1995 Fiscal Year Final Research Report Summary
Design of Bowl-shaped Molecules and Their Application to the Stabilization of Highly Reactive Species
| Project/Area Number |
06453062
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
物質変換
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| Research Institution | The University of Tokyo |
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Principal Investigator |
OKAZAKI Renji The University of Tokyo, Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (70011567)
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| Project Period (FY) |
1994 – 1995
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| Keywords | Molecular cavity / Cyclophane / Calixarene / Sulfenic acid / Molecular mechanics calculation / X-ray crystallographic analysis / aromatic azide / nitrene |
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| Research Abstract |
In this study bowl-shaped molecules with calix [6] arene and cyclophane skeletons were designed and synthesized. First, the synthesis of some new bicyclic cyclophanes having some functional groups were carried out using an orcinol benzyl ether unit as a central bridge and a diphenylmethane unit as a peripheral ring. The structures of these cyclophanes were studied by NMR and X-ray crystallography to show that the diameter of their cavity is about 14@90. The thermolysis of a compound having a sulfoxide functionality in the cavity gave the first stable arenesulfenic acid. Second, bowl-shaped molecules having a calix [6] arene skeleton were synthesized using calix [6] arenes and 2,6-bis (bromomethyl) benzene derivatives with azide and t-butylthio substituents in the cavity and their structures were studied by NMR and X-ray crystallography. Here again, a stable arenesulfenic acid was synthesized by thermolysis of a sulfoxide. Both bromo and sulfenic acid derivatives were shown to have 1,2,3-alternate conformations. The photolysis of an azide derivative afforded unusual products derived from insertion of the intermediary nitrene into calixarene ring.
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