Very low‐pressure pyrolysis of cyclobutyl cyanide. The cyano stabilization energy

Abstract

AbstractA very low‐pressure pyrolysis (VLPP) apparatus has been constructed and shown to yield kinetic data consistent with other VLPP systems. The technique has been applied to the pyrolysis of cyclobutyl cyanide over the temperature range of 833–1203°K. The reaction was found to proceed via a single pathway to yield ethylene and vinyl cyanide. If A∞ is based on previous high‐pressure data for this reaction and for cyclobutane pyrolysis, then RRKM theory calculations show that the experimental unimolecular rate constants are consistent with the high‐pressure Arrhenius parameters given by where θ=2.303 RT in kcal/mole. If A∞ is adjusted relative to the more recent parameters for cyclobutane pyrolysis suggested by VLPP studies, then the Arrhenius expression becomes The cyano group reduces the activation energy for cyclobutane pyrolysis by 6±1 kcal/mole, and on the basis of a biradical mechanism this value may be attributed to the cyano stabilization energy.