| Budget Amount *help |
¥24,400,000 (Direct Cost: ¥24,400,000)
Fiscal Year 1985: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1984: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1983: ¥21,500,000 (Direct Cost: ¥21,500,000)
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| Research Abstract |
1) It has been found that photo-induced addition reactions between halogenonaphthoquinones and electron rich vinyl ethers proceeds via triplet exciplex. Solvent polarity is one of the most important controlling factors in this reaction, and thus in very polar acetonitrile exciplex tends to dissociate into solvated radical ions with decreasing net quantum yield of the reaction.
2) Irradiation of three components systems involving 4-methoxyphenol, tetraphneylporphyrin, and 1,4-benzoquinone in benzene led to the formation of diphenyl ether type dimer from the phenol. This reaction is initiated by porphyrin-photosensityzation, and besides the solvent polarity reduction potentials of quinones, their concentrations, the abilities to form a charge-transfer complex with the phenol were found important controlling factors.
3) Photoexcitation of bis-tyrosine-linked porphyrin with 2,6-dichloro-1,4benzoquinone gave a novel type of quinone-capped porphyrin in moderate yields. In these model compounds, the separations and relative orientations between two chromophores are important factors in derterming the rates of photo-induced intramolecular electron-transfer reactions.
4) In catalyzed isomerization from quadricyclane to norbornadien by cobaltporphyrin, attacking site is presumably the exo part of five-membered ring of quadricyclane.
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