tert-Butyl hydroperoxide → 4-Benzoyloxy-1-octyloxy-2,2,6,6-tetramethylpiperidine

HRID 1900300Notes

Reaction equation

HRID 1900300 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)([CH3:23])(C)C>[Mo](=O)(=O)=O.CCCCCCCC>[C:1]([O:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[N:13]([O:24][CH2:20][CH2:23][CH2:6][CH2:7][CH2:2][CH2:3][CH2:4][CH3:5])[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 2

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

Product 1

HCID 151699944-Benzoyloxy-1-octyloxy-2,2,6,6-tetramethylpiperidine

Reagents, catalysts & solvents 2

HCID 14802Molybdenum trioxideCatalystHCID 356OctaneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 55.3 grams (0.2 mmol) of 4-benzoyloxy-2,2,6,6-tetramethylpiperid ine, 2.8 grams of molybdenum trioxide and 250 ml of n-octane is heated to 120° C. A solution of 90.2 grams (0.7 mol) of 70% aqueous tert-butyl hydroperoxide is added dropwise to the hot reaction mixture. Water is removed by azeotropic distillation and collected in a Dean-Stark trap. The reaction mixture is heated at reflux till the red color of the intermediate N-oxyl compound disappears. Solids are removed by filtration, and the filtrate is concentrated under vacuum to give an oil. Purification of the oil by flash chromatography on silica gel (100:3 heptane: ethyl acetate) affords 4-benzoyloxy-l-octyloxy-2,2,6,6-tetramethylpiperidine as a mixture of octyloxy isomers. Further elution of the chromatographic column with 50:3 heptane:ethyl acetate affords the title compound as a mixture of octanediyl isomers.

Workup

  1. customWater is removed by azeotropic distillation
  2. customcollected in a Dean-Stark trap
  3. temperatureThe reaction mixture is heated
  4. temperatureat reflux till the red color of the intermediate N-oxyl compound
  5. customSolids are removed by filtration
  6. concentrationthe filtrate is concentrated under vacuum
  7. customto give an oil
  8. customPurification of the oil by flash chromatography on silica gel (100:3 heptane: ethyl acetate)

Sources & evidence

ORD record
ord-fb95c0f44e8a42b1a3977c78ca43490c
Source dataset
uspto-grants-1996_11
Patent number
US05574162

Reaction notes

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