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

Participants

Reaction Steps

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).

Provenance & Evidence