Hydrochloric Acid → 1-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

HRID 133654

Reaktionsgleichung

Reaktionsgleichung von HRID 133654
[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:23])([O-])[O-].[Na+].[Na+].OO.Cl.S([O-])([O-])=O.[Na+].[Na+]>O.C(#N)C.C1CCCCC1>[CH:20]1([O:23][N:13]2[C:14]([CH3:17])([CH3:16])[CH2:15][CH:10]([O:9][C:1](=[O:8])[C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:11][C:12]2([CH3:19])[CH3:18])[CH2:6][CH2:7][CH2:2][CH2:3][CH2:4]1

Komponenten

9

Edukt 5

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 10340Sodium CarbonateHCID 24437Sodium SulfiteHCID 5799672,2,6,6-Tetramethyl-4-piperidyl benzoate

Produkt 1

HCID 233720981-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittel3×HCID 6342AcetonitrileLösungsmittelHCID 8078CyclohexaneLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A mixture of 6.48 g (24.8 mmol) of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1/100th of a solution of 0.270 g of anhydrous sodium carbonate diluted with water to a mass of 100 g (0.00270 g, 0.0254 mmol), and 37 ml of acetonitrile is heated to 80° C. A solution of 3.68 g (54 mmol) of 50% aqueous hydrogen peroxide is added to the reaction mixture over 1.75 hours while the temperature is brought to and maintained at reflux. After the peroxide is added, the reaction mixture is heated at 80° C. for 5 hours, then kept at room temperature overnight. A total of 0.60 g (5.9 mmol) of concentrated hydrochloric acid in 8 ml of water is added to the reaction mixture in portions. After the addition of 25 ml of cyclohexane to the reaction mixture, the temperature is brought to reflux (62° C.). A solution of 0.134 g (0.496 mmol) of ferric chloride hexahydrate in 2.5 ml of water is added to the reaction mixture. A solution of 6.96 g (102 mmol) of 50% aqueous peroxide is added dropwise over 3.25 hours to the reaction mixture while the temperature is maintained at 62° C. After the peroxide is added, the reaction mixture is stirred at reflux for 2 hours. Upon cooling, residual peroxide is decomposed by the addition of aqueous sodium sulfite solution. Work-up with ethyl acetate and purification by flash chromatography afford 3.06 g (34% overall yield) of the title compound. GC assay is 92%.

Aufarbeitung

  1. temperaturemaintained
  2. temperatureat reflux
  3. temperaturethe reaction mixture is heated at 80° C. for 5 hours
  4. temperatureto reflux (62° C.)
  5. temperatureis maintained at 62° C
  6. temperatureat reflux for 2 hours
  7. temperatureUpon cooling
  8. customWork-up with ethyl acetate and purification by flash chromatography
  9. customafford

Quellen und Nachweise

ORD-Eintrag
ord-ae0eb46bda7d432f9ca21094875c68ef
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07390904B2

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