| Project/Area Number |
11640526
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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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 | The University of Tokyo |
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Principal Investigator |
KOBAYASHI Keiji The University of Tokyo, Graduate School of Arts and Sciences, Professor, 大学院・総合文化研究科, 教授 (50012456)
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| Co-Investigator(Kenkyū-buntansha) |
今久保 達郎 東京大学, 大学院・総合文化研究科, 助手 (60291332)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2001: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2000: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1999: ¥1,100,000 (Direct Cost: ¥1,100,000)
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| Keywords | Solid-State Reactions / Charge-Transfer / Clathrate Crystals / Tribochromism / Piezochromism / Ion Radical / 固相ラセミ化 / 固相求核置換反応 / カルボカチオン塩 / 固相酸触媒 / 転位反応 / 混晶 / 立体選択性 / カルボカチオン / 分子内転位 |
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| Research Abstract |
We have investigated the solid-state nucleophilic substitution reactions induced in the co-ground powder of thiophene-substituted tert-alcohols and DDQ or TCNQ followed by exposure to methanol vapor. It was revealed that the reaction is propagated by contact with methanol vapor and is proceeded via carbocation as an intermediate. A diol derivative afforded crystalline charge-transfer complexes with TCNQ and tetra-fluoro TCNQ, respectively. These crystals were isostructural, while their reactivities were different. The tetrafluoro TCNQ complexes undergo substitution reactions on grinding followed by exposure to methanol vapor, whereas the TCNQ complexes do not.
When a tri(benzothienyl) derivative was co-ground with DDQ, a novel type of thioindigoid compound was obtained. This compound showed tribochromic and piezochromic properties. The reversible change in color between red and black was attributed to occurrence of partial charge-transfer interactions in the solid state induced by grinding.
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