Hydrogen Peroxide → 1-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

HRID 133648Notes

Reaction equation

HRID 133648 reaction equation
[OH:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH:5]([O:10][C:11](=[O:18])[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH2:4][C:3]1([CH3:20])[CH3:19].N1[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=1[C:27](O)=O.OO.S([O-])([O-])=O.[Na+].[Na+].S(=O)(=O)(O)O>O=C1O[C@H]([C@H](CO)O)C(O)=C1O.N1C=CC=CC=1.O.C1CCCCC1>[CH:22]1([O:1][N:2]2[C:7]([CH3:9])([CH3:8])[CH2:6][CH:5]([O:10][C:11](=[O:18])[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[CH2:4][C:3]2([CH3:20])[CH3:19])[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1

Participants

10

Reactant 5

HCID 784Hydrogen PeroxideHCID 1018Picolinic acidHCID 1118Sulfuric AcidHCID 24437Sodium SulfiteHCID 6881781-Hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

Product 1

HCID 233720981-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidineYield 330.2%

Reagents, catalysts & solvents 4

HCID 54670067L-Ascorbic AcidCatalystHCID 962WaterSolventHCID 1049PyridineSolvent2×HCID 8078CyclohexaneSolvent

Conditions

Temperature
48 °C

Procedure

To a mixture of 3.01 g (10.9 mmol) of 1-oxyl-4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 20 ml of pyridine, and 12 ml of cyclohexane are added 0.153 g (0.55 mmol) of ferrous sulfate heptahydrate, 0.211 g (1.71 mmol) of picolinic acid, and 0.048 g (0.27 mmol) of ascorbic acid. Water (1 ml) is added to dissolve the metal salt. The mixture is heated to 48° C. A solution of 2.95 g (43.5 mmol) of 50% aqueous hydrogen peroxide is added dropwise over 1.25 hours to the reaction mixture while the temperature is brought to and maintained at 60-64° C. After the peroxide is added, the reaction mixture is allowed to cool slowly. After the reaction mixture is stirred overnight at room temperature, residual peroxide is decomposed by the addition of aqueous sodium sulfite solution. A mixture of 15 ml of concentrated sulfuric acid and 65 g of ice is carefully added to the reaction mixture to form a salt from the pyridine. The reaction mixture is extracted twice with ethyl acetate. The combined organic layers are washed with dilute sodium bicarbonate solution and saturated sodium chloride solution, then concentrated. Purification by flash chromatography on silica gel with 20:1 heptane-ethyl acetate affords 2.03 g (52% yield) of the title compound, a colorless syrup, GC assay 100%.

Workup

  1. dissolutionto dissolve the metal salt
  2. temperaturemaintained at 60-64° C
  3. temperatureto cool slowly
  4. additionis carefully added to the reaction mixture
  5. extractionThe reaction mixture is extracted twice with ethyl acetate
  6. washThe combined organic layers are washed with dilute sodium bicarbonate solution and saturated sodium chloride solution
  7. concentrationconcentrated
  8. customPurification by flash chromatography on silica gel with 20:1 heptane-ethyl acetate

Sources & evidence

ORD record
ord-861a3df0307548b0a3b66ebce0bd1282
Source dataset
uspto-grants-2008_06
Patent number
US07390904B2

Reaction notes

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