Design of CIEEL-active Dioxetanes having a New Triggering System

点击翻译按钮获取中文摘要

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.