8078CyclohexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
62 °C

Procedure

2,2′-Dipyridyl (0.056 g, 0.36 mmol) is stirred with 28 ml of acetonitrile. To the acetonitrile solution is added a solution of 0.098 g (0.36 mmol) of ferric chloride hexahydrate in 2 ml of water. This purple mixture is stirred for 10 minutes prior to adding 19 ml of cyclohexane and 5.00 g (18.1 mmol) of 1-oxyl-4-benzoyloxy-2,2,6,6-tetramethylpiperidine. A solution of 3.84 g (69.5 mmol) of 50% aqueous hydrogen peroxide is added to the reaction mixture dropwise over 2.25 hours while the temperature is brought to and maintained at 62° C. After the peroxide is added, the reaction mixture is heated at reflux for 1 hour. The reaction mixture is cooled, and peroxide is decomposed by the addition of aqueous sodium sulfite solution. Ethyl acetate is added, and the organic layer is washed with water. The organic layer is concentrated, and the concentrate is purified by flash chromatography with 20:1 heptane-ethyl acetate to afford 4.82 g (74% yield) of the title compound. GC assay is 100%.

Workup

  1. temperaturethe reaction mixture is heated
  2. temperatureat reflux for 1 hour
  3. temperatureThe reaction mixture is cooled
  4. washthe organic layer is washed with water
  5. concentrationThe organic layer is concentrated
  6. customthe concentrate is purified by flash chromatography with 20:1 heptane-ethyl acetate

Sources & evidence

ORD record
ord-bb4926820e6848b7bb3a1d36dd6f1466
Source dataset
uspto-grants-2008_06
Patent number
US07390904B2

Reaction notes

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