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

HRID 1493394Notes

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

Conditions

Temperature: 120 °C

Procedure

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 heated to 120° C. The reaction mixture is maintained at reflux 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 of the oil by flash chromatography (silica gel; 4:1 hexane:ethylacetate) affords 30.0 grams (53% yield) of the title compound as a white solid melting at 95-97° C.

Workup

temperatureThe reaction mixture is maintained
customis collected in a Dean-Stark trap
temperatureThe red mixture is heated
temperatureat reflux for three hours
additionafter the addition
customSolids are removed by filtration
concentrationthe filtrate is concentrated at reduced pressure
customto obtain a yellow oil
customPurification of the oil by flash chromatography (silica gel; 4:1 hexane:ethylacetate)

Sources & evidence

ORD record: ord-d42925e096764edaba94220e00d6207e
Source dataset: uspto-grants-1991_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05021481

Reaction notes

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