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SYNTHESIS OF AZULENE-EQUIVALENT HETEROCYCLES BY [4pi+6pi] CYCLOADDITIONS

[4pi 6pi] 环加成合成甘菊环等价杂环

基本信息

批准号：
08640679
负责人：
KATO Hiroshi
金额：
$ 1.28万
依托单位：
SHINSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08640679/
关键词：
MESOIONIC CYCLOADDITION AZULENE HETEROCYCLE EXTRUSION FULVENE 4π+6π シドノン

项目摘要

1. Efficient synthetic procedures of 2-tert-butyl-6-(dimethylamino and acetoxy)fulvene was established, and reaction products between these compounds and several mesoionic compounds were scrutinized by the use of preparative liquid chromatography, which was purchased by the present grant.2. These reactions, as expected, gave condensed heterocycles which are isoelectronic with azulene, by [4pi+6pi] cycloaddition-extrusion-elimination reactions. A corresponding 2-unsubstituted fulvene also underwent this type of reaction though in lower yields.3. The reactions between 2-tert-butyl-6,6-dimethylfulvene and mesoionic compounds gave both [4pi+6pi] and [4pi+2pi] cycloadducts.4. In some reactions of the dimethyl derivative, interesting rearrangement products were formed in some cases. Structures of these products were firmly established by X-ray analyzes and other spectroscopic methods, and the mechanisms for their formation was discussed.5. A mesoionic 4-oxazolone gave an interesting oxygenated dimer on contact with a trace amount of oxygen. Its structure was determined by X-ray analysis.6. Spectral analyzes of these pseudo-azulene heterocycles showed that the electron distribution of these molecules are similar to that of azulene and the molecules are strongly polarized.7. These reactions have been analyzed on the basis of MNDO calculation results, and it was concluded that these reactions can proceed concertedly by both [4pi+6pi] and [4pi+2pi] fashion. This conclusion supports the view that a bulky substituent on the 2-position of fulvene ring strongly controls the periselectivity of these reactions.

1.建立了2-叔丁基-6-（二甲氨基和乙酰氧基）富烯的高效合成方法，并利用本课题组购买的制备液相色谱仪对这些化合物与几种介离子化合物的反应产物进行了分析.通过[4pi+6pi]环加成-挤出-消除反应，得到了与甘菊环等电子的稠合杂环化合物。相应的2-未取代富烯也经历了这种类型的反应，但产率较低。2-叔丁基-6，6-二甲基富烯与介离子型化合物反应生成[4pi+6pi]和[4pi+2 pi]环加合物.在二甲基衍生物的某些反应中，在某些情况下形成有趣的重排产物。通过X-射线衍射分析和其他光谱方法确定了这些产物的结构，并对其形成机理进行了讨论.一个介离子4-恶唑酮得到一个有趣的含氧二聚体与微量的氧气接触。通过X射线衍射分析确定了其结构.光谱分析表明，这些类甘菊环杂环化合物的电子分布与甘菊环的电子分布相似，且具有较强的极化性.在MNDO计算结果的基础上对这些反应进行了分析，认为这些反应可以按[4pi+6pi]和[4pi+2 pi]两种方式协调进行。这一结论支持了富烯环2-位上的大取代基强烈控制这些反应的周选择性的观点。