Acetonitrile → 5,5,5-Trifluoro-4,4-dimethyl-3-oxopentanenitrile

HRID 1049993ノート

反応式

HRID 1049993 の反応式
[CH3:1][C:2]#[N:3].[Li]CCCC.[F:9][C:10]([F:19])([F:18])[C:11]([CH3:17])([CH3:16])[C:12](OC)=[O:13]>C1COCC1>[F:9][C:10]([F:19])([F:18])[C:11]([CH3:17])([CH3:16])[C:12](=[O:13])[CH2:1][C:2]#[N:3]

参加物

5

反応物 3

HCID 6342AcetonitrileHCID 53485768Methyl 3,3,3-trifluoro-2,2-dimethylpropanoateHCID 178418339Butyllithium

生成物 1

HCID 569543105,5,5-Trifluoro-4,4-dimethyl-3-oxopentanenitrile収率 31.7%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

To a mixture of MeCN (3.32 mL, 97 mmol) in THF (300 mL) cooled to −78° C. was added n-BuLi (56.4 mL, 141 mmol). The mixture was stirred at −30° C. for 30 min. Then to the mixture was added methyl 3,3,3-trifluoro-2,2-dimethylpropanoate (15 g, 88 mmol) dropwise. The mixture was stirred at 25° C. for 10 h. The mixture was quenched with aqueous NH4Cl and extraced with DCM/MeOH (10:1). The organic layer was dried over Na2SO4, filtered and concentrated. The crude material was purified by silica column chromatography (PE/EA=10:1). All fractions found to contain product by TLC (PE/EA=5:1, Rf=0.6) were combined and concentrated to yield a light yellow solid of 5,5,5-trifluoro-4,4-dimethyl-3-oxopentanenitrile (5 g, 27.9 mmol, 31.7% yield): 1H NMR (400 MHz, CDCl3) δ: 3.75 (s, 2H), 1.41 (s, 6H).

後処理

  1. stirringThe mixture was stirred at 25° C. for 10 h
  2. customThe mixture was quenched with aqueous NH4Cl
  3. dry with materialThe organic layer was dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude material was purified by silica column chromatography (PE/EA=10:1)
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-3fd28f33402248129c2a967dc393ab41
出典データセット
uspto-grants-2016_07
特許番号
US09382238B2

反応ノート

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