Synthesis and Inclusion Behavior of Heavy Unsaturated Crown Ethers

我们已经合成了含顺碳-碳双键的不饱和硫杂冠醚和含硒冠醚。本研究合成了同时具有碳-碳单键和顺-碳-碳双键的部分不饱和硫杂冠醚，并考察了它们的反应活性和络合行为。具有全部顺-碳-碳双键的不饱和硫杂冠醚可被m-CPBA或t-BuOCl在低温下氧化得到相应的亚硫醚，而光化学反应或在室温下与t-BuOCl或NBS反应得到相应的顺反异构化化合物。不饱和硫杂冠醚的氧化还原行为与不饱和硫杂冠醚的氧化还原行为不同。分离得到了一些不饱和的硒冠醚与三氟乙酸银的络合物，并对溶液中银离子的包合行为进行了研究。还可以通过分步反应合成12、18和24元部分不饱和的硫杂冠醚。部分不饱和硫杂冠醚的热反应生成了相应的顺反异构化产物。考察了部分不饱和硫杂冠醚的氧化还原性质和络合行为，阐明了它们与相应的不饱和体系和饱和体系的区别。

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.