CREATION AND CHARACTERIZATION OF CARBENES HAVING UNUSUAL STRUCTURE

具有不寻常结构的卡宾的产生和表征

• 批准号: 10640577
• 负责人: TAKAHASHI Yusuke
• 金额: $ 2.43万
• 依托单位: MIE UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640577/
• 关键词: Photoisomerization; Carbenes; Cyclobutylidene; Sigmatropy; Substituent Effect; Methylenecyclopropane; Benzocyclobutenylidene; メチリデンシクロプロパン; シクロプチリデン; Photoisomerization; Carbenes; Cyclobutylidene; Sigmatropy; Substituent Effect; Methylenecyclopropane; Benzocyclobutenylidene; メチリデンシクロプロパン; シクロプチリデン

Although it has been reported that irradiation of diphenylmethylenecyclopropane in solution results in its isomer, 2,2-diphenyl-1-methylenecyclopropane, little has been known on the mechanism. The present study provides experimental support for the intermediacy of 2,2-diphenylcyclobutylidene. The detailed product analysis showed that 2,2-diphenylcyclobutene is formed in addition to 2,2-diphenyl-1-methylenecyclopropane. Similar photoreaction under oxygen afforded 2,2-diphenylcyclobutanoneas well.In contrast to parent phenylcarbene, benzocyclobutenylidene has never been observed directly. We are interested in this particular carbene and have attempted to generate benzocyclobutenylidene from precursors in order to investigate its reactivity.Photolysis of N-(2-phenylazyridyl)imine of benzocyclobutenone results in dimers and trimers of benzocyclobutenylidene. Similar photolysis in the presence of alkenes or methanol leads to formation of cyclopropanes or methoxybenzocyclobutene. It is most likely that benzocyclobutenylidene is involved in the photoreactions.Although the steady-state photolyses of the N-(2-phenylazyridyl)imine afford products suggestive of benzocyclobutenylidene, it is elusive even under our laser flash photolytic conditions. However, it is shown that pyridine seems to trap bensocyclobutelideneto give a ylide.

尽管据报道，二苯基甲基苯基丙烷在溶液中的辐射导致其异构体，2,2-二苯基-1-甲基苯基丙烷丙烷，但在该机制上几乎没有知道。本研究为2,2-二苯基环丁基二烯的中间摄氏提供了实验支持。详细的产品分析表明，除2,2-二苯基-1-甲基苯基丙烷外，还形成了2,2-二苯基环丁烯。在氧气下，相似的光反应可为2,2-二苯基环戊烯烯酸烯烯烯配对。与母体苯基苯乙烯相比，从未直接观察到苯基二苯基苯基苯基苯基。我们对这种特殊的碳烯感兴趣，并试图从前体中产生苯基二苯基苯基苯基，以研究其反应性。苯二氯丁烯酮的N-（2-苯基吡啶基）亚氨酸的含量分解会导致苯二甲基丁基二烯基烯基的二聚体和三聚体。在存在烯醇或甲醇存在下的类似光解会导致果丙烷或甲氧基苯并糖环丁烯的形成。尽管N-（2-苯基吡啶基）亚胺的稳态光片剂具有暗示苯二甲基苯基苯基二烯，但即使在我们的激光闪光灯光溶解光溶解光溶解液条件下，苯基二苯基苯基苯基二苯基苯基二烯也参与了光电反应。但是，据表明，吡啶似乎会捕获Bensocyclobutelideneto给出Ylide。