Adamantylideneadamantane- 1,2-dioxetane. An Investigation of the Chemiluminescence and Decomposition Kinetics of an Unusually Stable 1,2-Dioxetane

Abstract: The thermolysis of adamantylideneadamantane dioxetane 1 was investigated. The activation energy for cleavage of 1 was found to be ca. 37 kcal/mol and essentially solvent independent. The thermal decomposition of 1 is chemiluminescent. The yield and nature of the chemically produced excited states were determined by chemical titration and found to be ca. 2% singlet and ca. 15 % triplet. Photolysis of 1 leads to the adiabatic formation of singlet and triplet adamantanone with yields of 8 and 40%, respectively. A detailed kinetic analysis of the photochemical reactions of adamantanone with trans-dicyanoethy-lene was carried out. Chemiluminescence from the thermolysis of 1,2-dioxe-tanes is a recently discovered phenomenon.2 Interest in this reaction stems not only from the experimental observation of the "cold light " phenomenon but also from a theoretical problem of understanding a mechanism for the conversion of ground state reactants into excited state products. An understanding of these reactions may lead to the ability to predict the design of chemiluminescent reactions and to es-tablish a more complete picture of potential energy surface