| Project/Area Number |
09640629
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Organic chemistry
|
|---|
| Research Institution | Niigata University |
|---|
Principal Investigator |
KAMATA Masaki Niigata University, Faculty of Education & Human Science, Department of Chemistry, Associate professor, 教育人間科学部, 助教授 (40185971)
|
|---|
| Project Period (FY) |
1997 – 1999
|
| Project Status |
Completed (Fiscal Year 1999)
|
| Budget Amount *help |
¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1999: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥1,900,000 (Direct Cost: ¥1,900,000)
|
|---|
| Keywords | cyclic peroxides / 1,2-dioxolane / 1,2-dioxane / aryl shift / photo-fragmentation / photo-rearrangement / mechanism / photoreaction / 転位反応 / 高原子価鉄オキソ中間体 / 抗マラリア化合物 / アリール移動 / 光電子移動反応 / 熱分解反応 |
|---|
| Research Abstract |
1) Variety of arylated 1,2-dioxolanes and 1,2-dioxanes were prepared by using original modified methods of electron transfer photo-oxygenation. As a result, new synthetic methods were established for the unknown derivatives of above cyclic peroxides while improvements of the yields for the known derivatives were performed.
2) It was found that O-O bond cleaved diradical intermediates of above cyclic peroxides in the direct photo-irradiation occurred rearrangements and fragmentations. It was also found that aryl shift generally proceeded for the substrates possessing electron donating aromatic substituents such as p-methoxyphenyl group.
3) It was found that the dioxyl-diradical intermediate mechanism and the concerted-like bond cleavage mechanism were simultaneously operated in the thermal reaction of the cyclic peroxides.
4) It was found that C-O bond cleaved cation radical intermediates occurred rearrangements and fragrnentations in the pyrylium salt sensitized photo-electron transfer reactions.
5) Non-photochemical single electron transfer reduction of the cyclic peroxides induced by Fe(II)and Fe(III) bromides were performed. As a result, it was found that O-O bond cleaved mono-oxyl-radical intermediates underwent rearrangements and fragmentations.
|
