Acetonitrile → 3-(2-Bromophenyl)-3-oxopropanenitrile

HRID 1452761ノート

反応式

HRID 1452761 の反応式
[H-].[Na+].[CH3:3][C:4]#[N:5].C[O:7][C:8](=O)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[Br:15]>C1COCC1>[Br:15][C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=1[C:8](=[O:7])[CH2:3][C:4]#[N:5]

参加物

5

反応物 3

HCID 6342AcetonitrileHCID 11894Methyl 2-bromobenzoateHCID 24758Sodium hydride

生成物 1

HCID 107043343-(2-Bromophenyl)-3-oxopropanenitrile収率 59%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a suspension of NaH (60% dispersion, 1.14 g, 28.4 mmol) in dry THF (50 mL) under N2 was added CH3CN followed by 2-bromo-benzoic acid methyl ester (2 mL, 14.2 mmol). The reaction mixture was refluxed for 1.5 hour, then cooled to 0° C., quenched with water (1 mL), and concentrated in vacuo. The residue was diluted with water and the aqueous layer was extracted with hexane (2×), then acidified to pH 3-4 with 1N aqueous HCl. The milky aqueous layer was extracted with CHCl3 (3×), the combined organic layers were dried over sodium sulfate, filtered, and concentrated. Purification on silica gel with 0-35% EtOAc in hexane as eluent provided 1.89 g (59 % yield) of 3-(2-bromo-phenyl)-3-oxo-propionitrile as a yellow oil. 1H-NMR (d6-DMSO) δ: 11.8 (broad m, 1H, tautomers), 7.73 (broad s, 1H), 7.42 (m, 3H), 4.99 (s, 0.3H, tautomer), 4.64 (s, 0.6H, tautomer); HPLC/MS m/z: 223.9, 225.9 [MH]+.

後処理

  1. temperatureThe reaction mixture was refluxed for 1.5 hour
  2. customquenched with water (1 mL)
  3. concentrationconcentrated in vacuo
  4. additionThe residue was diluted with water
  5. extractionthe aqueous layer was extracted with hexane (2×)
  6. extractionThe milky aqueous layer was extracted with CHCl3 (3×)
  7. dry with materialthe combined organic layers were dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification on silica gel with 0-35% EtOAc in hexane as eluent

出典と根拠

ORDレコード
ord-affff15bdd044483903bbf465b170102
出典データセット
uspto-grants-2009_01
特許番号
US07473783B2

反応ノート

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