Design and Synthesis of Highly Efficient Chemiluminescent Substrates

高效化学发光底物的设计与合成

• 批准号: 09640650
• 负责人: MATSUMOTO Masakatsu
• 金额: $ 1.22万
• 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: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640650/
• 关键词: Chemiluminescence; 1,2-Dioxetane; Thermal stability; Trigger; Charge transfer; 赤色発光

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.

1.热稳定二氧杂环丁烷的设计：合成了双环二氧杂环丁烷、5-烷基-1-芳基-4，4-二甲基-2-氧杂双环[3.2.O]庚烷。其中，带有5-叔丁基的二氧杂环丁烷被发现具有显着的热稳定性。甚至与六元环稠合的二氧杂环丁烷（已报道其通常远不如其五元环类似物稳定）也被发现通过3，3-空间相互作用变得非常热稳定。新触发体系的设计：通过去质子化或去保护（触发），带有酚基的二氧杂环丁烷产生不稳定的带有氧苯基阴离子的二氧杂环丁烷，其通过分子内电荷转移机制快速分解发光，其中氧苯基阴离子作为电子供体。间氨基苯基的阴离子也作为芳族电子供体而不是酚部分来诱导二氧杂环丁烷分解以发射闪烁红光。荧光团的设计：合成了6个2-萘基上不同位置带有叔丁基二甲基硅氧基的二氧杂环丁烷，研究了它们在氟化物诱导下的荧光分解。在5-、7-或8-位具有触发剂（甲硅烷氧基）的萘基取代的二氧杂环丁烷发射红光，而在3-或6-位具有触发剂的它们的类似物提供闪烁的蓝光。还合成了带有苯并呋喃、苯并噻吩或苯并噻唑的二氧杂环丁烷。

项目成果

N.Watanabe, M.Matsumoto,: "Synthesis of 3-alkoxy-3-aryl-4, 4-diisopropyl-1, 2-dioxetanes and their base-induced chemiluminescence" Tetrahedron. 4287-4298 (1999)

N.Watanabe，M.Matsumoto，：“3-烷氧基-3-芳基-4, 4-二异丙基-1, 2-二氧杂环丁烷及其碱诱导化学发光的合成”四面体。

M.Matsumoto, N.Watanabe,: "Chemiluminescence of spiro[1, 2-dioxetane-3, 1'-dihydroisobenzofuran]s, spiro[1, 2-dioxetane-3, 1'-isochroman]s and a spiro[1, 2-dioxetane-3, 1'-(2-" Tetrahedron Lett.38. 5825-5828 (1997)

M.Matsumoto, N.Watanabe,：“螺[1, 2-二氧杂环丁烷-3, 1-二氢异苯并呋喃]、螺[1, 2-二氧杂环丁烷-3, 1-异色满] 和螺[1]的化学发光

N.Watanabe, H.Suganuma, H.Kobayashi, H.Mutoh, Y.Katao, and M.Matsumoto: "Synthesis of 3-alkoxy-3-aryl-4,4, disopropy-1,2-dioxetanes and their base-induced chemiluminescence" Tetrahedron. 55. 4287-4298 (1999)

N.Watanabe、H.Suganuma、H.Kobayashi、H.Mutoh、Y.Katao 和 M.Matsumoto：“3-烷氧基-3-芳基-4,4，二异丙-1,2-二氧杂环丁烷及其碱的合成

M.Matsumoto, H.Murakami, and N.Watanabe: "Thermal decomposition of 1-(aminophenyl)-5-tert-butyl-4,4-dimethyl-2,6,7-trioxabicyclo [3.2.0] heptanes, unusual O-O bond cleavage competing with normal fragmentation of 1,2-dioxetanes." J.Chem.Soc.Chem.Commun.231

M.Matsumoto、H.Murakami 和 N.Watanabe：“1-(氨基苯基)-5-叔丁基-4,4-二甲基-2,6,7-三氧杂双环[3.2.0]庚烷的热分解，不寻常

M.Matsumoto, N.Watanabe,: "Base-induced cyclization of 7-aryl-2, 2, 4, 4-tetramethyl-6-oxaheptan-3-ones : intramolecular nucleophilic addition of an anion of the benzyl ether to the" J.Chem.Soc.Chem.Commun.2395-2396 (1997)

M.Matsumoto, N.Watanabe,：“碱诱导的 7-芳基-2, 2, 4, 4-四甲基-6-氧六庚烷-3-酮的环化：苄基醚阴离子的分子内亲核加成”