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

HRID 1456917Notes

Reaction equation

HRID 1456917 reaction equation
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]

Participants

8

Reactant 6

HCID 7854PropionitrileHCID 25517Ammonium ChlorideHCID 386654-HeptanamineHCID 22102258HCID 22102258, compoundHCID 221022694-IsocyanatoheptaneHCID 178455853HCID 178455853, compound

Product 1

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

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

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).

Workup

  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)

Sources & evidence

ORD record
ord-cf3c814ed9a349b5a962fcfd44c9550d
Source dataset
uspto-grants-1998_12
Patent number
US05846941

Reaction notes

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