Design and Synthesis of Highly Efficient Chemiluminescent Substrates

1.热稳定性二氧杂环烷的设计：合成了双环二氧六环化合物5-Alkyl-1-aryl-4，4-dimethyl-2-oxabicyclo[3.2.O]heptanes。其中，含有5-叔丁基的二氧杂环己烷具有显著的热稳定性。即使是与六元环融合的二氧杂环烷，据报道通常远不如它们的五元环类似物那么稳定，也被发现通过3，3-空间相互作用变得非常稳定。新触发系统的设计：通过去质子化或去保护(触发)，含酚基团的二氧杂环己烷产生含氧苯负离子的不稳定的二氧杂环己烷，该二氧杂环己烷通过分子内电荷转移机制迅速分解而发光，其中氧基苯基阴离子作为电子供体。间氨基苯基阴离子也是苯酚以外的芳香族电子供体，可以诱导二氧杂环己烷分解发出闪光红光。荧光团的设计：合成了6个在不同位置含有2-萘基和叔丁基二甲基硅氧基的二氧杂环己烷，并研究了它们在氟化物诱导下的化学发光分解。在5、7或8位具有触发剂(硅氧基)的萘基取代二氧杂环烷发出红光，而它们在3或6位具有触发剂的类似物提供闪光蓝光。还合成了含苯并呋喃、苯并噻吩苯或苯并噻唑的二氧杂环己烷。

1. Design of Thermally Stable Dioxetanes : Bicyclic dioxetanes, 5-Alkyl-1-aryl-4,4-dimethyl-2-oxabicyclo[3.2.O]heptanes were synthesized. Among them, dioxetanes bearing a 5-tert-butyl were found to possess marked thermal stability. Even dioxetanes fused with six-membered ring, which have been reported to be in general far less stable than their five-membered ring analogs, were found to become very stable thermally by means of 3,3-steric interaction.2. Design of New Triggering System : By deprotonation or deprotection (triggering), a dioxetane bearing a phenolic group produce an unstable dioxetane bearing an oxyphenyl anion, which decomposes rapidly to emit light by intramolecular charge transfer mechanism where an oxyphenyl anion acts as an electron donor. An anion of m-aminophenyl group acts also as an aromatic electron donor other than phenolic moiety to induce decomposition of a dioxetane to emit flash red light.3. Design of Fluorophore : Six dioxetanes bearing a 2-naphthyl with a tert-butyldimethylsiloxy at the various position were synthesized and their fluoride-induced chemiluminescent decomposition was examined. Naphthyl-substituted dioxetanes having a trigger (siloxy) at the 5-, 7-, or 8-position emitted red light, while their analogs with a trigger at the 3- or 6-position afforded flash blue light. Dioxetanes bearing a benzofuran, benzothiophene, or benzothiazole were also synthesized.