Propionitrile → 1-Ethyl-1-(2-propenyl)-3-butenylamine

HRID 1456917ノート

反応式

HRID 1456917 の反応式
C(C(N=C=O)CCC)CC.NC(CCC)CCC.[CH2:19]([C:21]([N:28]=C=O)([CH2:25][CH:26]=[CH2:27])[CH2:22][CH:23]=[CH2:24])[CH3:20].C(#N)CC.C([Mg]Br)C=C.CCOCC.[NH4+].[Cl-]>CCOCC>[CH2:19]([C:21]([NH2:28])([CH2:25][CH:26]=[CH2:27])[CH2:22][CH:23]=[CH2:24])[CH3:20]

参加物

8

反応物 6

HCID 7854PropionitrileHCID 25517Ammonium ChlorideHCID 386654-HeptanamineHCID 221022581-Ethyl-1-(2-propenyl)-3-butenyl isocyanateHCID 221022694-IsocyanatoheptaneHCID 178455853HCID 178455853、化合物

生成物 1

HCID 499620991-Ethyl-1-(2-propenyl)-3-butenylamine収率 34%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

実験手順

1-Propylbutyl isocyanate: This intermediate was prepared from commercially available 4-aminoheptane by the procedure of V. S. Goldesmidt and M. Wick, Liebigs Ann. Chem., 575, 217 (1952). (b) 1-Ethyl-1-(2-propenyl)-3-butenyl isocyanate: A solution of propionitrile (14.5 g, 264 mmol) in dry Et2O (40 mL) was added dropwise to 1.0M allyl magnesium bromide/Et2O (880 mL). The reaction mixture was mechanically stirred at reflux for 2 h, after which time it was cooled to 0°. A saturated aqueous solution of NH4Cl (320 mL) was added cautiously to the cooled reaction mixture. The organic phase was separated, dried (MgSO4), cooled to 0° and then mixed at the same temperature with 1M HCl/Et2O (200 mL). The resulting solid was collected and dried under reduced pressure (ca 27 g). The latter material dissolved in CH2Cl2 (200 mL). The solution was washed with a 10% aqueous solution of Na2CO3 (2 X) and then brine, dried (MgSO4) and concentrated to dryness to afford a yellow oil. The oil was distilled (82°-85°/20 Torr) to give 1-ethyl-1-(2-propenyl)-3-butenylamine as a colorless liquid (11.6 g, 34%); 1H NMR(CDCl3) δ0.89 (t, J=7Hz, 3H), 1.39 (q, J=7 Hz, 2H), 2.11 (d, J=7 Hz, 2H), 5.06-5.14 (m, 4H), 5.80-5.89 (m, 2H).

後処理

  1. temperatureat reflux for 2 h
  2. temperatureafter which time it was cooled to 0°
  3. customThe organic phase was separated
  4. dry with materialdried (MgSO4)
  5. temperaturecooled to 0°
  6. additionmixed at the same temperature with 1M HCl/Et2O (200 mL)
  7. customThe resulting solid was collected
  8. customdried under reduced pressure (ca 27 g)
  9. dissolutionThe latter material dissolved in CH2Cl2 (200 mL)
  10. washThe solution was washed with a 10% aqueous solution of Na2CO3 (2 X)
  11. dry with materialbrine, dried (MgSO4)
  12. concentrationconcentrated to dryness
  13. customto afford a yellow oil
  14. distillationThe oil was distilled (82°-85°/20 Torr)

出典と根拠

ORDレコード
ord-cf3c814ed9a349b5a962fcfd44c9550d
出典データセット
uspto-grants-1998_12
特許番号
US05846941

反応ノート

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