Intramolecular electron-transfer-induced cleavage of dioxetanes observed in fast-atom bombardment tandem mass spectrometry

Eur. J. Mass Spectrom. 7, 441–445 (2001)
DOI: 10.1255/ejms.459

Intramolecular electron-transfer-induced cleavage of dioxetanes observed in fast-atom bombardment tandem mass spectrometry

Mamoru Ohashi,^* Masakazu Takanashi, Nobuko Watanabe and Masakatsu Matsumoto
Department of Chemistry, Kanagawa University, Tsuchiya, Hiratsuka, Kanagawa, 259-1293 Japan
Takumi Saisu and Haruki Niwa
Department of Applied Physics and Chemistry, The University of Electro-Communications, Chofu, Tokyo, 182-8585 Japan

ABSTRACT:

Phenolic spiroadamantyl-substituted dioxetanes are well known base-induced chemiluminescent compounds. Fast-atom bombardment collision- induced dissociation tandem mass spectrometry (FAB CID-MS/MS) of five phenolic spiroadamantyl-substituted dioxetanes in the negative-ion mode clearly showed that a highly efficient cleavage of the dioxetane rings took place to produce the corresponding phenolate ion almost exclusively. The mass spectrometric behavior of these compounds reflects the highly efficient intramolecular electron-transfer-induced cleavage of dioxetane rings, which participates in the highly efficient base-triggered chemiluminescent reactions of these compounds in solution.

Keywords: fast-atom bombardment, tandem mass spectrometry, 1,2-dioxetane, electron-transfer, admantanone, chemiluminescence

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