• Title/Summary/Keyword: Photoproduct

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Photoreactions of 2-(Pentamethyldisilanyloxy)phenylpentamethyldisilane

  • Park, Seung-Ki
    • Bulletin of the Korean Chemical Society
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    • v.29 no.5
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    • pp.1018-1024
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    • 2008
  • Photolysis of 2-(pentamethyldisilanyloxy)phenylpentamethyldisilane 1 in methanol provides five photoproducts 3, 4, 5, 6, and 7. Compounds 3 and 4 were probably formed from the methanol addition reactions of silene intermediate 2 and the formation of 5, 6, and 7 can best be explained by the nucleophilic attack of methanol to silicon atom in pentamethyldisilanyloxy or pentamethyldisilanyl group of the photoexcited state of 1. Irradiation of 1 in n-hexane gives a photoproduct 6 via silyl radical intermediate 8 and a novel intramolecular cyclization photoproduct 11 via silene 9 and silyl radical intermediate 10. Irradiation of 1 in deaerated methylene chloride in the presence of acetone affords a novel photoproduct 11 and phenol 7 but the expected photoproducts from the reaction of the silene intermediate with acetone were not obtained.

Photocycloaddition of 5,7-Dimethoxycoumarin to 5-Fluorouracil

  • Shim, Sang-Chul;Ra, Choon-Sup;Chae, Kyu-Ho
    • Bulletin of the Korean Chemical Society
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    • v.1 no.4
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    • pp.121-123
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    • 1980
  • $C_4$-Photocycloaddition of 5,7-dimethoxycoumarin(DMC) to 5-fluorouracil(5-FU) was studied in frozen aqueous solution. The major photoproduct was diagnosed and isolated by TLC and column chromatography. The structure of isolated photoproduct was identified as a $C_4$-cycloaddition product of DMC and 5-FU by the characteristics of its UV, IR, NMR, mass spectra, elemental analysis, and photosplitting.

Photochemical Formation of 3-Methoxycyclohex-2-en-1-ones from 1,3-Cyclohexanedione and 2-Allyl-3-hydroxycyclohex-2-en-1-one in Methanol in the Presence of Quinones

  • Kim, Sung-Sik;Chang, Ji-Ae;Kim, Ae-Rhan;Mah, Yoon-Jung;Kim, Hyun-Jin;Kang, Chan
    • Journal of Photoscience
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    • v.7 no.3
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    • pp.111-114
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    • 2000
  • Irradiation of 1,3-cyclohexanedione and p-benzoquinone in methanol gave 3-methoxycyclohex-2-en-1-one. Allyl derivative of the 1,3-diketone was prepared as enol from and irradiated in methanol in the presence of p-benzoquinone to give the same type of photoproduct, i.e., 2-allyl-3-methoxycyclohex-2-en-1-one. Allyldibenzoylmethane was synthesized and irradiated with p-benzoauinone in methanol but no remarkable amount of photoproduct was obtained.

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A Novel Photoreaction of (2-Hydroxyethoxyphenyl)pentamethyldisilane

  • Park, Seung Ki;Seong, Won-Je
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1331-1336
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    • 2009
  • Photolysis of (2-hydroxyethoxyphenyl)pentamethyldisilane 2 in benzene provides a novel intramolecular cyclization photoproduct 9 which was probably formed from the intramolecular reaction to form a seven-membered ring in silatriene intermediate 7 and then the photochemical disrotatory ring closure of 1,3-butadiene moiety to cyclobutene. Irradiation of 2 in methanol afforded photoproducts 5 and 6 which were formed by the nucleophilic attack of methanol to $\beta$ or $\alpha$ silicon atom in pentamethyldisilanyl group of the photoexcited state of 2. Compounds 10 and 11 were also formed by the same way as in the formation of the photoproducts 5 and 6 in the photolysis of (2-allyloxyethoxyphenyl)pentamethyldisilane 3 in methanol solvent. Photoreaction of (2-acetoxyethoxyphenyl) pentamethyldisilane 4 in methanol gave a photoproduct 12 which was formed via the elimination of dimethylsilylene species in the photoexcited state of 4.

Solvent Effects on Action Spectra for The Photodecomposition of N-Acetylphenylalanyl-L-Tryptophan and 3-Methyl Indole

  • Yoon, Min-Joong;Chung, Bong-Sik
    • Bulletin of the Korean Chemical Society
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    • v.5 no.5
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    • pp.194-198
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    • 1984
  • The UV action spectra and quantum yields for photodestruction of tryptophan (Trp) in peptide such as N-acetylphenylalanyl-L-tryptophan (NAPT) and 3-methyl indole (scatole) were determined in aerated aqueous and organic solvents. The photodestruction of aqueous NAPT was shown to be initiated by photoionization without requirement of threshold energy, as demonstrated by the similarity of fluence effect curves obtained for the action at various wavelengths and the wavelength dependence of quantum yield comparable to that reported for the photoionization of L-Trp. N-formylkynurenine (NFK)-type photoproduct, which is a photodynamic sensitizer, was not found to be involved in the photodestruction of Trp in NAPT in aqueous solution. In contrast, the action spectra of NAPT and scatole in organic solvents have revealed evidences for the significant role of internal photosensitization by NFK-type photoproduct in photolysis of Trp in peptide.

Photoreactions of (2-Alkoxymethylphenyl)pentamethyldisilanes

  • Park, Seung-Ki
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1305-1309
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    • 2006
  • Photolysis of (2-hydroxymethylphenyl)pentamethyldisilane 1 in methanol provides a novel intramolecular photoproduct 4 via silene intermediate 2 but the photoreaction of (2-acetoxymethyl- or allyloxymethylphenyl) pentamethyldisilanes 5 or 10 in methanol affords unexpected photoproducts 8 or 13, respectively, instead of expected intramolecular photoproducts.

Cycloaddition Reaction on 1,4,5,8-Tetraazaphenanthrene Photoexcited Triplet State to Some Olefins

  • Park, Seung-Ki;Shim, Sang-Chul
    • Bulletin of the Korean Chemical Society
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    • v.8 no.1
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    • pp.27-30
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    • 1987
  • Photocycloaddition of 1,4,5,8-tetraazaphenanthrene to olefins proceeds through a biradical triplet-state intermediate as proven by the photoproduct stereochemistry, quantum yield measurements, sensitization, quenching, and fluorescence and phosphorescence quenching studies.