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

HRID 1493392Notes

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

Conditions

Temperature: 135 °C

Procedure

A mixture of 10.5 grams (40.2 mmol) of 4-benzoyloxy2,2,6,6 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 (under a 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, washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to yield an oil. Purification of the oil by flash chromatography (silica gel; 100:3 heptane:ethyl acetate) affords 12.8 grams of the title compound.

Workup

customSolids are removed by filtration
washThe cyclohexane solution is washed twice with water
washwashed with saturated sodium chloride solution
dry with materialdried over anhydrous magnesium sulfate
concentrationconcentrated under reduced pressure
customto yield an oil
customPurification of the oil by flash chromatography (silica gel; 100:3 heptane:ethyl acetate)

Sources & evidence

ORD record: ord-87f8d6d784324d63a350adfdba29f362
Source dataset: uspto-grants-1991_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05021481

Reaction notes

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