• Title/Summary/Keyword: [5+2] Cycloaddition

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Kinetics and Mechanism of 1,3-Cycloaddition of 3.4.5.6-Tetrachlorobenzene-2-Diazo-1-Oxide (3.4.5.6-Tetrachlorobenzene-2-Diazo-1-Oxide의 1,3-환상부가에 대한 반응 속도론적 및 반응 메카니즘에 관한 연구)

  • Hong, Soon-Yung
    • Journal of the Korean Chemical Society
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    • v.14 no.3
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    • pp.271-275
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    • 1970
  • The effect of dimethyl maleate on the rate of thermolysis of 3,4,5,6-Tetrachlorobenzene-2-Diazo-1-Oxide in 1-chloronaphthalene at $130.2^{\circ}$ was investigated: In a separate experiment, the effect of dimethyl fumarate upon the same reaction at the same temperature was investigated. The rate of thermolysis was decreased by dimethyl maleate, while dimethyl fumarate accelerated the reaction. Some kinetic parameters of the thermolysis of 3,4,5,6-Tetrachlorobenzene-2-Diazo-1-Oxide were calculated. A mechanism of isomerization of dimethyl maleate to dimethyl fumarate by 3,4,5,6-Tetrachlorobenzene-2-Diazo-1-Oxide was proposed.

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Synthesis, X-Ray Crystal Structure and Coupling Reactions of 4,5-($1^{\prime},2^{\prime}$-diphenylethylenedithio)-1,3-dithiole-2-thione (dPhEDT-DTT)

  • 이하진;노동윤
    • Bulletin of the Korean Chemical Society
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    • v.19 no.3
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    • pp.340-344
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    • 1998
  • A facile synthesis of 4,5-(1',2'-diphenylethylenedithio)-1,3-dithiole-2-thione (dPhEDT-DTT) is carried out via a Diels-Alder type [2+4] cycloaddition reaction of 1,3-dithiol-2,4,5-trithione oligomer and t-stilbene. Molecular structure of dPhEDT-DTT is determined by x-ray crystallography: space group P1, a=11.694(3) Å, b=12.117(3) Å, c=14.688(3) Å, α=113.12(2)°, β=102.23(2)°, γ=107.02(2)°, V= 1699.1(7) Å3, Z=2. It turns out that dPhEDT-DTT crystallizes as a racemic compound consisting of (R,R) and (S,S) enantiomers. Coupling reaction of dPhEDT-DTO undergone in neat P(OEt)3 yields TTF(SEt)4 instead of ET derivative. When PR3 (R=OEt, OPh, Ph) is used in benzene, toluene or xylene, however, dPhEDT-DTO is decomposed.

Cycloaddition of Carbon Dioxide to Allyl Glycidyl Ether Using Silica-supported Ionic Liquid as a Catalyst (실리카에 고정화된 이온성액체를 촉매로 이용한 알릴글리시딜에테르와 이산화탄소의 부가반응)

  • Shim, Hye-Lim;Lee, Mi-Kyung;Yu, Jeong-In;Park, Dae-Won
    • Clean Technology
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    • v.14 no.3
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    • pp.166-170
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    • 2008
  • In this study, imidazolium salt ionic liquid on amorphous silica was prepared and its catalytic performance in the cycloaddition of $CO_2$ with allyl glycidyl ether (AGE) to produce heterocyclic carbonate was investigated. The ionic liquid was generated on chloropropyl functionalized silica through the immobilization of imidazole. The prepared catalyst was characterized using a number of instrumental analysis including XRD, BET, $^{29}Si$ MAS-NMR and SEM. $^{29}Si$ MAS-NMR showed that the ionic liquid formed adduct with the chloropropyl groups attached to the silica surface. The immobilized ionic liquid showed very good catalytic activity for the cycloaddition of $CO_2$ with AGE, showing 55-61% of AGE conversion with over 85% of the carbonate selectivity at $80-120^{\circ}C$. Its AGE conversion and selectivity to the carbonate were even higher than the homogeneous analog, 1-n-butyl-3-methyl imidazolium bromide (BMImBr).

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Synthesis of Pyrazolylquinoxalines and Pyrazolylpyrrolo[1,2-a]-quinoxalines (Pyrazolylquinoxaline류 및 Pyrazolylpyrrolo[1,2-a]-quinoxaline류의 합성)

  • Kim, Ho Sik;Lee, Seong Uk;Jeong, Won Young;Han, Sung Wook;Kim, Dong Il;Yoshihisa Kurasawa
    • Journal of the Korean Chemical Society
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    • v.45 no.4
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    • pp.318-324
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    • 2001
  • The reaction of 6-chloro-2-hydrazinoquinoxaline(4) or 6-chloro-2-hydrazinoquinoxaline 4-oxide(7) with alkyl (ethoxymethylene)cyanoacetates gave pyrazolylquinoxalines(5, 8). The reaction of compounds 8 with dimethyl acetylenedicarboxylate resulted in the 1,3-dipolar cycloaddition reaction and then ring transformation to afford pyrazolylpyrrolo[1,2-a]quinoxalines(9).

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Preparation, Characterization and Catalytic Performance of Ionic Liquid Immobilized onto Polystyrene-based Polymer for the Synthesis of Allyl Glycidyl Carbonate (폴리스티렌계 고분자에 고정화된 이온성 액체 촉매의 제조와 알릴글리시딜카보네이트 합성 반응 특성)

  • Lee, Mi-Kyung;Choi, Hye-Ji;Park, Dae-Won
    • Korean Chemical Engineering Research
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    • v.48 no.5
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    • pp.621-626
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    • 2010
  • In this study, imidazole-based ionic liquid on polystyrene was prepared and its catalytic performance in the cycloaddition of $CO_2$ with allyl glycidyl ether(AGE) to produce allyl glycidyl carbonate was investigated. The ionic liquid was generated on the polystyrene-based polymer through the immobilization of imidazole. The prepared catalyst was characterized using a number of instrumental analysis including EA, FT-IR, TGA and SEM. The immobilized ionic liquid showed very good catalytic activity for the cycloaddition of $CO_2$ with AGE, having 80% of AGE conversion with over 96% of the carbonate selectivity at $120^{\circ}C$ under 1.48 MPa $CO_2$ pressure. The immobilized ionic liquid can be used for the reaction up to four consecutive runs without significant loss of its catalytic activity.

Ring-Opening Polymerization of Substituted 3,4-Dihydro-2H-pyrans. Syntheses of Alternating Vinyl Copolymers of Dimethyl Dicyanofumarate and Electron-Rich Olefins

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • v.7 no.5
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    • pp.372-376
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    • 1986
  • Substituted 3,4-dihydro-2H-pyrans ($1_{a-e}$) were prepared by (4 + 2) cycloaddition reaction of dimethyl dicyanofumarate with the corresponding electron-rich olefins. The compounds $1_{a-e}$ were ring-open polymerized by cationic initiators to obtain polymers of 1:1 alternating sequence. Polymerizations were carried out with boron trifluoride etherate in methylene chloride at $-78^{\circ}C$. All the polymers obtained were soluble in common solvents and were reprecipitated by pouring its chloroform solution into diethyl ether. All the compounds $1_{a-e}$ were not as reactive as the corresponding pyrans derived from ${\alpha}$ -cyanoacrylate.

Theoretical Studies on the Photo-Skinsensitizing Psoralens (II)

  • Kim, Ja-Hong;Shim, Sang-Chul
    • Bulletin of the Korean Chemical Society
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    • v.2 no.3
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    • pp.112-114
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    • 1981
  • The photocycloaddition reaction of 8-methoxypsoralen with purine and/or pyrimidine bases is studied as a model for the charge transfer interactions of psoralens with DNA bases by the FMO method. The results indicate that, in the case of the molecular complex formation between psoralens and purine and/or pyrimidine bases, the most probable photocycloaddition should occur in the following order: Thy (5,6)<>(3,4) 8-MOP, Cyt(5,6)<>(3,4)8-MOP, Ade (7,8)<>(3,4)8-MOP, Gua(7,8)<>(3,4)8-MOP. The theoretical results for the photocycloaddition reaction are also correlated with the experimental results. The photoadducts between 8-methoxypsoralen and adenine are likely to be C4-cycloadducts through the cycloaddition of 3,4-pyrone double bond of 8-methoxypsoralen to 7,8-double bond of adenine.

A Synthetic Approach to 11-Oxabicyclo[6.2.1]undecyl Bicyclics

  • 정희선;김훈;강호정
    • Bulletin of the Korean Chemical Society
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    • v.18 no.7
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    • pp.754-760
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    • 1997
  • Through a sequence of reactions including Diels-Alder cycloaddition of a furan diene as the key step, 11-oxatricyclo[6.2.1.01,6]undecyl rings were synthesized from 5-methylfurfural with the goal of developing a synthetic protocol to 11-oxabicyclo[6.2.1]undecyl system. The strategy to incorporate an oxygen atom at C6 carbon of tricyclic 11 or 16 by Baeyer-Villiger oxidation was unsuccessful, implicating that there is too much steric congestion around the carbonyl ketone. As an alternative approach, bicyclic 23 and 24 were prepared from 2-methylfuran via known tricyclic 20. Cyclization of bicyclic 23 and 24 under several reaction conditions also failed to produce hydroxylated product 25 and 26.