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

HRID 133654노트

반응식

HRID 133654 반응식
[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

참가 물질

9

반응물 5

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

생성물 1

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

시약·촉매·용매 3

HCID 962Water용매3회HCID 6342Acetonitrile용매HCID 8078Cyclohexane용매

반응 조건

온도
80 °C

실험 절차

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%.

후처리

  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

출처 및 근거

ORD 기록
ord-ae0eb46bda7d432f9ca21094875c68ef
출처 데이터셋
uspto-grants-2008_06
특허 번호
US07390904B2

반응 노트

불러오는 중…