2001 Fiscal Year Final Research Report Summary
Design and Analysis of the Solid-State Organic Reactions
| Project/Area Number |
11640526
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Organic chemistry
|
|---|
| Research Institution | The University of Tokyo |
|---|
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)
|
|---|
| Project Period (FY) |
1999 – 2001
|
| Keywords | Solid-State Reactions / Charge-Transfer / Clathrate Crystals / Tribochromism / Piezochromism / Ion Radical |
|---|
| 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.
|
