Benzoyl Peroxide → 3-(3-Cyanomethyl-5-methyl-phenyl)-acrylonitrile

HRID 426167

反応式

HRID 426167 の反応式
[CH3:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]#[N:12])[CH:5]=[C:6]([CH3:8])[CH:7]=1.C1C(=O)[N:17](Br)[C:15](=O)C1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[C-]#N.[K+]>C(Cl)(Cl)(Cl)Cl.C(O)C.[W]>[C:15]([CH2:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]#[N:12])[CH:5]=[C:6]([CH3:8])[CH:7]=1)#[N:17]

参加物

8

反応物 4

HCID 7187Benzoyl PeroxideHCID 9032Potassium CyanideHCID 67184N-bromobutanimideHCID 667054533-(3,5-Dimethyl-phenyl)-acrylonitrile

生成物 1

HCID 667054363-(3-Cyanomethyl-5-methyl-phenyl)-acrylonitrile収率 36.7%

試薬・触媒・溶媒 3

HCID 23964Tungsten触媒HCID 702Ethanol溶媒HCID 5943Carbon Tetrachloride溶媒

実験手順

A mixture of 3-(3,5-Dimethyl-phenyl)-acrylonitrile (93) (15.7 g, 0.1M), NBS (18.58 g, 0.11M) and benzoyl peroxide (2.42 g, 10 mmol) in carbon tetrachloride (120 ml) was refluxed for 3 hr. under a light of 500 W tungsten lamp. After cooling to room temperature, the mixture was filtered and the filterate was evaporated in vacuo. The residue was dissolved in ether, washed with aqueous saturated sodium bicarbonate solution, dried with anhydrous magnesium sulfate, filtered, and evaporated in vacuo to give a crude product as a light yellow solid (94). A mixture of the crude product (94) and potassium cyanide (9.75 g, 0.15M) in ethanol (60 ml) and distilled water (30 ml) was refluxed for 2 hr. After cooling to room temperature, the mixture was evaporated in vacuo and the residue was partitioned between EA-ether (1:1) and water. The organic layer was taken, dried with anhydrous magnesium sulfate, filtered, and evaporated in vacuo. The residue was purified by silica gel column chromatography (eluent, ether: hexanes (from 1:1 to 2:1)) to afford 6.68 g (36%) of a pale yellow oil. 1H NMR (300 MHz, CDCl3) δ 2.39 (3H, s), 3.74 (2H, s), 5.91 (1H, d, J=16.5 Hz), 7.21 (3H, s), 7.34 (1H, d, J=16.5 Hz).

後処理

  1. temperaturewas refluxed for 3 hr
  2. filtrationthe mixture was filtered
  3. customthe filterate was evaporated in vacuo
  4. dissolutionThe residue was dissolved in ether
  5. washwashed with aqueous saturated sodium bicarbonate solution
  6. dry with materialdried with anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customto give a crude product as a light yellow solid (94)
  10. distillationdistilled water (30 ml)
  11. temperaturewas refluxed for 2 hr
  12. temperatureAfter cooling to room temperature
  13. customthe mixture was evaporated in vacuo
  14. customthe residue was partitioned between EA-ether (1:1) and water
  15. dry with materialdried with anhydrous magnesium sulfate
  16. filtrationfiltered
  17. customevaporated in vacuo
  18. customThe residue was purified by silica gel column chromatography (eluent, ether: hexanes (from 1:1 to 2:1))

出典と根拠

ORDレコード
ord-3c482401964344af85b327454b356966
出典データセット
uspto-grants-2012_01
特許番号
US08106064B2

関連ノート

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