Cyclohexanone → 1-(3-Hydroxy-3-methylbut-1-ynyl)cyclohexanol

HRID 341662ノート

反応式

HRID 341662 の反応式
[CH3:1][C:2]([OH:6])([C:4]#[CH:5])[CH3:3].C([Li])CCC.[C:12]1(=[O:18])[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1>O1CCCC1>[OH:6][C:2]([CH3:3])([CH3:1])[C:4]#[C:5][C:12]1([OH:18])[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1

参加物

5

反応物 3

HCID 7967CyclohexanoneHCID 82582-Methyl-3-butyn-2-olHCID 178418339Butyllithium

生成物 1

HCID 107499531-(3-Hydroxy-3-methylbut-1-ynyl)cyclohexanol収率 36.9%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

A solution of 2-methyl-3-butyne-2-ol (25 g, 0.297 mol) in tetrahydrofuran (250 ml) is cooled to −78° C. under a nitrogen atmosphere and to this solution, n-butyl lithium (1.6 molar solution in hexanes, 410 ml, 0.65 mol) is added slowly over 1.5-2.0 hours. The reaction mixture is stirred for 1 hour at −78° C. and a solution of cyclohexanone (46.2 ml, 0.44 mol) in tetrahydrofuran (46 ml) is added. The reaction mixture is stirred at −78° C. for one hour and allowed to come to ambient temperature and stirred at ambient temperature for 2-3 hours. The reaction mixture is cooled to 10° C. and quenched with ice cold water. The mixture is extracted with dichloromethane (3×250 ml), the organic phases are combined, washed with water, and dried over anhydrous sodium sulfate. The mixture is filtered, and the filtrate is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel to give 1-(3-hydroxy-3-methylbut-1-ynyl)cyclohexanol (20 g) as a colourless oil.

後処理

  1. additionis added slowly over 1.5-2.0 hours
  2. stirringThe reaction mixture is stirred at −78° C. for one hour
  3. customto come to ambient temperature
  4. stirringstirred at ambient temperature for 2-3 hours
  5. temperatureThe reaction mixture is cooled to 10° C.
  6. customquenched with ice cold water
  7. extractionThe mixture is extracted with dichloromethane (3×250 ml)
  8. washwashed with water
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationThe mixture is filtered
  11. customthe filtrate is evaporated under reduced pressure
  12. customThe residue is purified by column chromatography on silica gel

出典と根拠

ORDレコード
ord-9e077faabfd8415f9941fdbd21494e86
出典データセット
uspto-grants-2014_11
特許番号
US08895761B2

反応ノート

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