Dichloromethane → 2-t-Butyl-4-(5-hexynoyl)-6-methylphenol

HRID 231609

反応式

HRID 231609 の反応式
[C:1]([C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH3:11])[C:6]=1[OH:12])([CH3:4])([CH3:3])[CH3:2].C(Cl)Cl.[C:16](Cl)(=[O:22])[CH2:17][CH2:18][CH2:19][C:20]#[CH:21].[Sn](Cl)(Cl)(Cl)Cl>>[C:1]([C:5]1[CH:10]=[C:9]([C:16](=[O:22])[CH2:17][CH2:18][CH2:19][C:20]#[CH:21])[CH:8]=[C:7]([CH3:11])[C:6]=1[OH:12])([CH3:4])([CH3:3])[CH3:2]

参加物

5

反応物 4

HCID 6344DichloromethaneHCID 166782-tert-Butyl-6-methylphenolHCID 24287Tin tetrachlorideHCID 2759284Hex-5-ynoyl chloride

生成物 1

HCID 146720322-t-Butyl-4-(5-hexynoyl)-6-methylphenol収率 51.4%

反応条件

温度
-78 °C

実験手順

To a solution of 2-tert-butyl-6-methylphenol (1.2 g, 7.3 mmol) in methylene chloride (28 ml, 1.1 equiv.), stirred under argon at -78° C., is added 5-hexynoyl chloride (1.0 g) followed by tin tetrachloride (0.93 mL, 1.1 equiv.). After stirring 30 minutes at -78° C., the reaction is warmed to -50° C. and stirred 5 minutes more. The mixture is then quenched with 1N HCl/ether. The product is extracted from 1N HCl with 3 portions of ether, and the ether layers are combined and washed with water. The resulting ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give 2.14 g crude product. The product is flash chromatographed on silica gel using 10% EtOAc in hexane to give 0.97 g 2-t-butyl-4-(5-hexynoyl)-6-methylphenol. Crystallization from hexane gives crystals, mp 63°-64° C.

後処理

  1. temperaturethe reaction is warmed to -50° C.
  2. stirringstirred 5 minutes more
  3. customThe mixture is then quenched with 1N HCl/ether
  4. extractionThe product is extracted from 1N HCl with 3 portions of ether
  5. washwashed with water
  6. dry with materialThe resulting ether layer is dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give 2.14 g crude product
  10. customchromatographed on silica gel using 10% EtOAc in hexane

出典と根拠

ORDレコード
ord-97253f98aac7407fa153e1b9d13dad5b
出典データセット
uspto-grants-1989_07
特許番号
US04847303

関連ノート

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