| Project/Area Number |
61550636
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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 | Kyoto University |
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Principal Investigator |
KOMATAU Koichi Kyoto University, Lecture Faculty of Engineering, 工学部, 講師 (70026243)
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| Co-Investigator(Kenkyū-buntansha) |
KINOSHITA Tomomi Kyoto University, Instructor Faculty of Engineering, 工学部, 助手 (10026289)
TAKEUCHI Ken'ichi Kyoto University, Associate Professor Faculty of Engineering, 工学部, 助教授 (50026358)
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| Project Period (FY) |
1986 – 1987
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| Project Status |
Completed (Fiscal Year 1987)
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| Budget Amount *help |
¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1987: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1986: ¥1,600,000 (Direct Cost: ¥1,600,000)
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| Keywords | Carbanion / Carbocation / Cross-conjugation / Thermodynamic stability / Cyclic voltammetry / One-electron transfer / Intramolecular CT interaction / 炭化水素塩 / カチオン・アニオン反応 / pKa / NMR |
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| Research Abstract |
Under the present research project, novel aromatic carbanions were newly synthesized in order to clarify the correlation between the structure and electronicstability. Some of these anions were successfully transformed into other novel<pi>-electronic systems (ionic or neutral) of theoretical interest. The results are summarized a follows.
1. The di- and triphenyl dervatives (I) of the cyclopent[a]acenaphthylenide ion were newly synthesized via 4-step reactions from acecyclone. The spectral aswell as electrochemical study revealed that I can be applied as a new type of ligand in the organometallic chemistry. A further study is now under way.
2. A new stable carbocation (II) having strong intramolecular charge-transfer interaction was synthesized from the reaction product of I and the tropylium ion. II was further converted into a new cross-conjugated <pi>-system with a sesquifulvalene framework, which exhibits the characteristic <pi>-donor ability.
3. A totoally new stable carbanion (III) composed of the cyclopentadienide ring trisubstituted with widely cross-conjugated <pi>-system (the dibenzofluorenylidenemethyl group) was synthesized, and was shown to be one of the most stable all-hydrocarbon carbanions presently know, with its hydrocarbon's pKa_a 3.3.
4. Reactions between the anions I,III and various stable carbocations synthesized in our group were examined to clarify the relationship between the reaction mode (ionic dissociation, one-electron transfer, or covalent-bond formation) and the electronic nature of both the cation and anion. Several new organic salts composed of only carbon and hydrogen, the "hydrocarbon salts", were prepared.
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