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Synthesis and Inclusion Behavior of Heavy Unsaturated Crown Ethers

重质不饱和冠醚的合成及包合行为

基本信息

批准号：
18550042
负责人：
SHIMIZU Toshio
金额：
$ 2.64万
依托单位：
Tokyo Metropolitan University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550042/
关键词：
Thiacrown Ether Heavy Element Compound Unsaturated Cyclic Compound Host-Guest Chemistry Inclusion Metal Complex Titration Redox 飽和不飽和混合系セレナクラウンエーテル

项目摘要

The unsaturated thia-and selenacrown ethers with cis-carbon-carbon double bonds have already been synthesized by us. In this study, partially unsaturated thiacrown ethers possessing both carbon-carbon single bonds and cis-carbon-carbon double bonds were synthesized, and also reactivities and complexation behavior of those compounds were examined. The unsaturated thiacrown ethers with all cis-carbon-carbon double bonds could be oxidized by m-CPBA or t-BuOCl at low temperature to give the corresponding sulfoxides, and the photochemical reaction or the reaction with t-BuOCl or NBS at room temperature afforded the corresponding cis-trans isomerized compounds. The unsaturated selenacrown ethers showed different redox behavior with those of the conesponding unsaturated thiacrown ethers. Some complexes of the unsaturated selenacrown ethers with silver trifluoroacetate could be isolated, and the inclusion behavior with silver ion in solutions was also clarified. The 12, 18, and 24-membered partially unsaturated thiacrown ethers could also be synthesized by the step wise reactions. The thermal reaction of the partially unsaturated thiacrown ethers was found to afford the corresponding cis-trans isomerized products. The redox properties and the complexation behavior of the partially unsaturated thiacrown ethers were also examined, and the difference with those of the corresponding unsaturated and saturated systems could be clarified.

我们已经合成了具有顺式碳碳双键的不饱和硫杂冠醚和硒冠醚。本研究合成了同时具有碳-碳单键和顺式-碳-碳双键的部分不饱和硫杂冠醚，并检测了这些化合物的反应活性和络合行为。全顺式碳碳双键的不饱和硫杂冠醚可以在低温下被m-CPBA或t-BuOCl氧化生成相应的亚砜，在室温下进行光化学反应或与t-BuOCl或NBS反应得到相应的顺反异构化化合物。不饱和硒冠醚表现出与相应的不饱和硫杂冠醚不同的氧化还原行为。分离出一些不饱和硒冠醚与三氟乙酸银的配合物，并阐明了其与溶液中银离子的包合行为。 12、18和24元部分不饱和硫杂冠醚也可以通过逐步反应合成。发现部分不饱和硫杂冠醚的热反应产生相应的顺反异构化产物。还考察了部分不饱和硫杂冠醚的氧化还原性质和络合行为，并阐明了其与相应的不饱和和饱和体系的差异。