1999 Fiscal Year Final Research Report Summary
Development of Novel Cyclic Structures Possessing Inclusion, Self-Assembly, and Self-Organization Properties
| Project/Area Number |
10440182
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | HOKKAIDO UNIVERSITY |
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Principal Investigator |
TSUJI Takashi Hokkaido Univ., Grad.School of Science, Professor, 大学院・理学研究科, 教授 (20029482)
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| Co-Investigator(Kenkyū-buntansha) |
OHKITA Masakazu Hokkaido Univ., Grad.School of Science, Instructor, 大学院・理学研究科, 助手 (60211786)
IMAI Toshiro Hokkaido Univ., Grad.School of Science, Lecturer, 大学院・理学研究科, 講師 (80184802)
SUZUKI Takanori Hokkaido Univ., Grad.School of Science, Associate Professor, 大学院・理学研究科, 助教授 (70202132)
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| Project Period (FY) |
1998 – 1999
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| Keywords | supramolecule / inclusion / self-organization / self-assembly / macrocycle |
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| Research Abstract |
[l] Syntheses and Properties of Novel Receptors Possessing Hydrindacene Skeleton Hydrindacene skeleton is consisted of rigid central aromatic ring and flexible peripheral 5-membered rings, and its intermolecular interactions are expected to be adequately regulated by functionalizing those rings with suitable substituents. In this study, the development of title receptors was investigated on the basis of those expectations.
The preparation of several substituted derivatives followed by their X-ray structural analyses revealed that the 5-membered rings prefer an envelope conformation and the less bulky substituents (Rs) are disposed nearly parallel to each other at a distance of ca. 7.0 Å, twice the interlayer distance in graphite. Those structural chacteristics were exploited to the design of novel multiply functionalized receptor molecules which preferentially associate with specific stubstrates. Thus, the (Z) Rs = arylethynyl/R_L = alkoxycarbonyl derivatives seem to incorporate aromatic substrates between the arylethynyl groups, facilitated by the π-π stacking interactions. The Rs = alkoxycarbonyl/R_L = aryl derivatives were also prepared and utilized to construct macrocyclic receptors in which the former substituents are oriented to the inside of the cycles.
[2] Preparation of Functionalized Phenylene-ethynylene Macrocycles 1,4-Bridged dichloro-Dewar benzenes are accessible in 4 steps from DMAD and dichloroethylene. Functionalized m- and p-phenylene groups are conveniently incorporated into macrocycles by taking advantage of their equivalency to bent benzene derivatives. Thus, their alternating (2 : 2) coupling- cyclization with diethynylbenzenes followed by hydrolysis and aromatization provided functionalized phenylene-ethynylene macrocycles which were otherwise diffiucult to access.
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