Study on a new chemiluminscent reaction with organic phosphorus compounds

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A new chemiluminescent oxidation of organic phosphonates was investigated in detail. In the presence of bases, the generated phosphonate carbanions reacted with oxygen to give the corresponding carbonyl compounds with chemiluminescence. In the case of acridan derivatives with phosphoryl groups N-methyl acridone was formed and the emission was due to its fluorescence. It was also found that the oxidation proceeded through radical intermediates by ESR spectrum. On the other hand, 9-phosphoryl acridinium salts generated with diluted nitric acid in situ was oxidized by alkaline hydrogen peroxide with a light emission due to the fluorescence of acridone. In this reaction, the kight emission strongly depended upon the structure of phosphoryl groups, which indicated that this reaction involved the chemically initiated electron exchange chemiluminescence (CIEEL) mechanism and phospha-1,2-dioxetanes were crucial intermediates.The chemiluminescence of an iminodioxetane was also studied employing a keten-imine. A weakly light emission was observed when the iminomethyliden-10-methylacridan was oxidized with singlet oxygen or alkaline hydrogen peroxide. In order to compare with dioxentan or dioxetanone, SCF calculation was made and lower efficiency of dioxetanimine in chemiluminescence could be explained.In conclusion, a new chemiluminescence from phospha-1,2-dioxetanes was established by this study and the mechanism of these reactions was also revealed by detailed experiments. These fundamental results show the possibility of further application in other fields.