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Researches on the Effect of Spiro-Activation of Small Ring Compounds in Their Ring Cleavage Reactions.

小环化合物螺环活化对其开环反应影响的研究。

基本信息

批准号：
01430005
负责人：
NISHIDA Shinya
金额：
$ 17.92万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01430005/
关键词：
Spiro-activation of cyclopropane Ring cleavage of small rings Cycloaddition reactions TCNE Oxidation potential Ionization potential Cation radical 04Nucleophilic attack of the nitrogen in the chyano group スピロシクロプロパンスピロ活性化効果転位反応シクロ

项目摘要

In continuation of the study on spiro-activation of cyclopropanes, reactions of spiroindans, spiroindenes, spiroheptenes, and spiroheptadienes with TCNE were examined. Although the basic reaction courses were [pi2+pi2] and [pi2+sigma2] cycloaddition as those observed in the reactions of spirofluorene derivatives, varied reactions were observed to occur depending upon substituents on the substrates. One of the most interesting observation was that the reaction of 1, 1-dicyclopropylspiro [2.4] hepta-4, 6-diene with TCNE gave, in addition to the expected Diels-Alder adduct, an imine derivative, which should be produced after extensive rearrangement. Similar transformation was observed to occur also in the reactions of spiroindenes. Evidently, this should be one of the basic reactions to be considered when TONE was allowed to react with vinylcyclopropanes. The other interesting result was that oxidation potential as well as ionization potential of spiroheptanes and spiroheptenes were influenced by the substituents on the cyclopropane ring as expected, but those of spiroheptadienes were not subjected to the substituent effect. The results are of great interest with regard to the structure of five-membered unsaturated cation radicals. In addition to these studies, the stereochemistry of TCNE cycloaddition and the reaction of diphenyl-substituted spirofluorene derivatives were investigated. All results gave important basic knowledge with regard to the spiro-activation of cyclopropanes. Finally, it was found that even 1, 2-dicyclopropylethylene reacted with TCNE in the [pi2+sigma2] manner under certain reaction conditions. In relation to this result, the photochemical reaction of 1, 2-dicyclopropylethylene with chloranil was also examined. The results provided supporting evidences that the reaction involving cyclopropane cleavage might be characteristic to that of cation radical intermediates.

在对环丙烷的螺活化的研究的继续中，研究了螺茚满、螺茚、螺庚烯和螺庚二烯与TCNE的反应。虽然基本的反应过程是[pi 2 + pi 2]和[pi 2 + sigma 2]环加成，如在螺芴衍生物的反应中观察到的那些，但观察到根据底物上的取代基发生不同的反应。最有趣的观察结果之一是，1，1-二环丙基螺[2.4]庚-4，6-二烯与TCNE的反应除了得到预期的Diels-Alder加合物外，还得到亚胺衍生物，该衍生物应在大量重排后产生。在螺茚的反应中也观察到类似的转化。显然，当TONE与乙烯基环丙烷反应时，这应该是要考虑的基本反应之一。另一个有趣的结果是，螺庚烷和螺庚烯的氧化电位以及电离电位的环丙烷环上的取代基的影响，如预期的，但螺庚二烯的氧化电位以及电离电位不受取代基的影响。这些结果对于五元不饱和阳离子自由基的结构具有重要意义。此外，还研究了TCNE环加成反应和二苯基取代螺芴衍生物反应的立体化学。这些结果为环丙烷的螺环活化提供了重要的基础知识。最后，在一定的反应条件下，发现1，2-二环丙基乙烯与TCNE也以[pi ~ 2 + σ ~ 2]方式反应。与此相关，还研究了1，2-二环丙基乙烯与四氯苯醌的光化学反应。实验结果为环丙烷裂解反应可能是阳离子自由基中间体裂解反应的特征提供了有力的证据。