The Radiolysis and Photolysis of Cycloheptatriene

Abstract 1) In the photosensitized reaction of cycloheptatriene vapor, toluene was produced as the result of isomerization. The amount of toluene formation decreases as the pressure of cycloheptatriene increases. Isomerization to toluene proceeds through the excited molecule, which may be collisionally deactivated. 2) The ESR experiments at low temperatures show that cycloheptatrienyl radicals are formed by electron irradiation. However, the yield of the radical formation is low, nearly equal to that of benzene. 3) In the radiolysis of liquid cycloheptatriene the G values of the gaseous products and toluene are very small. The G value of the polymer seems to suggest the low yield of the radical formation at the initial step. We concluded that the major part of the absorbed energy results in the formation of the excited molecule, the electronic energy of which is readily converted to thermal energy.