Thermal decomposition of ethyl cyanoformate: kinetics and mechanism
Abstract
The thermal decomposition of ethyl cyanoformate was investigated between 310 and 405 °C at subambient pressures. Two parallel reactions account for the observed products CO2, C2H4, HCN, and EtCN, the last being the result of internal substitution with simultaneous loss of carbon dioxide, the reaction occurring heterogeneously, while the olefin-forming elimination was found to be homogeneous and molecular. The temperature dependence for this reaction is given by equation (i). ke/s–1= 1011·44 ± 0·25 exp –42,600 ± 610/RT(340–405 °C)(i) The energy of activation of this and analogous reactions of compounds of formula XCO2C2H5 are linearly correlated with Taft's polar constants σ* for the group X.