• Title/Summary/Keyword: cycloaddition

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Strain-promoted alkyne-azide cycloaddition for PET molecular imaging study

  • Jeong, Hyeon Jin;Kim, Dong Wook
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.1 no.1
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    • pp.15-22
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    • 2015
  • $^{18}F$-labeling reaction of bioactive molecule via click chemistry is widely used to produce $^{18}F$-labeled radiotracer in the field of radiopharmaceutical science and molecular imaging. In particular, bioorthogonal strain-promoted alkyne-azide cycloaddition (SPAAC) reaction has received much attention as an alternative ligation method for radiolabeling bioactive molecules such as peptides, DNA, proteins as well as nanoparticles. Moreover, SPAAC based pretargeting method could provide tumor images successfully on positron emission tomography system using nanoparticle such as mesoporous silica nanoparticles.

Synthesis and Cycloaddition Reactions of N-Aryl-2-furohydrazonyl Chlorides

  • S, Shawali-Ahmad;M, Hassaneen-Hamdi;A, Ibrahim-Hossin
    • Archives of Pharmacal Research
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    • v.13 no.2
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    • pp.126-131
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    • 1990
  • The novel N-phenyl-2-furohydrazonyl chloride 4A and its p-nitro analog 4B have been prepared and identified. The cycloaddition reactions of nitrilimines 5A and 5B, derived by base catalyzed dehydrochlorination of 4A and 4B respectively, to a variety of dipolarophiles were investigated. The results showed that 4A and 4B are usuful precursors for synthesis of differently substituted 3-(2-furyl)-2-pyrazoline derivatives and their pyrazoles and analogs.

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Synthesis of Dendrimer Containing Dialkylated-fluorene Unit as a Core Chromophore via Click Chemistry

  • Han, Seung-Choul;Jin, Sung-Ho;Lee, Jae-Wook
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.137-142
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    • 2012
  • The convergent synthetic strategy for the emissive dendrimers having the chromophore at core via the coppercatalyzed 1,3-dipolar cycloaddition reaction between alkyne and azide was described. 2,7-Diazido-9,9-dioctyl-9H-fluorene, designed to serve as the core in dendrimer, was stitched with the alkyne-functionalized Frechettype and PAMAM dendrons by the click chemistry leading to the formation of the corresponding fluorescent dendrimers in high yields. The preliminary photoluminescence studies indicated that 2,7-diazido-9,9-dioctyl-9H-fluorene showed no fluorescence due to the quenching effect from the electron-rich ${\alpha}$-nitrogen of the azido group but the dendrimers fluoresced due to the elimination of the quenching through the formation of the triazole ring.

Studies on Tropolones (Ⅲ) Structures and Reaction Mechanisms of the Adducts of Dichloroketene and Cyclopentadienes (Tropolone 類에 關한 硏究 (III) Dichloroketene과 Cyclopentadiene 類의 添加物의 構造와 그 反應機構)

  • Jae Hu Shim
    • Journal of the Korean Chemical Society
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    • v.13 no.1
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    • pp.89-95
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    • 1969
  • The structural investigations on the adducts, formed from dichloroketene with cyclopentadiene, methyl and ethylcyclopentadiene, have been carried out by means of infrared and nuclear magnetic resonance spectroscopy and also by their chemical behaviors. It was confirmed by this study that the adducts were formed by 1, 2-cycloaddition reaction and had the fundamental structure of bicyclo [3. 2. 0]-7,7-dichloro-2-heptene-6-one. These results were well agreed with the hypothesis that a diradical intermediate was formed as the first step in 1, 2-cycloaddition. The reaction mechanism for the process in which tropolones were formed from these adducts was also discussed.

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Ab Initio Study of Mechanism of Forming Germanic Bis-Heterocyclic Compound between Dimethyl-Germylene Carbene (Me2Ge=C:) and Acetone

  • Lu, Xiuhui;Che, Xin;Lian, Zhenxia;Li, Yongqing
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.89-94
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    • 2011
  • The mechanism of the cycloaddition reaction of forming germanic bis-heterocyclic compound between singlet dimethylgermylene carbene and acetone has been investigated with CCSD(T)//B3LYP/6-$31G^*$ method. From the potential energy profile, it can be predicted that, this reaction has one dominant channel. The presented rule of this dominant channel is that the two reactants firstly form a four-membered ring carbene (RC4) through the [2+2] cycloaddition reaction. Due to $sp^2$ hybridization of carbene C atom in RC4, RC4 further combines with acetone to form a reactant complexe (RC5). Due to the further $sp^3$ hybridization of carbene C atom in RC4, RC5 isomerizes to a germanic bisheterocyclic compound (P6) via the transition state (TS5).

Efficient Cycloaddition Reaction of Carbon Dioxide with Epoxide by Rhodamine Based Catalyst Under 1 atm Pressure

  • Gong, Qing;Luo, Huadong;Cao, Di;Zhang, Haibo;Wang, Wenjing;Zhou, Xiaohai
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.1945-1948
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    • 2012
  • Rhodamine B (RhB) and rhodamine 6G (Rh6G) were employed as catalysts for the synthesis of cyclic carbonate from carbon dioxide and epoxide. It turned out that the catalytic activity of Rh6G was nearly 29 times higher than that of RhB at 1 atm pressure, $90^{\circ}C$. Furthermore, the catalytic efficiency of RhB and Rh6G was greatly enhanced with triethylamine as co-catalyst. Under the optimized conditions, the best isolated yield (93%) of cyclic carbonate was achieved without organic solvent and metal component.

HMO Correlation Diagrams for a few Competing 1,2-and 1,4-Cycloaddition Reactions (경쟁 1,2-와 1,4-고리화 첨가반응의 상관도)

  • Byung Kak Park
    • Journal of the Korean Chemical Society
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    • v.21 no.3
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    • pp.155-160
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    • 1977
  • HMO correlation diagrams for some competing 1,2-and 1,4-cycloaddition reactions have been made to elucidate the reaction mechanism. The main conclusions obtained from this study are as follows. 1) The crossing between the highest occupied molecular orbital and the lowest unoccupied molecular orbital was not observed, which indicates that the reaction proceeds thermally, in agreement with the experimental results. 2) From the consideration of the energy barrier in the process of the energy transformation going from reactants to product, the two-step mechanism via a diradical intermediate is preferred over the concerted one. 3) The existance of diradical intermediates can account for the observed product distributions.

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Synthesis of Novel 1,2-Diazepino[3,4-b] quinoxalines and pyridazino[3,4-b] quinoxalines (새로운 1,2-다이아제피노 [3,4-b]퀴녹살린류와 피리다지노 [3,4-b] 퀴녹살린류의 합성)

  • Kim, Ho-Sik;Lee, Seong-Uk;Jeong, Geuk;Lee, Man-Kil;Kurasawa, Yoshihisa
    • YAKHAK HOEJI
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    • v.44 no.4
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    • pp.325-333
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    • 2000
  • The 1,3-dipolar cycloaddition reaction of the quinoxaline 4-oxides 2 with 2-chloroacrylonitrile gave the 2,3-dihydro-1H-1,2-diazepino[3,4-b]quinoxalines 3, which were converted into the 2,3,4,6-tetrahydro-1H-1,2-diazepino[3,4-b]quinoxalines 5-7. The reaction of compounds 3 with selenium dioxide in acetic acid/water resulted in ring transformation to give the 1,4-dihydro-4-oxopyridazino[3,4-b]quinoxalines 8.

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Chemisorption and orientation of Selenopheneon Si(100)-$2{\times}1$

  • Lee, Han-Koo;Kim, Ki-Jeong;Kim, Hyeong-Do;Shin, Hyun-Joon;Kim, Bong-Soo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.372-372
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    • 2010
  • We have investigated adsorption of selenophene on Si(100) at room temperature using high resolution photoemission spectroscopy (HRPES) and near edge X-ray absorption fine structure (NEXAFS) in the partial electron yield (PEY) mode. The Si 2p, C 1s, Se 3d spectra of selenophene on Si(100) show that selenophene is nondissociatively chemisorbed on Si(100)-$2{\times}1$ through [2+2] cycloaddition. NEXAFS has been conducted to characterize the adsorption geometry of selenophene on Si(100). Since the $\pi^*$ orbital of C=C bond show good angular dependence in carbon K-edge NEXAFS spectra, the angle $53{\pm}5^{\circ}$ determined from NEXAFS spectra. This majority structure is consistent with the [2+2] cycloaddition of selenophene to the dimer of the Si(100)-$2{\times}1$ surface.

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How Does the 2-Thiophenecarboxaldehyde Behaves on the Ge(100) Surface

  • Lee, Myungjin;Shin, Minjeong;Lee, Hangil
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.136-136
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    • 2013
  • High-resolution photoemission spectroscopy (HRPES) measurements were collected and density functional theory (DFT) calculations were conducted to track the coverage dependent variation of the absorption structure of 2-thiophenecarboxaldehyde (C4H3SCHO: TPCA) on the Ge(100) surface at room temperature. In an effort to identify the most probably adsorption structures on the Ge(100) surface, we deposited TPCA molecules at a low coverage and at a high coverage and compared the differences between the electronic features measured using HRPES. The HRPES data provided three possible adsorption structures of TPCA on the Ge(100) surfaces, and DFT calculations were used to determine the plausibility of the structures. HRPES analysis, corroborated by DFT calculations, indicated that an S-dative bonded structure was the most probable adsorption structure at relatively lower coverage levels, the [4+2] cycloaddition structure was the second most probable structure, and the [2+2]-C=O cycloaddition structure was the last probable structure on the Ge(100) surfaces at relatively higher coverage levels.

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