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Design of CIEEL-active Dioxetanes having a New Triggering System

具有新型触发系统的 CIEEL 活性二氧杂环丁烷的设计

基本信息

批准号：
15550043
负责人：
WATANABE Nobuko
金额：
$ 1.92万
依托单位：
Kanagawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550043/
关键词：
Chemiluminescence substrate Triggering Dioxetane Aryl sulfide anion Aryl methanide anion Aryl amide anion 化学発光 CIEEL アリルチオラートアニオンアリールメチル型カルバニオン

项目摘要

New CIEEL-active dioxetanes having a new triggering system were designed and synthesized. The dioxetanes realized were 5-t-butyl-4,4-dimethyl-2,6,7-trioxabicyclo-[3.2.0]heptanes, which bear an electron-donor, such as aryl sulfide anion, arylmethanide anion, and arylamide anion at the 1-position instead of typical areneoxide anion.1.Aryl sulfide anion (aryl-S^-) system : Dioxetanes bearing an acylthiophenyl group was synthesized. Since benzenethiol is stronger acid than phenol, dioxetanes bearing a thiophenolic moiety could be triggered by a weak base such as amines. In fact, they decomposed on treatment with a primary amine to emit yellow light with moderate chemiluminescent efficiency in DMSO. Even in an aqueous system, they gave light without significant decrease of chemiluminescent efficiency. A dimeric dioxetane having a disulfide function could be also triggered with Bu_4N hydroxide.2.Arylmethanide anion (aryl-C^-) system : Dioxetanes bearing a phenyl moiety substituted with a methyl having an electron-withdrawing group were treated with TBAF/DMSO to emit light with maximum wavelength at 758〜530 nm. The order of the base-induced decomposition rates coincided with the order of acidity for parent carbon acids. A dioxetane bearing a 3-(1-cyanoethenyl)phenyl group was also found to undergo the Michael-addition-induced chemiluminescent decomposition. When chlorobis (methoxycarbonyl)methanide was used as a nucleophile, the CT-induced decomposition of an intermediary dioxetane bearing a phenymethanide competed with the intramolecular cyclopropanation. These results show a possibility that the rate of an intramolecular competitive reaction can be estimated by examining the product ratio in the spent reaction mixture,.3.Arylamide anion (aryl-N^-) system : Dioxetane bearing acylaminophenyl and iridole were synthesized and confirmed to emit light by the treatment with base. These are a first example of dioxetane active toward N-triggering.

设计并合成了具有新触发体系的CIEEL活性二氧杂环丁烷。合成的二氧杂环丁烷为5-叔丁基-4，4-二甲基-2，6，7-三氧杂双环[3.2.0]庚烷，其1-位带有电子给体，如芳基硫醚阴离子、芳基甲烷阴离子和芳基酰胺阴离子，而不是典型的芳氧阴离子。由于苯乙烷的酸性比苯酚强，因此带有噻吩部分的二氧杂环丁烷可以被弱碱如胺触发。事实上，它们在用伯胺处理时分解，在DMSO中以中等的荧光效率发射黄光。即使在水性体系中，它们也发光而不显著降低荧光效率。2.芳基甲烷阴离子（aryl-C^-）体系：带有一个吸电子基团的甲基取代的苯基的二氧杂环丁烷经TBAF/DMSO处理后，其最大发光波长为758 ~ 530 nm。碱诱导分解速率的顺序与母体碳酸的酸度顺序一致。带有3-（1-氰基乙烯基）苯基的二氧杂环丁烷也被发现进行迈克尔加成诱导的荧光分解。当氯双（甲氧羰基）甲烷被用作亲核试剂，CT诱导的分解的中间体二氧杂环丁烷轴承苯甲烷竞争的分子内环丙烷化。这些结果表明，可以通过检测反应混合物中产物的比例来估计分子内竞争反应的速率。3.芳基酰胺阴离子（aryl-N^-）体系：合成了带有酰胺基苯基和环吲哚的二氧杂环丁烷，并通过碱处理证实了其发光。这是二氧杂环丁烷对氮触发有活性的第一个例子。