Kinetics of the diels–alder addition of ethene to cyclohexa-1,3-diene and its reverse reaction in the gas phase

The addition of ethene to cyclohexa-1,3-diene has been studied between 466 and 591 K at pressures ranging from 27 to 119 torr for ethene and 10 to 74 torr for cyclohexa-1,3-diene. The reaction is of the “Diels–Alder” type and leads to the formation of bicyclo[2.2.2]oct-2-ene. It is homogeneous and first order with respect to each reagent. The rate constant (in l./mol sec) is given by The retron-Diels–Alder pyrolysis of bicyclo[2.2.2]oct-2-ene has also been studied. In the ranges of 548–632 K and 4–21 torr the reaction is first order, and its rate constant (in sec^?1) is given by The reaction mechanism is discussed. The heat of formation and the entropy of bicyclo[2.2.2]oct-2-ene are estimated.