| Project/Area Number |
10044091
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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 | OSAKA PREFECTURE UNIVERSITY |
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Principal Investigator |
MIZUNO Kazuhiko OSAKA PREFECTURE UNIVERSITY, COLLEGE OF ENGINEERING, PROFESSOR, 工学部, 教授 (10109879)
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| Co-Investigator(Kenkyū-buntansha) |
MAEDA Hajime OSAKA PREFECTURE UNIVERSITY, COLLEGE OF ENGINEERING, RESEARCH ASSOCIATE, 工学部, 助手 (40295720)
SUGIMOTO Akira OSAKA PREFECTURE UNIVERSITY, COLLEGE OF ENGINEERING, ASSOCIATE PROFESSOR, 工学部, 助教授 (00081323)
CALDWELL Richard a. THE UNIVERSITY OF TEXAS AT DALLAS, DEPARTMENT OF CHEMISTRY, PROFESSOR
コールドウェル リチャー 米国テキサス大学, ダラス校, 教授
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1999: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1998: ¥1,600,000 (Direct Cost: ¥1,600,000)
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| Keywords | 1,n-Biradical / Exciplex / Cyclopropane / Photoisomerization / Photocycloaddition / Aromatic Hydrocarbon / Substituent Effect / Laser Flash Photolysis / ビニリデンシクロプロパン / 光転位反応 / 光定常状態 / 光異性化 |
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| Research Abstract |
Photochemical properties and direct observations of reactive species in cis-trans photoisomerizations, photorearrangements, and photocycloadditions via 1,n-biradicals and exciplexes were examined and the following results were obtained.
1) Photoirradiation of 1,2-diphenylcyclopropane derivatives bearing one or two p-acetylphenyl group(s) caused cis-trans isomerization to give 45 : 55 photostationary state, accompanying with the formation of ring-opening products, 1,3-diphenylpropene derivatives. Nano-second order laser flash photolysis indicated that the photoisomerization proceeds via triplet 1,3-biradicals whose lifetimes are ca. 15 ns, and that the substituent effect at para position are negligible except for heavy atom effect by bromide group.
2) Photoirradiation of cis- and trans-1-diphenylvinylidene-2,3-dimethylcyclopropane in direct or in the presense of triplet sensitizer caused cis-trans isomerization. Cis/trans ratios in photostationary states were 50 : 50 in direct irradiation, 30 : 70 in the presense of triplet sensitizer, respectively.
3) Aromatic hydrocarbons such as pyrene and phenanthrene reacts with electron-deficient alkenes such as methyl cinnamate and cinnamonitrile under photoirradiation conditions, to give (2π+ 2π) photocycloadducts at 4,5-position of pyrene and 9,10-position of phenanthrene in high yields. Prolonged irradiation of a solution containing pyrene and electron-deficient alkene give 1 : 2 adduct efficiently. Intramolecular photocycloaddition of aromatic hydrocarbons connecting alkene moiety at appropriate position gave (2π+ 2π) photocycloadducts more selectively.
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