4786-19-0Relevant academic research and scientific papers
Elimination kinetics of β-hydroxynitriles in the gas phase
Chuchani, Gabriel,Dominguez, Rosa M.,Rotinov, Alexandra,Quijano, Jairo,Valencia, Cristina,Vicente, Bernardo,Franco, Dimas
, p. 19 - 23 (2007/10/03)
The gas-phase elimination kinetics of primary, secondary and tertiary β-hydroxynitriles were examined in static seasoned vessels over the temperature range 360-450 °C and pressure range 47-167 Torr (1 Torr = 133.3 Pa). These reactions are homogeneous, unimolecular and follow a first-order rate law. The rate coefficients are given by the Arrhenius equation: for 3-hydroxypropionitrile log k1 = (14.29 ± 0.47) - (234.9 ± 6.3) kJ mol-1 (2.303 RT)-1; for 3-hydroxybutyronitrile log k1 = (13.76 ± 0.10) - (222.6 ± 0.7) kJ mol-1 (2.303RT)-1; and for 3-hydroxy-3-methylbutyronitrile log k1 (s-1) = (13.68 ± 0.68) - (212.5 ± 8.7) kJ mol-1 (2.303RT)-1. The decomposition rates of the β-hydroxynitriles increase from primary to tertiary carbon containing the OH group. The rates for the β-hydroxynitriles are found to be slower than those for the corresponding β-hydroxyacetylene analogs. The value of log A from 13.7 to 14.4 and the small positive ΔS≠ indicate a mechanism different from a six-centered cyclic transition state. These data appear to indicate that a four-membered cyclic transition state or a quasi-heterolytic mechanism is conceivable. Copyright
Production of Acrylonitrile and Other Unsaturated Nitriles from Alkenes and Alkynes
Henis, Neil B.,Miller, Larry L.
, p. 2526 - 2529 (2007/10/02)
Passage of unsaturated organic molecules trough a 13.56-MHz radio-frequency discharge, in the presence of cyanogen, results in the formation of unsaturated nitriles.Acrylonitrile was the major product from ethylene, propylene, acrolein, methyl vinyl ketone, or 1,1,1-trifluoropropylene. 1-Butene, 2-butene, and isobutylene gave mixtures of nitrile products with the CN situated at vinylic or allylic positions. 2-Butyne gave 1-cyanopropyne.Other compounds gave only low yields of nitriles and considerable polymer.The effects of power, pressure, flow rate, and ratios of reactants on the yields of acrylonitrile from propylene and cyanogen were studied.A typical power yield of acrylonitrile was 30 g kW-1 h-1.Maximum material yields of nitrile products were obtained at intermediate powers and pressures.The products are consistent with a reaction scheme involving attack of initially formed cyano radicals on the organic substrate.This step forms activated radical intermediates, which decay through elimination of an atom or group.The atom or group which is most weakly bound is preferentially lost.
