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

HRID 133652

反応式

HRID 133652 の反応式
[CH3:1][C:2]1([CH3:11])[CH2:7][CH:6]([OH:8])[CH2:5][C:4]([CH3:10])([CH3:9])[NH:3]1.[OH:12]O.[Cl-].[Na+].CS(O)(=O)=O.[CH2:21]1[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1>O.C(#N)C.O.O.[O-][W]([O-])(=O)=O.[Na+].[Na+].C(=O)(O)[O-].[Na+].CS(O)(=O)=O>[CH:21]1([O:12][N:3]2[C:4]([CH3:10])([CH3:9])[CH2:5][CH:6]([OH:8])[CH2:7][C:2]2([CH3:11])[CH3:1])[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22]1

参加物

11

反応物 5

HCID 784Hydrogen Peroxide2 回HCID 5234Sodium Chloride2 回HCID 6395Methanesulfonic AcidHCID 8078CyclohexaneHCID 754714-Hydroxy-2,2,6,6-tetramethylpiperidine

生成物 1

HCID 113228111-Cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-ol収率 68%

試薬・触媒・溶媒 5

HCID 6395Methanesulfonic Acid触媒2 回HCID 150191Sodium Tungstate Dihydrate触媒HCID 516892Sodium Bicarbonate触媒HCID 962Water溶媒4 回HCID 6342Acetonitrile溶媒2 回

反応条件

温度
36.5 °C

実験手順

A mixture of 0.108 g (1.29 mmol) of sodium bicarbonate and 0.265 g (0.803 mmol) of sodium tungstate dihydrate in 2 ml of water is added to a mixture of 10.00 g (63.6 mmol) of 2,2,6,6-tetramethylpiperidin-4-ol and 9 ml of acetonitrile. A solution of 12.11 g (178 mmol) of 50% aqueous hydrogen peroxide is added to the reaction mixture dropwise over 3.75 hours as the reaction temperature is maintained at 35-38° C. The reaction mixture is heated at 35-38° C. for an additional 2 hours. The reaction mixture is diluted with acetonitrile and cyclohexane, and then saturated sodium chloride solution and solid sodium chloride are added. The aqueous layer is extracted twice with a mixture of cyclohexane and acetonitrile. The aqueous layer is discarded. To the combined organic layers are added cyclohexane and acetonitrile to bring the total amount of solvent to 65 ml and 95 ml, respectively. The reaction mixture is heated to near reflux, and a solution of 0.528 g (1.95 mmol) of ferric chloride hexahydrate and 0.628 g (6.53 mmol) of methanesulfonic acid in 5 ml of water is added over several minutes. A solution of 17.22 g (253 mmol) of 50% aqueous hydrogen peroxide is added to the reaction mixture dropwise over 4.75 hours as the reaction temperature is maintained at reflux (60° C.). A solution of 0.170 g of ferric chloride hexahydrate and 0.206 g of methanesulfonic acid in 2 ml of water is added to the reaction mixture 2.5 hours after the peroxide addition is begun. A solution of 0.178 g of ferric chloride hexahydrate and 0.205 g of methanesulfonic acid in 2 ml of water is added to the reaction mixture 4 hours after the peroxide addition is begun. The reaction mixture is heated at reflux for 30 minutes after the peroxide is added. Work up according to the procedure of Example 54 gives 11.07 g (68% yield) of the title compound. GC assay is 92%.

後処理

  1. temperatureThe reaction mixture is heated at 35-38° C. for an additional 2 hours
  2. extractionThe aqueous layer is extracted twice with a mixture of cyclohexane and acetonitrile
  3. additionTo the combined organic layers are added cyclohexane and acetonitrile
  4. temperatureThe reaction mixture is heated
  5. temperatureto near reflux
  6. temperatureis maintained
  7. temperatureat reflux (60° C.)
  8. temperatureThe reaction mixture is heated
  9. additionis added

出典と根拠

ORDレコード
ord-108932958ea247a7a7b8d8fb4391b1cc
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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