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

HRID 1975577Notes

Reaction equation

HRID 1975577 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
1200 °C

Procedure

A mixture of 55.3 grams (0.2 mol) of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2.8 grams of molybdenum trioxide and 250 ml of n-octane is heated to 1200° 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-1-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-93e8171d5d3a4630a86f71e3d9d3b8e3
Source dataset
uspto-grants-1994_02
Patent number
US05286865

Reaction notes

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