1,4-Dihydroxy-2,2,6,6-tetramethylpiperidine → HCID 12068227, compound

HRID 1975555Notes

Reaction equation

HRID 1975555 reaction equation
C(OO)(C)(C)C.[OH:7][CH:8]1[CH2:13][C:12]([CH3:15])([CH3:14])[N:11]([OH:16])[C:10]([CH3:18])([CH3:17])[CH2:9]1.[CH2:19]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH3:20]>[Mo](=O)(=O)=O.O>[OH:7][CH:8]1[CH2:13][C:12]([CH3:14])([CH3:15])[N:11]([O:16][CH:19]([CH3:20])[C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:10]([CH3:18])([CH3:17])[CH2:9]1

Participants

6

Reactant 3

HCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidineHCID 6410tert-Butyl hydroperoxideHCID 7500Ethylbenzene

Product 1

HCID 12068227HCID 12068227, compoundYield 53%

Reagents, catalysts & solvents 2

HCID 14802Molybdenum trioxideCatalystHCID 962WaterSolvent

Procedure

A solution of 70% aqueous tert-butyl hydroperoxide (74.8 grams, 609 mmol) is added over 30 minutes to a mixture of 35.0 grams (203 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 2.0 grams of molybdenum trioxide, and 200 ml of ethylbenzene which 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 red mixture is heated at reflux for three hours after the addition is complete in order to discharge the red color of the N-oxyl compound. Solids are removed by filtration, and the filtrate is concentrated at reduced pressure to obtain a yellow oil. Purification by flash chromatography (silica gel; 4:1 hexane:ethyl acetate) affords 30.0 grams (53% yield) of the title compound as a white solid melting at 95°-97° C.

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 red mixture is heated
  6. temperatureat reflux for three hours
  7. additionafter the addition
  8. customSolids are removed by filtration
  9. concentrationthe filtrate is concentrated at reduced pressure
  10. customto obtain a yellow oil
  11. customPurification by flash chromatography (silica gel; 4:1 hexane:ethyl acetate)

Sources & evidence

ORD record
ord-9d10e847d5504ca39b28cd002eeb02ec
Source dataset
uspto-grants-1994_02
Patent number
US05286865

Reaction notes

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