• Title/Summary/Keyword: Cyclization

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Application of Suspension-Polymerized Spherical PAN beads as a Precursor of Spherical Activated Carbon (현탁중합으로 합성된 구형 PAN 수지의 구형 활성탄의 전구체로서의 활용)

  • Hyewon, Yeom;Hongkyeong, Kim
    • Journal of Institute of Convergence Technology
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    • v.12 no.1
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    • pp.13-18
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    • 2022
  • Polyacrylonitrile was synthesized through suspension polymerization and then sieved to obtain spherical beads with a size of 200~510 ㎛. PAN was copolymerized with 2 mol% MMA monomer which is known to promote cyclization and crosslinking of nitrile group. The resonance cyclization reaction of the nitrile group in the synthesized PAN beads was observed near 170℃ with thermal analysis and FT-IR. The reaction conversion of the nitrile group in spherical beads was 23% during heat treatment, which was lower than that of the well-oriented PAN fiber used as a precursor of carbon fiber. This is because the stereo-regularity of molecular chains in the form of a random coil (spherical bead) is much lower than that of PAN fiber. It was confirmed that the compressive strength of the spherical PAN bead was greatly improved through the resonance cyclization and shrinkage according to the heat treatment, and it was also observed that the pores in PAN beads were formed after the heat treatment.

Palladium-Catalyzed Cross-Coupling Reaction and Gold-Catalyzed Cyclization for Preparation of Ethyl 2-Aryl 2,3-Alkadienoates and α-Aryl γ-Butenolides

  • Mo, Jun-Tae;Hwang, Hoon;Lee, Phil-Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.2911-2915
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    • 2011
  • Efficient synthetic method for the preparation of ethyl 2-aryl-2,3-alkadienoates through Pd-catalyzed selective allenyl cross-coupling reactions of aryl iodides with organoindiums generated in situ from indium and ethyl 4-bromo-2-alkynoate was developed. The cyclization reaction of ethyl 2-aryl-2,3-alkadienoates catalyzed by $AuCl_3$ and AgOTf in the presence of AcOH or TfOH produced various ${\alpha}$-aryl ${\gamma}$-butenolides or ${\gamma}$-substituted ${\alpha}$-aryl ${\gamma}$-butenolides.

Optimization of the Reaction Conditions for Synthesis of 3-(Aryloxy)quinoline Derivatives via Friedländer's Cyclization Reaction

  • Khan, Mohammad Ashrafuddin;El-Gamal, Mohammed I.;Oh, Chang-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.6
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    • pp.1848-1852
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    • 2013
  • 6,7-Dimethoxy-2-methyl-3-(4-nitrophenoxy)quinoline was synthesized by Friedl$\ddot{a}$nder's cyclization reaction. Different bases and solvents were tested in order to optimize the reaction conditions. The highest yields were obtained using piperidine in refluxing ethanol. Further reactions were carried out in order to prepare different diarylamide and diarylurea derivatives in moderate to high yields in order to examine their anticancer activities.

Analysis of the functional domains of CFTase gene cloned from Xanthomonas oryzae #5 using recombinant deletion mutant

  • Kim, Byeong-U;Yu, Dong-Ju;Ryu, Hye-Gyeong;Park, Ju-Hui
    • 한국생물공학회:학술대회논문집
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    • 2001.11a
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    • pp.727-730
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    • 2001
  • Various recombinant deletion mutants were constructed from cycloinulo - oligosaccharide fructanotransferase(CFTase) gene of Xanthomonas oryzae #5 . The mutants were expressed in Escherichia coli DH5${\alpha}$. We were able to obtain three recombinant proteins were purified, and examine their CFTase and hydrolyzing activity. N-terminal deletion mutant had both CFTase activity and hydrolyzing activity. however, in C-terminal and N,C-terminal deletion mutant disappeared CFTase activity, but hydrolyzing activity remained. From there results, it seems that the C-terminal region(amino acid $1173{\sim}1333$) is important for cyclization.

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Synthesis of Tetracyclic Pyrido[2,3-b]azepine Derivatives as Analogues of Mirtazapine via N-Acyliminium Ion Cyclization

  • Lee, Jae-Yeol;Bang, Sung-Hun;Lee, Sook-Ja;Song, Yun-Seon;Jin, Chang-Bae;Park, Ho-Koon;Lee, Yong-Sup
    • Bulletin of the Korean Chemical Society
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    • v.23 no.11
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    • pp.1623-1628
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    • 2002
  • Tetracyclic pyrido[2,3-b]azepine derivatives 4a-d and 4f as analogues of mirtazapine were synthesized via N-acyliminium ion cyclization by using aromatic rings such as benzene and thiophene ring as a ${\pi}-nucleophile$, and evaluated for the binding affinity for ${\alpha}2-adrenoceptor$. Among tested compounds, 2,3,9,13b-tetrahydro-1H-benzo[f]pyrrolo[2,1-a]pyrido[2,3-c]azepine (4a) was the most potent (Ki = 0.26 ${\mu}M)$ but showed about 3-fold less binding affinity than mirtazapine (Ki = 0.08 ${\mu}M)$ for a2-adrenoceptor.

Characteristics of the Intermediates in the Cyclization Reactions of Heterocycle-fused[1,4]oxazine Derivatives: Stepwise versus Concerted

  • Shin, Dong-Soo;Park, Jong-Keun
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2219-2225
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    • 2007
  • The reaction mechanisms for the cyclizations of N-methyl-2-(2-chloropyridin-3-yloxy)acetamide to 1-methylpyrido[ 3,2-b][1,4]oxazin-2-one and 1-methyl-pyrido[2,3-b][1,4]oxazin-2-one were investigated using ab initio Hartree-Fock, second-order Moller-Plesset perturbation, single point coupled cluster with both single and double substitution, and density functional theory methods. The 5-membered spiro intermediate (2) is optimized from the cyclization of the acyclic reactants through the proton-transfer reaction, and this intermediate proceeds continuously to the 6-membered intermediate through either a stepwise or a concerted reaction. In the stepwise reaction, an N-bridge-type intermediate as a stable structure is optimized, whereas, in the concerted reaction, the O-bridge-type intermediate is not optimized.

Polyhydroxyamic Acid from 3,3′ - Dihydroxybenzidine and Pyromellitic Dianhydride as a Fire-safe Polymer

  • Park, Seung Koo;Farris, Richard J.;Kantor, Simon W.
    • Fibers and Polymers
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    • v.5 no.2
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    • pp.83-88
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    • 2004
  • In order to assess the potential of the hydroxy-containing polyamic acid (PHAA) synthesized from 3,3'-dihydroxy benzidine and pyromellitic dianhydride for a fire-safe polymer, the cyclization pathway of PHAA has been investigated using a model compound prepared from 2-aminophenol and phthalic anhydride. The reaction was monitored. by $^1{H-nuclear}$ magnetic resonance. N-(2-hydroxyphenyl) phthalamic acid is converted to N-(2-hydroxyphenyl) phthalimide at ca. 175$^{\circ}C$, showing endothermic reaction. The imide structure is rearranged to the benzoxazole structure over ca. $400^{\circ}C$. These results are similar with that of PHAA. According to pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) data, water and carbon dioxide are released during the cyclization and rearrangement reaction. One DMAc molecule is complexed with one carboxyl acid group in PHAA, which accelerates the imidization process to release more easily the flame retardant, water.

Influence of oxidative atmosphere of the electron beam irradiation on cyclization of PAN-based fibers

  • Shin, Hye Kyoung;Park, Mira;Kim, Hak-Yong;Park, Soo-Jin
    • Carbon letters
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    • v.16 no.3
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    • pp.219-221
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    • 2015
  • In order to study the impact of atmosphere during electron beam irradiation (EBI) of polyacrylonitrile (PAN) precursor fibers, the latter were stabilized by EBI in both air and oxygen atmospheres. Gel-fraction determination indicated that EBI-stabilization under an oxygen atmosphere leads to an enhanced cyclization in the PAN fibers. In the Fourier-transform infrared spectroscopy analysis, the PAN fibers stabilized by EBI under an oxygen atmosphere exhibited a greater decrease in the peak intensity at 2244 cm−1 (C≡N vibration) and a greater increase in the peak intensity at 1628 cm−1 (C=N absorption) than the corresponding PAN fibers stabilized under an air atmosphere. From the X-ray diffraction analysis it was found that oxygen uptake in PAN fibers leads to an increase in the amorphous region, produced by cyclization.

A Study on Chemical Cyclodehydration of Aromatic Poly(ether-amide-amic acid)s (방향족 폴리(에테르-아미드-아미드산) 중합체의 화학적 탈수 고리화 반응)

  • Ahn, Young Moo
    • Textile Coloration and Finishing
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    • v.7 no.4
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    • pp.39-44
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    • 1995
  • A study has been made about some correlations in the chemical cyclization of precursors, poly(ether-amide-amic acid)s by treating in solution a mixture of acetic anhydride and pyridine in the presence of 4,4-dimethyl formamide, with the poly(ether-amic acid)s being respectively reacted between trimellitic anhydride chloride and 3 kinds of diamines, i.e., 4,4'-bis(m-aminophenoxy) benzophenone, 2,2'-bis[4-(m-aminophenoxy) phenyl] propane and 4,4'-bis(m-aminophenoxy) diphenyl sulfone. The cyclization of imide ring in the poly(ether-amide-amic acid)s may be regarded as an intramolecular acylation of amide group by o-carboxyl group. As a result of this reseach, the effects on the conversion to poly(ether-amide-imide)s have been found by changing the ratio of cosolvents in the cyclization mixture.

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Determination of Reactivity by MO Theory (XXV), Theoretical Studies of $\omega$-Alkenyl Radical Cyclization

  • Lee, Ik-choon;Lee, Bon-Su;Song, Chang-Hyun;Kim Chan-Kyung
    • Bulletin of the Korean Chemical Society
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    • v.4 no.2
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    • pp.84-87
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    • 1983
  • Transition state structures were calculated for A and M routes of ${\omega}$-alkenyl radical cyclization (n = 2∼4) using MINDO/3-RHF method. Results of our analysis of HOMO level changes indicated that the transition state stability is not controlled by the decoupling effect alone as Bischof suggested, but in greater degree it is determined by through-bond interaction of the HOMOs with the framework $HO-{\sigma}$ or $LU-{\sigma}^*$ orbitals. In case of larger n (n > 4), the product stability was considered to be the main cause of M route dominance in the cyclization.