Synthesis and Inclusion Behavior of Heavy Unsaturated Crown Ethers

我们已经合成了具有顺式碳碳双键的不饱和硫杂和硒杂冠醚。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代冠醚，并研究了其反应活性和络合行为。含碳碳双键的不饱和硫代冠醚在低温下可被m-CPBA或t-BuOCl氧化生成相应的亚砜，在室温下与t-BuOCl或NBS发生光化学反应或与它们反应生成相应的顺反异构化产物。不饱和硒代冠醚表现出与相应的不饱和硫代冠醚不同的氧化还原行为。通过对不饱和硒代冠醚与三氟乙酸银配合物的分离，阐明了它们与银离子在溶液中的包结行为。12、18和24元部分不饱和硫代冠醚也可以通过分步反应合成。部分不饱和硫代冠醚的热反应得到了相应的顺反异构化产物。研究了部分不饱和硫代冠醚的氧化还原性质和络合行为，并与相应的不饱和和饱和体系进行了比较。

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.