Intramolecular charge-transfer-induced chemiluminescent decomposition of 1,2-dioxetanes bearing a phenylmethanide anion

Dioxetanes () bearing a phenyl moiety substituted with a methylene or methine having an electron-withdrawing group(s) (–CH2-Ew or –CH(X)-Ew) and dioxetane () bearing a 3-(1-cyanoethenyl)phenyl group were synthesized. Treatment of dioxetanes () with tetrabutylammonium fluoride (TBAF) caused their decomposition with accompanying emission of light with maximum wavelength at 530–758 nm. The Michael addition of a bis(methoxycarbonyl)methanide anion to dioxetane () produced initially an unstable dioxetane bearing a phenylmethanide anion, decomposition of which gave light with maximum wavelength at 710–740 nm. Intramolecular cyclopropanation without decomposition of the dioxetane ring took place concurrently for the Michael reaction-induced decomposition of with the bis(methoxycarbonyl)chloromethanide anion.