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

HRID 133630

반응식

HRID 133630 반응식
OO.[OH:3][N:4]1[C:9]([CH3:11])([CH3:10])[CH2:8][CH:7]([OH:12])[CH2:6][C:5]1([CH3:14])[CH3:13].[CH2:15]1[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1.CO>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.O.O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Fe+2].CS(O)(=O)=O>[CH:15]1([O:3][N:4]2[C:9]([CH3:10])([CH3:11])[CH2:8][CH:7]([OH:12])[CH2:6][C:5]2([CH3:14])[CH3:13])[CH2:20][CH2:19][CH2:18][CH2:17][CH2:16]1

참가 물질

9

반응물 4

HCID 784Hydrogen Peroxide2회HCID 887MethanolHCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidineHCID 8078Cyclohexane

생성물 1

HCID 113228111-Cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-ol수율 59%

시약·촉매·용매 4

HCID 6395Methanesulfonic Acid촉매2회HCID 62662Ferrous sulfate heptahydrate촉매2회HCID 94433Tetrabutylammonium hydrogen sulfate촉매HCID 962Water용매

실험 절차

A solution of 80.2 g (1.18 mol) of 50% aqueous hydrogen peroxide is added at 70° C. over 12 hours to a mixture of 17.2 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 0.556 g (2.00 mmol) of iron(II) sulfate heptahydrate, 0.679 g (2.0 mmol) of tetrabutylammonium hydrogen sulfate, 0.15 ml (2.0 mmol) of methanesulfonic acid, 44 ml of cyclohexane, and 200 ml of methanol. Five hours after the peroxide addition is started, a solution of 0.556 g (2.0 mmol) of iron(II) sulfate heptahydrate and 0.15 ml (2.0 mmol) of methanesulfonic acid in 4 ml of water is added to the reaction mixture. Shortly after the peroxide addition is completed, the reaction mixture tests negative for hydrogen peroxide. Methanol is distilled from the reaction mixture at reduced pressure, and water and saturated sodium bicarbonate solution are added to the reaction mixture. A total of 60 ml of 12% by weight sodium borohydride in 14 N sodium hydroxide solution is added to the reaction mixture to convert any 4-oxo derivative of the title compound to the desired product. The reaction mixture is extracted with dichloromethane, and the organic layer is neutralized by the addition of hydrochloric acid followed by sodium bicarbonate. After drying, the organic layer is concentrated, and the crude product is purified by flash chromatography on silica gel to afford 15.0 g (59% yield) of the title compound, an off white solid having a melting point of 72-75° C. Structure is confirmed by mass spectrometry and NMR analysis.

후처리

  1. distillationMethanol is distilled from the reaction mixture at reduced pressure, and water and saturated sodium bicarbonate solution
  2. additionare added to the reaction mixture
  3. additionA total of 60 ml of 12% by weight sodium borohydride in 14 N sodium hydroxide solution is added to the reaction mixture
  4. extractionThe reaction mixture is extracted with dichloromethane
  5. additionthe organic layer is neutralized by the addition of hydrochloric acid
  6. customAfter drying
  7. concentrationthe organic layer is concentrated
  8. customthe crude product is purified by flash chromatography on silica gel

출처 및 근거

ORD 기록
ord-7edca11e155c4039b43018ea7c1a346e
출처 데이터셋
uspto-grants-2008_06
특허 번호
US07390904B2

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