1993 Fiscal Year Final Research Report Summary
Development of Chiral Cyclophanes for Molecular Recognition and Their Application
| Project/Area Number |
04650764
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Chiba University |
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Principal Investigator |
OGURA Katsuyuki Chiba University, Applied Chemistry, Professor, 工学部, 教授 (60114253)
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| Co-Investigator(Kenkyū-buntansha) |
FUJITA Makoto Chiba University, Applied Chemistry, Lecturer, 工学部, 講師 (90209065)
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| Project Period (FY) |
1992 – 1993
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| Keywords | Cyclophane / Chiral / Molecular recognition / Optical rotation / Intermolecular interaction / Azo group / Photo-isomerization |
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| Research Abstract |
The purpose of this project is to prepare optically active cyclophanes, which are composed of two chiral 1,1'-binaphthol moieties and two aromatic bridges, in order to investigate intramolecular interaction and reversible record of light information by the change of optical rotation.
1. Many kinds of optically active cyclophanes (1) were synthesized : In the reaction of chiral 1,1'-binaphthol (2) (2 mol equiv) with dihalide (3) in the presence of potassium carbonate in acetone, and semi-bridged intermediate (4) was obtained in an excellent yield. When 2 and 4 (1 : 1 mol ratio) were slowly added to a suspesion of either potassium carbonate in acetone or sodium hydride in DMF, the expected cyclophane (1) was given in a good yield (40-70%). Use of p, p'-bis(bromomethyl)benzophenone as 2 afforded a carbonyl-contained 1, from which we synthesized a chiral double-cyclophane (4) having two units of 1.
2. Intermolecular interaction of 1 with various molecules (guests) can be investigated by the change of optical rotation : Interaction with the guest changes the conformation of 1 to cause the change of optical rotation. We showed that the equilibrium constant for complexation of 1 and the guest can be evaluated by the change of optical rotation.
3. The chiral cyclophane having azo group is utilized for reversible record of light information : Ultraviolet irradiation isomerizes trans azo group to cis one. This phenomenon can be detected by the change of optical rotation. Heating converted the cis geometry to trans one to return the optical rotation back to the starting point.
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