Acetic Acid → N-cyclohexyloxy-4-oxo-2,2,6,6-tetramethylpiperidine

HRID 133655

반응식

HRID 133655 반응식
[CH3:1][C:2]1([CH3:11])[CH2:7][C:6](=[O:8])[CH2:5][C:4]([CH3:10])([CH3:9])[NH:3]1.OO.[C:14]([OH:17])(=O)[CH3:15].S([O-])([O-])=O>O.C1CCCCC1.O.O.[O-][W]([O-])(=O)=O.[Na+].[Na+].C(=O)(O)[O-].[Na+].C(#N)C>[CH:14]1([O:17][N:3]2[C:4]([CH3:10])([CH3:9])[CH2:5][C:6](=[O:8])[CH2:7][C:2]2([CH3:11])[CH3:1])[CH2:15][CH2:6][CH2:7][CH2:2][CH2:1]1

참가 물질

10

반응물 4

HCID 176Acetic AcidHCID 784Hydrogen Peroxide2회HCID 1099SulfiteHCID 132202,2,6,6-Tetramethyl-4-piperidone

생성물 1

HCID 22019868N-cyclohexyloxy-4-oxo-2,2,6,6-tetramethylpiperidine수율 732.4%

시약·촉매·용매 5

HCID 150191Sodium Tungstate Dihydrate촉매2회HCID 516892Sodium Bicarbonate촉매2회HCID 962Water용매3회HCID 6342Acetonitrile용매HCID 8078Cyclohexane용매

반응 조건

온도
32.5 °C

실험 절차

A mixture of 0.115 g (1.37 mmol) of sodium bicarbonate and 0.275 g (0.834 mmol) of sodium tungstate dihydrate in 2 mol of water is added to a mixture of 10.00 g (64.4 mmol) of 2,2,6,6-tetramethylpiperidin-4-one and 9 ml of acetonitrile at 300 C. A solution of 11.83 g (174 mmol) of 50% aqueous hydrogen peroxide is added dropwise to the reaction mixture over 4.25 hours while the reaction temperature is maintained at 30-35° C. Approximately 3.25 hours after the peroxide addition is begun, a mixture of 0.056 g of sodium bicarbonate and 0.134 g of sodium tungstate dihydrate in 1 ml of water is added to the reaction mixture. After a total reaction time of 6.5 hours, the reaction mixture is diluted with cyclohexane. The aqueous layer is extracted twice with a mixture of 2:1 cyclohexane-acetonitrile. The total amount of cyclohexane used is 60 ml. Acetonitrile (60 ml) is added to the combined organic layers. The reaction mixture is heated to 45° C. and a solution of 0.334 g (1.24 mmol) of ferrous chloride tetrahydrate and 0.312 g (5.20 mmol) of glacial acetic acid in 5 ml of water is added. A solution of 14.95 g (220 mmol) of 50% aqueous hydrogen peroxide is added dropwise to the reaction mixture over 4.25 hours as the reaction mixture is maintained at the reflux temperature of 60° C. The reaction mixture is cooled, and 10% aqueous sulfite solution is added to decompose excess peroxide. The aqueous layer is extracted with a 2:1 mixture of acetonitrile-cyclohexane and then with ethyl acetate. The combined organic layers are concentrated, and the concentrate is purified by flash chromatography with 100:7.5 heptane-ethyl acetate to afford 9.65 g (59% yield) of the title compound, a white solid, mp 33-37. GC assay is 99%.

후처리

  1. additionis added to the reaction mixture
  2. extractionThe aqueous layer is extracted twice with a mixture of 2:1 cyclohexane-acetonitrile
  3. additionAcetonitrile (60 ml) is added to the combined organic layers
  4. temperatureThe reaction mixture is heated to 45° C.
  5. temperatureis maintained at the reflux temperature of 60° C
  6. temperatureThe reaction mixture is cooled
  7. extractionThe aqueous layer is extracted with a 2:1 mixture of acetonitrile-cyclohexane
  8. concentrationThe combined organic layers are concentrated
  9. customthe concentrate is purified by flash chromatography with 100:7.5 heptane-ethyl acetate

출처 및 근거

ORD 기록
ord-df3d6b0ccebc4e53a81482e49cc11b7b
출처 데이터셋
uspto-grants-2008_06
특허 번호
US07390904B2

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