Design and Synthesis of Highly Efficient Chemiluminescent Substrates

1. 热稳定二氧乙烷的设计：双环二氧乙烷，5-烷基-1-芳基-4,4-二甲基-2-氧杂环[3.2]。合成了O]庚烷。其中，含有5-叔丁基的二氧乙烷具有显著的热稳定性。即使与六元环熔合的二氧乙烷，通常远不如它们的五元环类似物稳定，也发现通过3,3位相互作用在热上变得非常稳定。新型触发系统的设计：含酚基的二氧乙烷通过去质子化或去保护（触发），生成含氧苯基阴离子的不稳定二氧乙烷，氧苯基阴离子作为电子供体通过分子内电荷转移机制迅速分解发光。2 .间氨基苯基阴离子除酚基部分外，还作为芳香电子供体，诱导二氧乙烷分解并发出闪光红光。荧光团的设计：合成了6种含2-萘基和不同位置的叔丁基二甲基硅氧基的二氧乙烷，并对它们的氟化物诱导化学发光分解进行了研究。在5-、7-或8位上有一个触发点（硅氧烷）的萘取代二氧乙烷发出红光，而在3-或6位上有一个触发点的萘取代二氧乙烷发出闪光的蓝光。还合成了含苯并呋喃、苯并噻吩或苯并噻唑的二氧乙烷。

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.