Sodium hydride → 4-(3,5-Bis(trifluoromethyl)benzyloxy)-3-phenylbutanenitrile

HRID 349712ノート

反応式

HRID 349712 の反応式
[C:1]([CH2:3][CH:4]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[C:5]([O:7][CH3:8])=O)#[N:2].[Li+].[BH4-].[F:17][C:18]([F:32])([F:31])[C:19]1[CH:20]=[C:21]([CH:24]=[C:25]([C:27]([F:30])([F:29])[F:28])[CH:26]=1)CBr.[H-].[Na+]>C1COCC1.CN(C=O)C>[F:17][C:18]([F:31])([F:32])[C:19]1[CH:20]=[C:21]([CH:24]=[C:25]([C:27]([F:28])([F:29])[F:30])[CH:26]=1)[CH2:8][O:7][CH2:5][CH:4]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[CH2:3][C:1]#[N:2]

参加物

7

反応物 4

HCID 24758Sodium hydrideHCID 1225733,5-Bis(trifluoromethyl)benzyl bromideHCID 4148881Lithium borohydrideHCID 18464584Methyl 3-cyano-2-phenylpropanoate

生成物 1

HCID 866027574-(3,5-Bis(trifluoromethyl)benzyloxy)-3-phenylbutanenitrile収率 55%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Methyl 3-cyano-2-phenylpropanoate (350 mg, 1.90 mmol) was treated with LiBH4 (2.28 mmol) in THF (20 ml) at 50° C. for 2 hours until completion of the reaction. It was quenched with water and extracted with ethyl acetate. The organic phase was washed with water, brine and dried with Na2SO4 before being concentrated to dryness. The crude product was then mixed with 3,5-bis(trifluoromethyl)benzyl bromide in DMF (20 ml) and sodium hydride (91 mg, 2.28 mmol) was added. The reaction mixture was stirred at room temperature for 30 minutes and quenched with water, and extracted with ethyl acetate. The organic phase was washed with water, brine and concentrated. The crude residue was purified by silica flash chromatography (15% ethyl acetate in hexanes) to afford the desired product (405 mg, 55% in two steps). 1H NMR (500 MHz, CDCl3) δ ppm 2.78 (dd, J=116.79, 7.32 Hz, 1 H) 2.88 (m, 1 H) 3.33 (m, 1 H) 3.81 (m, 2 H) 4.65 (s, 2 H) 7.27 (m, 2 H) 7.31 (m, 1 H) 7.37 (m, 2 H) 7.73 (s, 2 H) 7.80 (s, 1 H).

後処理

  1. customIt was quenched with water
  2. extractionextracted with ethyl acetate
  3. washThe organic phase was washed with water, brine
  4. dry with materialdried with Na2SO4
  5. concentrationbefore being concentrated to dryness
  6. additionwas added
  7. customquenched with water
  8. extractionextracted with ethyl acetate
  9. washThe organic phase was washed with water, brine
  10. concentrationconcentrated
  11. customThe crude residue was purified by silica flash chromatography (15% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-0ef09c58181743c3ac63cd465813d4cb
出典データセット
uspto-grants-2007_02
特許番号
US07179926B2

反応ノート

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