295311-79-4Relevant academic research and scientific papers
Fluoride-triggered decomposition of m-sililoxyphenyl-substituted dioxetanes by an intramolecular electron transfer (CIEEL) mechanism
Nery, Ana L. P.,Roepke, Sascha,Catalani, Luiz H.,Baader, Wilhelm J.
, p. 2443 - 2446 (1999)
The synthesis of the protected phenolate-substituted 1,2-dioxetanes 1 and 2, containing the substituent directly linked to the peroxidic ring or separated by a methylene group, is reported. The activation parameters and chemiluminescence quantum yield upon unimolecular and catalyzed decomposition of 1 and 2 are in agreement with the occurrence of an intramolecular CIEEL mechanism in the catalyzed decomposition of these dioxetanes.
Studies on the intramolecular electron transfer catalyzed thermolysis of 1,2-dioxetanes
Nery, Ana L. P.,Wei?, Dieter,Catalani, Luiz H.,Baader, Wilhelm J.
, p. 5317 - 5327 (2007/10/03)
This work reports the synthesis and the chemiluminescence properties of the dioxetanes: 4-ethyl-4-methyl-3-(3-methoxyphenyl)-1,2-dioxetane (I), 4-ethyl-4-methyl-3-(3-tert-butyldimethylsilyloxyphenyl)-1,2-dioxetane (II), 4,4-dimethyl-3-(3-methoxybenzyl)-1,2-dioxetane (III) and 4,4-dimethyl-3-(3-tert-butyldimethylsilyloxybenzyl)-1,2-dioxetane (IV). While in the thermal decomposition of I-IV preferential formation of triplet excited states is observed, in the presence of fluoride ions the decomposition rate constants of II and IV increase drastically and singlet excited states are formed with high quantum yields. These results are discussed based on the CIEEL ('Chemically Initiated Electron Exchange Luminescence') mechanism where the decomposition of the dioxetanes should be initiated by an intramolecular electron transfer from the phenolate ion (generated by fluoride catalyzed deprotection of the silyloxy group), either directly bound to the peroxidic ring (II) or separated from it by a methylene bridge (IV). (C) 2000 Elsevier Science Ltd.
