1996 Fiscal Year Final Research Report Summary
Synthesis and Properties of Novel pi-Electronic Hydrocarbons Having sigma-pi Interaction
| Project/Area Number |
07454165
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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 | KYOTO UNIVERSITY |
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Principal Investigator |
KOMATSU Koichi Kyoto University, Institute for Chemical Research, Professor, 化学研究所, 教授 (70026243)
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| Project Period (FY) |
1995 – 1996
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| Keywords | sigma-pi conjugation / C-C hyperconjugation / bicyclo [2.2.2] octene / silole / germole / cation radical / benzyne / anthracene |
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| Research Abstract |
1.Synthesis of the Cyclopentadienylpi-System Annelated with Bicyclooctene Frameworks.
Bicyclo [2.2.2] octene (abbreviated as BCO) was used as the structural unit for the synthesis of pi-systems having novel properties. Thus, a series of substituted cyclopentadienyl derivatives annelated with two BCO units have been synthesized and their redox behaviors investigated in detail.
2.Synthesis of Sila-and Germacyclopentadienes Annelated with BCO Units.
The above silole and germole derivatives have been newly synthesized and their spectral properties fully characterized. The presence of sigma-pi interaction has been investigated based on the results of UV data and MO calculations.
3.Generation of the Benzyne Annelated with Two BCO Units.
The generation of the above mentioned benzyne has been confirmed by trapping experiment. This benzyne has also been converted to the biphenylene derivative and its unique redox behaviors were clarified.
4.Synthesis and Properties of the Anthracene Annelated with Four BCO Units.
The above mentioned anthracene derivative has been newly synthesized by the use of double Diels- Alder reaction of the BCO dimer with p-benzoquinone as a dienophile. The notable increase in HOMO level owing to the sigma-pi interaction has been demonstrated by the use of electrochemical and organochemical redox reactions. The stable cation radical and dication have successfully been generated from this anthracene derivative.
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