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.

我们已经合成了带有顺式碳碳双键的不饱和thia和selenacrown ethers。在这项研究中，合成了具有碳碳单键和顺式碳碳双键的部分不饱和硫克氏醚，还检查了这些化合物的反应性和络合行为。具有所有顺式碳碳双键的不饱和thiacrown Ether可以在低温下用M-CPBA或T-Buocl氧化以给出相应的亚氧化甲氧化物，以及光化学反应或在室温下与T-Buocl或NBS的反应，可为相应的CIS-Trans-Trans-Trans-Trans-Trans-Trans-Trans-Trans-Trans-Trans-Trans-Transizatizatizon somagermerizatizonmermerizatizon-Amymermerizatizon-GymOunds提供。不饱和的Selenacrown Ethers与对应的不饱和硫龙醚的氧化还原行为不同。可以分离出具有银三氟乙酸银的不饱和苏伦克龙醚的一些复合物，并且还阐明了溶液中银离子的包含行为。 12、18和24元的部分不饱和的硫克醚也可以通过阶跃反应来综合。发现部分不饱和硫克氏醚的热反应提供了相应的顺式跨性异构产物。还检查了部分不饱和硫克洛恩醚的氧化还原性能和络合行为，并且可以阐明相应的不饱和和饱和系统的差异。