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

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Synthesis and Ring-Opening Polymerization of 1,2-Disubstituted Cyclobutanes

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • v.7 no.3
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    • pp.210-213
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    • 1986
  • 1,1-Dicyano-2-ethoxycyclobutane (1a) was prepared by [2 + 2] cycloaddition reaction of vinylidene cyanide with ethyl vinyl ether. 1,1-Dicyano-2-phenylcyclobutane (1b) was prepared by the reactions involving the reduction of cinnamyl alcohol, chlorination, cyanomethylation, bromination, and ring-closure reaction. Compound 1a was ring-opening polymerized with NaCN or n-butyllithium to give a low molecular weight polymer. The compound 1b however, failed to polymerize by either anionic or radical catalysts.

Synthesis of Propylene Carbonate over Metal containing Ionic Liquid Catalysts (금속 함유 이온성 액체 촉매상에서의 프로필렌 카보네이트의 합성)

  • Moon, Ye-Ji;Ji, Dahye;Kim, Dong-Woo;Kim, Hyeon-Gook;Cho, Deug-Hee
    • Applied Chemistry for Engineering
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    • v.27 no.2
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    • pp.153-157
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    • 2016
  • In this study, three different metal-containing ionic liquid catalysts were prepared by metal insertion and characterized by various physicochemical analytic methods. The catalytic performance of the metal containing ionic liquids in the cycloaddition of $CO_2$ with propylene oxide (PO) to produce propylene carbonate (PC) was investigated under the solvent free condition. The order of approximate rate constants ($K_{app}$) for the metal containing ionic liquid catalysts was $(MeIm)_2ZnCl_2$, > $(MeIm)_2FeCl_2$ > $(MeIm)_2CuCl_2$. These results are in accord with the experimentally obtained activity order of the different metal containing ionic liquid catalysts.

CONFORMATIONAL ANALYSIS ON THE C$_4$-PHOTOCYCLODIMERS OF 4,$5^1$,8-TRIMETHYLPSORALEN

  • Kim, Ja-Hong
    • Journal of Photoscience
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    • v.2 no.2
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    • pp.99-101
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    • 1995
  • A semiempirical methods(PM3-CI-UHF, MM2) for the evaluation of ground and excited state electronic structures of electron-donating substituents are applied to 4, 5', 8-trimethylpsoralen(TMP) with TMP dimer. Three types of product have been proposed; (1) pyrone< >pyrone, (2) pyrone< >furan, (3) hetero dimer resulting from the C$_4$-cycloaddition between the furan end of one TMP moiety and the pyrone end of the other, with cis-syn configuration.

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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.

The Importance of $\pi$-Nonbonded Secondary Orbital Interaction on the Stereoselectivity in the (4+2) Cycloaddition Reactions of Allene Compounds (알렌화합물의 (4+2) 고리화반응에서 입체 선택성에 대한 $\pi$-비결합 2차 궤도함수 상호작용의 중요성)

  • Ikchoon Lee;Keun Bae Rhyu;Byung Choon Lee
    • Journal of the Korean Chemical Society
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    • v.31 no.2
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    • pp.133-142
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    • 1987
  • Stereoselectivities of (4+2) cycloaddition reactions of cyclopentadiene with the methyl-substituted allenic acids and esters were investigated by application of $\pi$-nonbonded interaction ($\pi$-NBI) theory. 2-FMO method has been found to be adequate for determination of endo selectivities of diene(LUMO)-dienophile (LUMO) interaction in the thermal reactions and diene (HOMO)-dienophile (LUMO) interaction in the Lewis acid catalyzed reactions. $\pi$-isoconjugate diene structure was formed by through-bond interaction of allene moiety with methyl group in the cumulated diene system; the methyl substituent acts as a conjugative chain and causes inter-level narrowing effect of the FMO's. In dienophiles which do not form $\pi$-isoconjugate diene system, methyl group acts merely as an electron donating group. In thermal reactions, the stereoselectivities are controlled by $\pi$-nonbonded secondary orbital interaction ($\pi$-NSOI) of methyl substituent, which behaves similarly as an ethylene molecule.

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Catalytic Application of Metal-Organic Frameworks for Chemical Fixation of CO2 into Cyclic Carbonate (CO2로부터 5원환 탄산염의 화학적 고정화 반응을 위한 Metal-Organic Frameworks의 촉매적 응용)

  • Ji, Hoon;Naveen, Kanagaraj;Kim, Dongwoo;Cho, Deug-Hee
    • Applied Chemistry for Engineering
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    • v.31 no.3
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    • pp.258-266
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    • 2020
  • The chemical fixation of CO2 into cyclic carbonates is considered to be one of the most promising way to alleviate global warming and produce fine chemicals. In this work, the catalytic applicability of metal-organic frameworks (MOFs) as porous crystalline materials for the synthesis of five-membered cyclic carbonate from CO2 and epoxides was reviewed. In addition, we have briefly classified the materials based on their different structural features and compositions. The studies revealed that MOFs exhibited good catalytic performance towards cyclic carbonate synthesis because of the synergistic effect between the acid sites of MOFs and nucleophile. Moreover, the effect of structure of designed MOFs and mechanism for the cycloaddition of CO2 were suggested.

THEORETICAL ANALYSIS ON THE PHOTOCHEMISTRY OF COUMARIN DERIVATIVES

  • Kim, Ja-Hong;Sohn, Sung-Ho;Kim, Jung-Sung
    • Journal of Photoscience
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    • v.2 no.2
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    • pp.95-98
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    • 1995
  • The photodimers with cyclobutane rings and C$_2$ symmetry, derived from coumarin (syn, head to tail and anti, head to head) have been calculated by PM3-UHF-CI and Molecular Mechanics force field. The photocycloaddition to coumarin and 5,7-dimethoxycoumarin(DMC) dimers were deduced to be formed by their preferable frontier orbital interactions and via more stable cycloaddition by the C$_3$, C$_4$ bond. These results are consistent with the coumarin dimer model that the theoretical C$_4$-photocyclodimer of coumarin is predicted much more than the experimental C$_4$-photocyclodimer.

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