Study on a new chemiluminscent reaction with organic phosphorus compounds

有机磷化合物新型化学发光反应的研究

• 批准号: 06805077
• 负责人: MOTOYOSHIYA Jiro
• 金额: $ 0.77万
• 依托单位: Shinshu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06805077/
• 关键词: Chemiluminescence; Phosphonate carbanion; dioxetane; phospha-1,2-dioxetane; acridine; スファー1、2-ジオキセタン; オキセタンイミン; クリジン

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.

研究了一种新的化学发光氧化有机膦化合物的方法。在碱的存在下，生成的膦酸碳负离子与氧反应生成相应的具有化学发光的羰基化合物。在含磷基衍生物的情况下，形成了N-甲基吖啶酮，其发射是由于其荧光。ESR谱还发现，氧化是通过自由基中间体进行的。另一方面，用稀硝酸原位生成的9-磷酰吖啶盐被碱性过氧化氢氧化，并因吖啶酮的荧光而发光。在该反应中，Kight发射强烈依赖于磷酰基的结构，这表明该反应涉及化学引发的电子交换化学发光(CIEEL)机理，而磷酸-1，2-二氧杂环己烷是关键的中间体。用单线态氧或碱性过氧化氢氧化亚氨基亚甲基-10-甲基吖啶时，观察到微弱的发光。为了与二氧杂环己烷或二氧杂环己酮进行比较，进行了SCF计算，解释了二氧杂环己胺的化学发光效率较低的原因。综上所述，本研究建立了一种新的二氧杂环己烷的化学发光，并通过详细的实验揭示了这些反应的机理。这些基本结果显示了在其他领域进一步应用的可能性。

项目成果

Jiro Motoyoshiya,et al.: "Direct Chemiluminescence of Dioxetanemine Derined from 9-(N-tert-Butyliminomethylidene)-10-methylacridan. Comparison of……" Heterocyclic Communications. 2(in print). (1995)

Jiro Motoyoshiya 等人：“由 9-(N-叔丁基亚氨基亚甲基)-10-甲基吖啶丹衍生的二氧环丁胺的直接化学发光。比较...”(Heterocycl Communications) (1995 年)。

Jiro Motoyoshiya,et al.: "Direct Chemiheminescence of Dioxetanimine Derived from 9-(N-tert-Butyliminomethyliden)-10-Methylacridon.…" Heterocyclic Communications. 1. 259-264 (1995)

Jiro Motoyoshiya 等人：“源自 9-(N-叔丁基亚氨基甲基)-10-甲基吖啶酮的二氧杂环丁胺的直接化学半化学。…”Heterocycling Communications。

Jiro Motoyoshiya,et al.: "Direct Chemihuminescence of Dio xetanimine Deriverd from 9-(N-tert-Butyliminomethyliden)-10-Methylacriolan." Heteroeyelic.Communications.1. 259-264 (1995)

Jiro Motoyoshiya 等人：“来自 9-(N-叔丁基亚氨基甲基)-10-甲基丙烯酰胺的 Dio xetanimine 衍生物的直接化学腐烂。”

Jiro Motoyoshiya, Mayumi Mori, Susumu Narita, and Sadao Hayashi: "DIRECT CHEMILUMINESCENCE OF DIOXETANIMINE DERIVED FROM 9- (N-tert-BUTYLIMINOMETHYLIDENE) -10-METHYLACRIDAN.COMPARISON OF DIOXETANES BY SCF CALCULATIONS" Heterocyclic Communications. Vol.1.

Jiro Motoyoshiya、Mayumi Mori、Susumu Narita 和 Sadao Hayashi：“从 9-（N-叔丁基亚氨基亚甲基）-10-甲基丙烷衍生的二氧杂环丁胺的直接化学发光。通过 SCF 计算比较二氧杂环丁烷”杂环通讯。