Hydrogen Peroxide → 1-Cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-ol

HRID 133659

Reaktionsgleichung

Reaktionsgleichung von HRID 133659
CS(O)(=O)=O.[OH:6][N:7]1[C:12]([CH3:14])([CH3:13])[CH2:11][CH:10]([OH:15])[CH2:9][C:8]1([CH3:17])[CH3:16].[C:18](#N)[CH3:19].OO>O.CS(O)(=O)=O.C1CCCCC1>[CH:19]1([O:6][N:7]2[C:12]([CH3:13])([CH3:14])[CH2:11][CH:10]([OH:15])[CH2:9][C:8]2([CH3:17])[CH3:16])[CH2:18][CH2:10][CH2:9][CH2:8][CH2:16]1

Komponenten

8

Edukt 4

HCID 784Hydrogen PeroxideHCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidineHCID 6342AcetonitrileHCID 6395Methanesulfonic Acid

Produkt 1

HCID 113228111-Cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-olAusbeute 69 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6395Methanesulfonic AcidKatalysator2×HCID 962WaterLösungsmittel3×HCID 8078CyclohexaneLösungsmittel

Reaktionsbedingungen

Temperatur
62 °C

Versuchsvorschrift

A solution of 0.234 g (0.842 mmol) of ferrous sulfate heptahydrate, 3 ml of water, and 0.293 g (3.05 mmol) of methanesulfonic acid is added to a mixture of 5.00 g (29.0 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 45 ml of acetonitrile, and 32 ml of cyclohexane, which has been heated to 62° C. A solution of 8.07 g (119 mmol) of 50% aqueous hydrogen peroxide is added dropwise over 2.25 hours to the reaction mixture while the temperature is maintained at reflux. A solution of 0.069 g of ferrous sulfate heptahydrate and 0.188 g of methanesulfonic acid in 2 ml of water is added to the reaction mixture 2 hours after the peroxide addition is started. A solution of 0.065 g of ferrous sulfate heptahydrate and 0.108 g of methanesulfonic acid in 1 ml of water is added to the reaction mixture 3.5 hours after the peroxide addition is started. After a total reaction time of 4.5 hours at reflux, the reaction mixture is allowed to cool. Excess peroxide is quenched with aqueous sodium sulfite solution. The aqueous layer is extracted with a 2:1 mixture of acetonitrile and cyclohexane, and the combined organic layers are washed with sodium hydroxide solution. To the organic layer are added 6 ml of t-butyl alcohol, 6 ml of water, 0.4 g of sodium hydroxide, and 0.70 g of sodium borohydride. The mixture is stirred for 3 hours, and the aqueous layer is extracted with ethyl acetate. The combined organic layers are washed with aqueous citric acid, aqueous sodium bicarbonate, and then concentrated. Purification by flash chromatography with 1:1 heptane-ethyl acetate affords 5.10 g (69% yield) of the title compound as a light yellow syrup, GC assay 93%.

Aufarbeitung

  1. temperatureis maintained
  2. temperatureat reflux
  3. temperatureAfter a total reaction time of 4.5 hours at reflux
  4. temperatureto cool
  5. customExcess peroxide is quenched with aqueous sodium sulfite solution
  6. extractionThe aqueous layer is extracted with a 2:1 mixture of acetonitrile and cyclohexane
  7. washthe combined organic layers are washed with sodium hydroxide solution
  8. additionTo the organic layer are added 6 ml of t-butyl alcohol, 6 ml of water, 0.4 g of sodium hydroxide, and 0.70 g of sodium borohydride
  9. extractionthe aqueous layer is extracted with ethyl acetate
  10. washThe combined organic layers are washed with aqueous citric acid, aqueous sodium bicarbonate
  11. concentrationconcentrated
  12. customPurification by flash chromatography with 1:1 heptane-ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-dd31eee20c0e4543bd25253d27ca678c
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07390904B2

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