• Title/Summary/Keyword: Photoaddition

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Photoaddition Reactions of N-Methylthiophthalimide with $\alpha$-Silyl-n-electron Donors via Single Electron Transfer-Desilylation and Hydrogen Atom Abstraction Pathways

  • Yoon, Ung-Chan;Oh, Sun-Wha;Moon, Seong-Chul;Hyung, Tae-Gyung
    • Journal of Photoscience
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    • v.9 no.1
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    • pp.17-22
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    • 2002
  • Studies have been conducted to explore photoaddition reactions of N-methylthiophthalimide with $\alpha$-silyl-n-electron donors Et$_2$NCH$_2$SiMe$_3$, n-PrSCH$_2$SiMe$_3$ and EtOCH$_2$SiMe$_3$. Photoaddition of $\alpha$-silyl amine Et$_2$NCH$_2$SiMe$_3$ to N-methylthiophthalimide occurs in $CH_3$CN and benzene to produce non-silicon containing adduct in which thiophthalimide thione carbon is bonded to $\alpha$-carbon of $\alpha$-silyl amine in place of the trimethylsilyl group. In contrast, photoaddition of EtOCH$_2$SiMe$_3$ to N-methylthiophthalimide generates two diastereomeric adducts in which thiophthalimide thione carbon is connected to $\alpha$-carbon of $\alpha$-silyl ether in place of u-hydrogen. Based on a consideration of the oxidation potentials of u-silyl-n-electron donors and the nature of photoadducts, mechanism for these photoadditions involving single electron transfer(SET) -desilylation and H atom abstraction pathways are proposed.

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Photoaddition Reactions of trans-1,2-Bispyrazylethylene to Tetramethylethylene (테트라메틸에틸렌에 대한 트란스-1,2-비스피라질에틸렌의 광첨가반응)

  • Sang Chul Shim;Jin Ho Cho
    • Journal of the Korean Chemical Society
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    • v.23 no.5
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    • pp.325-328
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    • 1979
  • trans-1,2-Bispyrazylethylene (BPE) undergoes photoaddition reaction to tetramthylethylene (TME) which appears to involve radical intermediates under conditions where the corresponding hydrocarbons are unreactive. This photoaddition reaction involves abstraction of an allylic hydrogen atom of TME by $^1(n,\;{\pi}^*)$ states of BPE having radical character. The major photoadduct is isolated by column chromatography and fractional vacuum sublimation and characterized to be 2,3-dimetyl-5,6-bispyrazyl-2-hexene.

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Comparison of Photoaddition Reactions of Aromatic Carbonyl Compounds with Silyl Thioketene Acetal vs. Silyl Ketene Acetal

  • Lee, In Ok;Yoon, Ung Chan;Cho, Dae Won
    • Rapid Communication in Photoscience
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    • v.2 no.3
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    • pp.76-78
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    • 2013
  • Photoaddition reactions of aromatic carbonyl compounds with silyl thioketene acetals have been explored. The results of this study show that the acetonphenone react with dimethyl substituted silyl thioketene acetal competitively via either single electron transfer (SET)-desilylation or [2+2]-cycloaddition pathways to produce b-hydroxyester and oxetanes. In contrast, photochemical reactions of the benzaldehyde with dimethyl substituted silyl thioketene acetal mainly lead to the formation of oxetanes arising by [2+2] cycloaddition. A comparison of the results with those of silyl ketene acetal revealed that replacement of sulfur atom in ${\alpha}$-silyl donor substrate bring about dramatic changes in chemoselectivities as well as excited state reaction mechanism.

PHOTOADDITION REACTIONS OF 1,4-DIPHENYLBUT-1-EN-3-YNE TO p-QUINONES

  • Kim, Sung-Sik;So, Mi-Hyun
    • Journal of Photoscience
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    • v.3 no.2
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    • pp.61-64
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    • 1996
  • Photoaddition reactions of p-quinones to 1, 4-diphenylbubl-en-3-yne (BEY) have been investigated. Irradiation (300 nm) of BEY and 1, 4-benzoquinones in dichloromethane afforded quinone methides. I rradiation of 1, 4-naphthoquinone and BEY leaded to the formation of unstable spiro oxetene intermediate, followed by the rearrangement to give quinone methide, and finally the oxidative photocyclization. In contrast, irradiation 2, 3-dichloro-1, 4-naphthoquinone (or anthraquinone) and BEY yielded another type of quinone methides in one pot.

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Photochemistry of Conjugated Polyacethylenes: Photoaddition Reactions of 1-Phenyl-1,3,5-hexatriynes to Tetrahydrofuran

  • Shim, Sang Chul;Lee, Cheon Seok;Lee, Seong Taek
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.654-658
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    • 1992
  • Photolysis of 1-phenyl-1,3,5-hexatriynes in deaerated tetrahydrofuran gave photoreduction and photoaddition products, while photolysis of 1-phenyl-1,3,5-hexatriynes in deaerated alcoholic solvents (methanol, i-propanol) yielded dark red products, probably oligomers or decomposition products of reactants, as exclusive major products. A plausible mechanism for the reaction is proposed.