• Title/Summary/Keyword: cycloaddition

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Synthesis of Spiroannulated Dihydrofuran Compounds Utilizing Cerium(IV) Ammonium Nitrate (Cerium(IV) Ammonium Nitrate를 이용한 Spiroannulated 다이하이드로퓨란 화합물의 합성)

  • Kim, Byung-SO
    • Journal of the Korean Society of Industry Convergence
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    • v.5 no.4
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    • pp.385-390
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    • 2002
  • An efficient synthesis of spiroannulated dihydrofurans is achieved from 1,3-dicarbonyl compounds and exocyclic alkenes in the presence of cerium ammonium nitrate(IV) in moderate yields. In the case of entries 3-9, as a single product was seen. Especially, reaction of 15 with methylenecyclohexane afforded the two regioisomeric cyclo adducts 21 and 22. The structures of these adducts were confirmed by IR and NMR-Spectra.

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MO Theoretical Studies on Stereoelectronic Control in the Addition Reaction of 1, 4-Benzoquinone-4-(O-methyloxime)$^*$

  • Ik-Choon Lee;Eun-Sook Han
    • Bulletin of the Korean Chemical Society
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    • v.4 no.1
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    • pp.41-44
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    • 1983
  • The chlorine addition and Diels-Alder cycloaddition of cyclopentadiene to 1, 4-benzoquinone-4-(O-methyloxime) have been studied MO theoretically. It has been shown that the reactions occur predominantly to the quinone ring double bond which is oriented anti to the nitrogen lone pair due to an n-${\sigma}^*$ interaction between the nitrogen lone pair, n, and the app. vicinal bond, causing the ${\pi}$ bond to be weakened and destabilized due to the less conjugation from reduced delocalization.

Photoreaction of 8-Methoxypsoralen with Thymine

  • Shim, Sang-Chul;Kim, Yong-Zu
    • Bulletin of the Korean Chemical Society
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    • v.4 no.2
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    • pp.95-99
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    • 1983
  • Photoreaction of 8-methoxypsoralen (8-MOP) with thymine (${\ge}$ 300 nm) was carried out in the dioxane-water frozen state. One major and two minor monoaddition products between 8-MOP and thymine were isolated by various chromatographic methods. Major monoadduct was characterized to be a C4 cycloaddition product formed between 5,6-double bond of thymine and 3,4-double bond of 8-MOP with cis-anti stereochemistry. Two minor adducts were proved to be stereoisomers of this major adduct.

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.

Photocycloaddition Reaction of trans-Cinnamonitrile Derivatives with Tetramethylethylene

  • Chae, Myeong-Yun;Yoon, Suk-Kyoon;Shim, Sang-Chul
    • Bulletin of the Korean Chemical Society
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    • v.6 no.2
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    • pp.95-98
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    • 1985
  • Stereospecific [2 + 2] cycloadducts are obtained as major products when trans-cinnamonitrile derivatives are irradiated with excess tetramethylethylene. The fluorescence quenching studies, weak exciplex fluorescence, and sensitization by benzophenone suggest that this stereospecific photochemical cycloaddition reaction involves singlet exciplex intermediate formed between cinnamonitrile derivatives and tetramethylethylene.

Photocycloaddition Reaction of 1,2-Bispyrazylethylene to Tetracyanoethylene

  • Shim, Sang-Chul;Shim, Hyun-Kwan
    • Bulletin of the Korean Chemical Society
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    • v.1 no.4
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    • pp.123-126
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    • 1980
  • Benzene solution of trans-1,2-bispyrazylethylene and electron deficient olefin, tetracyanoethylene, as a ${\pi}$-acceptor gave 1,2-bispyrazyl-3,3,4,4-tetracyanocyclobutane, a 2${\pi}$ + 2${\pi}$ cycloaddition product, on irradiation with 350 nm UV light. Fluorescence studies revealed the reaction to proceed through a singlet exciplex. The fluorescence of trans-1,2-bispyrazylethylene was quenched very efficiently by tetracyanoethylene with the quenching constant of 1.6 ${\times}$ 10$^{10}$M$^{-1}$s$^{-1}$ while electron rich olefin, tetramethylethylene, did not quench the fluorescence of bispyrazylethylene.

Effect of Photopolymerization on the Rate of Photocrosslink in Chalcone-based Oligomeric Compounds

  • Choe, Dong Hun;O, Sang Jun;Ban, Si Yeong;O, Gwang Yong
    • Bulletin of the Korean Chemical Society
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    • v.22 no.11
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    • pp.1207-1212
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    • 2001
  • A new photochemically bifunctional epoxy and dimethacrylate compounds were synthesized for investigating the photosensitivity under UV irradiation. Photosensitivity of the synthesized chalcone-based compounds was investigated by using UV-visible absorption and Fourier transformed infrared (FT-IR) spectroscopies. The result of spectroscopic analysis substantiated that the two chalcone-based compounds have functions of both photocrosslinking and photopolymerization by UV exposure in the presence of photoinitiator. Two kinds of photochemical reactions proceeded competitively during UV exposure. Particularly, we studied the effect of photopolymerization on the rate of photocrosslink due to cycloaddition in the two oligomeric compounds.

Synthetis of 4H,6H-Furo[3,4-c]isoxazole Derivatives as New Potent Fungicides and Their Structure Activity Relationship

  • 김형진;황광진;이재현
    • Bulletin of the Korean Chemical Society
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    • v.18 no.5
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    • pp.534-540
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    • 1997
  • 4H,6H-Furo[3,4-c]isoxazoles (Ⅰ-Ⅳ), potential fungicides, have been designed and synthesized via intramolecular [2+3] cycloaddition of nitroalkyne 3 as a key step. The broad spectrum of fungicidal activities of furoisoxazoles (Ⅰ-Ⅳ) were observed on plant pathogens at 250 ppm. Furoisoxazoles Ⅱ, Ⅲ with chlorophenyl at 6-position and methyl or alkylated oxime group at 3-position gave effective control of plant diseases. The furoisoxazole Ⅳ with a chlorophenyl group at 4-position also resulted in high fungicidal activities.