Chemiluminescence in autoxidation of phosphonate carbanions. Phospha-1,2-dioxetanes as the most likely high-energy intermediates

Jiro Motoyoshiya, Tsuneaki Ikeda, Shuji Tsuboi, Tatsuya Kusaura, Yoshino Takeuchi, Satoko Hayashi, Sachiko Yoshioka, Yutaka Takaguchi, Hiromu Aoyama

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27 Citations (Scopus)

Abstract

Autoxidation of the phosphonate carbanions derived from 9-phosphono-10-hydroacridanes provided chemiluminescence ascribed to the excited acridone anion. The intramolecular CIEEL (chemically initiated electron exchange luminescence) mechanism can be applied to this chemiluminescence because of the much higher emission efficiency compared to that of 9-phosphono-10-methylacridanes. The effect of the phosphonate substituents on the emission efficiency and especially on the rates of the chemiluminescence decay can be interpreted to originate from the valence deviation of the phosphorus atoms, which is connected with the substituent effect on the geometrical selectivity in the olefination reaction of the phosphonate carbanions. The enhanced chemiluminescence in the presence of the fluorophores was also detected in autoxidation of the carbanions of diethyl diphenylmethylphosphonate and fluorenylphosphonate. Although the evidence is circumstantial, these results strongly support the belief that phospha-1,2-dioxetane is the most likely high-energy intermediate generating the excited molecules.

Original languageEnglish
Pages (from-to)5950-5955
Number of pages6
JournalJournal of Organic Chemistry
Volume68
Issue number15
DOIs
Publication statusPublished - Jul 25 2003
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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    Motoyoshiya, J., Ikeda, T., Tsuboi, S., Kusaura, T., Takeuchi, Y., Hayashi, S., Yoshioka, S., Takaguchi, Y., & Aoyama, H. (2003). Chemiluminescence in autoxidation of phosphonate carbanions. Phospha-1,2-dioxetanes as the most likely high-energy intermediates. Journal of Organic Chemistry, 68(15), 5950-5955. https://doi.org/10.1021/jo030046l