Hydrogen Peroxide → N-cyclohexyloxy-4-oxo-2,2,6,6-tetramethylpiperidine

HRID 133646

反応式

HRID 133646 の反応式
[OH:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][C:5](=[O:10])[CH2:4][C:3]1([CH3:12])[CH3:11].[C:13](#N)[CH3:14].OO.S([O-])([O-])=O.[Na+].[Na+]>O.O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O.C1CCCCC1>[CH:14]1([O:1][N:2]2[C:7]([CH3:8])([CH3:9])[CH2:6][C:5](=[O:10])[CH2:4][C:3]2([CH3:12])[CH3:11])[CH2:13][CH2:5][CH2:4][CH2:3][CH2:11]1

参加物

8

反応物 4

HCID 784Hydrogen PeroxideHCID 6342AcetonitrileHCID 24437Sodium SulfiteHCID 986421-Hydroxy-2,2,6,6-tetramethyl-4-oxopiperidine

生成物 1

HCID 22019868N-cyclohexyloxy-4-oxo-2,2,6,6-tetramethylpiperidine収率 64%

試薬・触媒・溶媒 3

HCID 222302-Hydroxy-1,2,3-propanetricarboxylic acid hydrate (1:1)触媒2 回HCID 962Water溶媒2 回HCID 8078Cyclohexane溶媒

実験手順

A solution of 0.104 g (0.523 mmol) of ferrous chloride tetrahydrate and 0.168 g (0.799 mmol) of citric acid monohydrate in 1.5 ml of water is added to a mixture of 3.14 g (18.4 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 30 ml of acetonitrile, and 20 ml of cyclohexane that has been heated to the reflux temperature of 60°. A solution of 5.27 g (77 mmol) of 50% aqueous hydrogen peroxide is added dropwise over 2 hours to the reaction mixture while the temperature is maintained at reflux. A solution of 0.047 g of ferrous chloride tetrahydrate and 0.055 g of citric acid monohydrate in 0.5 ml of water is added to the reaction mixture 1.6 hours after the peroxide addition is started. After the peroxide is added, the reaction mixture is heated at reflux for 30 minutes, then allowed to cool slowly. Aqueous sodium sulfite solution is added to the reaction mixture 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. Purification by flash chromatography with 20:1 heptane-ethyl acetate affords 3.01 g (64% yield) of the title compound as a colorless liquid. GC assay is 99%.

後処理

  1. temperaturehas been heated to the reflux temperature of 60°
  2. temperatureis maintained
  3. temperatureat reflux
  4. temperaturethe reaction mixture is heated
  5. temperatureat reflux for 30 minutes
  6. temperatureto cool slowly
  7. extractionThe aqueous layer is extracted with a 2:1 mixture of acetonitrile-cyclohexane
  8. concentrationThe combined organic layers are concentrated
  9. customPurification by flash chromatography with 20:1 heptane-ethyl acetate

出典と根拠

ORDレコード
ord-eb007c38dc26430a97474414873e71c4
出典データセット
uspto-grants-2008_06
特許番号
US07390904B2

関連ノート

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