Chemiluminescent decomposition of a dioxetane bearing a 3-(1-cyanoethenyl)phenyl moiety induced by Michael addition of an anion of malonate

A thermally stable dioxetane bearing a 3-(1-cyanoethenyl)phenyl group (1) was synthesized. Michael addition of an anion of malonate (3a,b) to a dioxetane (1) substituted with a 3-(1-cyanoethenyl)phenyl moiety took place to give an intermediary dioxetane bearing a benzylic anion, which decomposes rapidly with accompanying emission of crimson light. When an anion of chloromalonate (3c) was used as a base, intramolecular cyclopropanation of 3c occurred concurrently with the Michael-addition-induced chemiluminescent decomposition.