Octane → 1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-ol

HRID 1756838Notes

Reaction equation

HRID 1756838 reaction equation
C(OO)(C)(C)C.C([O:15][CH:16]1[CH2:21][C:20]([CH3:23])([CH3:22])[N:19]([OH:24])[C:18]([CH3:26])([CH3:25])[CH2:17]1)(=O)C1C=CC=CC=1.[CH3:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34]>[Mo](=O)(=O)=O.O>[OH:15][CH:16]1[CH2:17][C:18]([CH3:25])([CH3:26])[N:19]([O:24][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[C:20]([CH3:22])([CH3:23])[CH2:21]1

Participants

6

Reactant 3

HCID 356OctaneHCID 6410tert-Butyl hydroperoxideHCID 6881781-Hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

Product 1

HCID 113466831-Octyloxy-2,2,6,6-tetramethylpiperidin-4-ol

Reagents, catalysts & solvents 2

HCID 14802Molybdenum trioxideCatalystHCID 962WaterSolvent

Procedure

A solution of 121.8 grams (946 mmol) of 70% aqueous tert-butyl hydroperoxide is added over a 3-hour period to a mixture of 101.5 grams (367 mmol)of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 1.3 gram of molybdenum trioxide, and 650 ml of n-octane that is preheated to 120° C. The reaction mixture is maintained at reflux temperature throughout the addition, and water is collected in a Dean-Stark trap. The reaction mixture is heated at reflux for 8.5 hours after the addition is complete in order to discharge the red color of the nitroxyl starting material. The crude reaction mixture is purified by flash chromatography (50:1 heptane: ethyl acetate) and then hydrolyzed using potassium hydroxide in ethanol to obtain the title compound as a colorless oil.

Workup

  1. customis preheated to 120° C
  2. temperatureThe reaction mixture is maintained
  3. temperatureat reflux temperature
  4. customis collected in a Dean-Stark trap
  5. temperatureThe reaction mixture is heated
  6. temperatureat reflux for 8.5 hours
  7. additionafter the addition
  8. customThe crude reaction mixture
  9. customis purified by flash chromatography (50:1 heptane: ethyl acetate)

Sources & evidence

ORD record
ord-1b2bfedaf4e2429296210cd561a2032e
Source dataset
uspto-grants-1995_08
Patent number
US05442071

Reaction notes

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