tert-Butyl hydroperoxide → 1-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

HRID 1708614Notes

Reaction equation

HRID 1708614 reaction equation
[C:1]([O:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[NH:13][C:12]([CH3:19])([CH3:18])[CH2:11]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:20]([O:24]O)(C)([CH3:22])[CH3:21].[CH2:26]1[CH2:31]CCC[CH2:27]1>[Mo](=O)(=O)=O>[C:1]([O:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[N:13]([O:24][CH:20]2[CH2:22][CH2:31][CH2:26][CH2:27][CH2:21]2)[C:12]([CH3:19])([CH3:18])[CH2:11]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6410tert-Butyl hydroperoxideHCID 8078CyclohexaneHCID 5799672,2,6,6-Tetramethyl-4-piperidyl benzoate

Product 1

HCID 233720981-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

Reagents, catalysts & solvents 1

HCID 14802Molybdenum trioxideCatalyst

Conditions

Temperature
135 °C

Procedure

A mixture of 10.5 grams (40.2 mmol) of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 16.1 grams (160.8 mmol) of 90% tert-butyl hydroperoxide, 600 mg of molybdenum trioxide and 60 ml of cyclohexane is placed in a Fischer-Porter pressure bottle (nitrogen atmosphere) in an oil bath. The bath temperature is gradually increased to 135° C. over a 2.25 hour period and then maintained at 135° C. for another 2.25 hours till the red color of the N-oxyl intermediate is discharged. Solids are removed by filtration. The cyclohexane solution is washed twice with water, then with saturated sodium chloride solution and dried over anhydrous magnesium sulfate, and finally concentrated under reduced pressure to obtain an oil. Purification by flash chromatography (silica gel; 100:3 heptane:ethyl acetate) affords 12.8 grams of the title compound.

Workup

  1. customis placed in a Fischer-Porter pressure bottle (nitrogen atmosphere) in an oil bath
  2. customSolids are removed by filtration
  3. washThe cyclohexane solution is washed twice with water
  4. dry with materialwith saturated sodium chloride solution and dried over anhydrous magnesium sulfate
  5. concentrationfinally concentrated under reduced pressure
  6. customto obtain an oil
  7. customPurification by flash chromatography (silica gel; 100:3 heptane:ethyl acetate)

Sources & evidence

ORD record
ord-508302a209e54a0084c09bae1ad8ddb6
Source dataset
uspto-grants-1994_10
Patent number
US05359069

Reaction notes

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