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

HRID 133664

反応式

HRID 133664 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(O)(=O)C.[CH2:17]1[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1.OO>O.C(#N)C>[CH:17]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])[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1

参加物

7

反応物 4

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 8078Cyclohexane2 回HCID 986421-Hydroxy-2,2,6,6-tetramethyl-4-oxopiperidine3 回

生成物 1

HCID 22019868N-cyclohexyloxy-4-oxo-2,2,6,6-tetramethylpiperidine収率 63%

試薬・触媒・溶媒 2

HCID 962Water溶媒2 回HCID 6342Acetonitrile溶媒3 回

反応条件

温度
61 °C

実験手順

1-Oxyl-2,2,6,6-tetramethylpiperidin-4-one (10.97 g, 64.4 mmol) is divided into 2 portions. A solution of 0.216 g (1.09 mmol) of ferrous chloride tetrahydrate and 0.185 9 (3.08 mmol) of glacial acetic acid in 3 ml of water is added to a mixture of 2 g of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 20 ml of acetonitrile, and 13 ml of cyclohexane that is heated to near reflux. A solution of 17.21 g (253 mmol) of 50% aqueous hydrogen peroxide is added to the reaction mixture dropwise over 4.75 hours as the reaction temperature is brought to and maintained at 60-62° C. As the peroxide is being added, a solution of the remaining portion of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one in 20 ml of acetonitrile is added to the reaction mixture dropwise over 3.5 hours. During the addition of the 1-oxyl compound, cyclohexane (47 ml) and acetonitrile (50 ml) are added to the reaction mixture in several portions. A total of 0.326 g of ferrous chloride tetrahydrate, 0.284 g of glacial acid, and 4 ml of water is added to the reaction mixture in 3 portions during the peroxide addition. Work up according to the procedure of Example 44 affords 10.31 g (63% yield) of the title compound. GC assay is 99%.

後処理

  1. temperatureis heated
  2. temperatureto near reflux
  3. additionare added to the reaction mixture in several portions

出典と根拠

ORDレコード
ord-bbeda8db3ff14d84839ea235e3d0d09f
出典データセット
uspto-grants-2008_06
特許番号
US07390904B2

関連ノート

読み込み中…