| Project/Area Number |
06453062
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
物質変換
|
|---|
| Research Institution | The University of Tokyo |
|---|
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)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
横山 正 東京大学, 教養学部, 教授 (80012417)
後藤 敬 東京大学, 大学院理学系研究科, 助手 (70262144)
|
|---|
| Project Period (FY) |
1994 – 1995
|
| Project Status |
Completed (Fiscal Year 1995)
|
| Budget Amount *help |
¥8,300,000 (Direct Cost: ¥8,300,000)
Fiscal Year 1995: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1994: ¥6,800,000 (Direct Cost: ¥6,800,000)
|
|---|
| Keywords | Molecular cavity / Cyclophane / Calixarene / Sulfenic acid / Molecular mechanics calculation / X-ray crystallographic analysis / aromatic azide / nitrene / 分子認識 / 不安定化学種 |
|---|
| 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.
|
