tert-Butyl hydroperoxide → 4-Acetamido-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine

HRID 1756839Notes

Reaction equation

[OH:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH:5]([NH:10][C:11](=[O:13])[CH3:12])[CH2:4][C:3]1([CH3:15])[CH3:14].C(OO)(C)(C)C.[CH2:22]1[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1>[Mo](=O)(=O)=O>[CH:22]1([O:1][N:2]2[C:7]([CH3:8])([CH3:9])[CH2:6][CH:5]([NH:10][C:11](=[O:13])[CH3:12])[CH2:4][C:3]2([CH3:15])[CH3:14])[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1

Participants

Conditions

Temperature: 140 °C

Procedure

A mixture of 10.0 grams (47 mmol) of N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 15.2 grams (118 mmol) of 70% aqueous tert-butyl hydroperoxide, 0.67 gram of molybdenum trioxide, and 75 ml of cyclohexane is heated at reflux and water is collected in a Dean-Stark trap. The reaction mixture is then transferred to a Fischer-Porter pressure bottle and heated at 140° C. (bath temperature) for four hours to discharge the red color of the nitroxyl starting material. The reaction mixture is filtered, and the filtrate is diluted with ethyl acetate (150 ml). The organic solution is stirred with 5% aqueous sodium sulfite (150 ml) for one hour to decompose any residual hydroperoxide, then washed with brine (150 ml), dried over anhydrous magnesium sulfate, and concentrated to obtain 12.6 grams of white solid. Recrystallization from heptane affords 10.4 grams of the title compound as a white solid melting at 139°-144° C.

Workup

temperatureis heated
temperatureat reflux
customwater is collected in a Dean-Stark trap
filtrationThe reaction mixture is filtered
additionthe filtrate is diluted with ethyl acetate (150 ml)
washwashed with brine (150 ml)
dry with materialdried over anhydrous magnesium sulfate
concentrationconcentrated

Sources & evidence

ORD record: ord-ba1728e289a544c0a3cfd558160b444d
Source dataset: uspto-grants-1995_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05442071

Reaction notes

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