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Approach to Biradical Chemistry utilizing Photoindeced Electron Transfer

利用光诱导电子转移的双自由基化学方法

基本信息

批准号：
12440173
负责人：
MIYASHI Tsutomu
金额：
$ 8.83万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

We studied the new generation and characterization of various biradicals generated in the photoinduced electron transfer reactions [(1)-(7) except for (6)] and a related direct irradiation reaction [(6)]. In the former, the keys step is a facile back electron transfer in a radical ion pair, which converts quantitatively the reactive radical cation intermediates to the corresponding diradicals.As results, we have found novel cation radicals and biradicals which undergo unprecedented reactions, and gained valuable insights into steric and electronic structures of controversial biradicals. The studies is still now in progress and thus, next year, we will apply a grant-in-aid to the Ministry of Education, Culture, Sports, Science, and Technology.(1) Photoinduced Electron Transfer Reactions of 2,2-Diaryl-1-methylenecyclopropane.(2) Photoinduced Electron Transfer Reactions of 5,5-Dimethyl-2,3-bis(α-styryl)-1,3-cyclobutadiene.(3) Photoinduced Electron Transfer Reactions of cis-and trans-2-Anisyl-3-methyl-1-methylenecyclopropane and cis-and trans-2-Anisyl-1-ethylidenecyclopropane.(4) Photoinduced Electron Transfer Reactions of 7-(Dianisylmethylene)-2,3-diazabicyclo[2.2.1]hept-2-ene.(5) Photoinduced Electron Transfer Reactions of 3,3-Dimethy1-4-methylene-2,2-bis(4-methoxyphenyl)cyclobutanone and 4-Isopropilidene-2-bis(4-methoxyphenyl)cyclobutanone.(6) Direct Irradiation reaction of 7-(Diarylmethylene)-2,3-diazabicyclo[2.2.1]hept-2-ene.(7) Photoinduced Electron Transfer Reactions of 1,2-Bis(α-styryl)benzenes and 3,4-bis(α-styryl)furans.

我们研究了光诱导电子转移反应[(1)-(7)(6)除外]和相关的直接辐照反应[(6)]中产生的各种双自由基的新一代和表征。在前者中，关键步骤是自由基离子对中容易的反向电子转移，将活性自由基阳离子中间体定量地转化为相应的双自由基。结果，我们发现了新的阳离子自由基和双自由基，它们经历了前所未有的反应，并对有争议的双自由基的空间和电子结构获得了有价值的见解。由于研究还在进行中，明年将向教育文化体育科学技术部申请支援金。”(1) 2,2-二芳基-1-亚甲基环丙烷的光诱导电子转移反应。(2) 5,5-二甲基-2,3-二（α-苯基）-1,3-环丁二烯的光诱导电子转移反应。(3)顺式和反式2-苯基-3-甲基-1-亚甲基环丙烷和顺式和反式2-苯基-1-乙基环丙烷的光诱导电子转移反应。(4) 7-（二酰基亚甲基）-2,3-重氮杂环[2.2.1]庚-2-烯的光诱导电子转移反应。(5) 3,3-二甲基1-4-亚甲基-2,2-二（4-甲氧基苯基）环丁酮和4-异丙烯-2-二（4-甲氧基苯基）环丁酮的光诱导电子转移反应。(6) 7-（二芳基亚甲基）-2,3-重氮杂环[2.2.1]庚-2-烯的直接辐照反应。(7) 1,2-二（α-苯基）苯和3,4-二（α-苯基）呋喃的光诱导电子转移反应。