2007 Fiscal Year Final Research Report Summary
Synthesis and Inclusion Behavior of Heavy Unsaturated Crown Ethers
| Project/Area Number |
18550042
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Tokyo Metropolitan University |
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Principal Investigator |
SHIMIZU Toshio Tokyo Metropolitan University, Graduate School of Urban Environmental Sciences, Professor (50192612)
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| Project Period (FY) |
2006 – 2007
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| Keywords | Thiacrown Ether / Heavy Element Compound / Unsaturated Cyclic Compound / Host-Guest Chemistry / Inclusion / Metal Complex / Titration / Redox |
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| Research Abstract |
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.
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