• Title/Summary/Keyword: thermal rearrangement

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Synthesis of 1, 1-Diheteroaryl Ethylenes by a Tandem Appel's Dehydration/Thermal Rearrangement Methodology

  • 이기정;허 열;전종갑
    • Bulletin of the Korean Chemical Society
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    • v.20 no.3
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    • pp.341-344
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    • 1999
  • The hydrazones of 2-acetylfuran, 2-acetylthiophene, and 2-acetylpyrrole, were allowed to react with S-methylthioacetimidate hydroiodide (8) to give azinoureas 10, and the reaction of 10 with Appel's dehydration conditions (triphenylphosphine/carbon tetrachloride/triethylamine) led to the corresponding azinocarbodiimides 11, which underwent thermal rearrangement under the reaction conditions to give 1,1-diheteroaryl ethylenes 13.

Synthesis of polyphenylcarbosilane via thermal rearrangement of polymethylphenylsilane in supercritical cyclohexane

  • Shin, Hee-Yong;Ryu, Jae-Hun;Bae, Seong-Youl;Lee, Yoon-Joo;Kwon, Woo-Teck;Kim, Young-Hee;Kim, Soo-Ryong
    • Journal of the Korean Applied Science and Technology
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    • v.30 no.1
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    • pp.9-15
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    • 2013
  • A new process for the synthesis of polyphenylcarbosilane (PPCS) via thermal rearrangement of polymethylphenylsilane (PMPS) in supercritical cyclohexane was proposed and investigated at reaction temperatures of $380-420^{\circ}C$, reaction times of 1-2 h, and a pressure of 15 MPa. The structure, molecular weight, and molecular weight distribution of the product were characterized by FT-IR, Si-NMR, and GPC. The ceramic yield was also measured by TGA analysis. High-quality PPCS with high molecular weight and ceramic yield can be synthesized via a supercritical process. Furthermore, this process, when compared to the conventional method, tends to moderate the reaction conditions such as reaction temperature and time. It is concluded that thermal rearrangement in supercritical fluid is an efficient and viable process in terms of the resulting yield, efficiency, and reaction time compared with those of the conventional PCS production process.

Mechanistic Investigation of the Copper(I)-Catalyzed Trifluoromethylthiolation Using Sulfonyl Hypervalent Iodonium Ylide as the SCF3 Source: A DFT Study

  • Park, Yoonsu;Jung, Yousung
    • Proceeding of EDISON Challenge
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    • 2014.03a
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    • pp.337-346
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    • 2014
  • Trifluoromethylthiol functional group(이하 -SCF3)은 약학적으로 유용한 물질이다. 이 연구는 최근 개발된 Shibata의 Direct trifluoromethylthiolation reaction의 반응 메커니즘을 계산화학적으로 평가했다. 반응 메커니즘은 크게 Carbene formation, Rearrangement, Electrophilic SCF3 reagent generation 세 단계로 나눌 수 있다. 각 과정에 대해 구조에 대한 full optimization이 진행되었고, 특히 alpha-carbene sulfonyl species의 thermal rearrangement에 관한 첫번째 계산화학적 평가가 이루어졌다.

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On the Properties and Synthesis of Nanostructured W-Cu alloys by Mechanical Alloying(II) Sintering Behavior of MA NS W-Cu Composite Powders (기계적 합금화 방법으로 제조된 nanostructured W-Cu 합금의 제조 및 물성 연구(II) -MA NS W-Cu 복합분말의 소결거동-)

  • 김진천
    • Journal of Powder Materials
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    • v.5 no.2
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    • pp.89-97
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    • 1998
  • Sintering behavior of nanostructured(NS) W-Cu powders prepared by mechanical alloying (MA) was investigated as a function of sintering temperature. MA NS W-2owt%Cu and W-3owt%Cu composite powders with the crystal size of 20-30 nm were annealed at 90$0^{\circ}C$, and thermal characteristics of those powders were investigated by DSC. Sintering behavior of MA NS W-Cu composite powders was investigated during the solid-state sintering and the Cu-liquid phase sintering. The new nanosintering phenonenon of MA W-Cu powders at solid-state sintering temperature was suggested to explain the W-grain growth in the inside of MA powders. The sintering densification of MA NS W-Cu powders was enhanced at Cu melting temperature by arrangement of MA powders, i.e., the first rearrangement of MA powders was occurred, and then the rearrangement of W-grains in the sintered parts was also took place during liquid-phase sintering, i.e., the second rearrangement was happened. Due to the double rearrangement process of MA NS W-Cu powders, the high sintered density with more than 96%o was obtained and the fine and high homogeneous state of W and Cu phases was achieved by sintering at 1200 $^{\circ}C$.

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Thermal Stress Analysis of Piping Systems in Steam-driven Power Engines (증기 동력기관 내 배관시스템의 열응력 해석)

  • Kim, C.H.;Chung, H.T.;Bae, J.S.;Jung, I.S.;Lee, S.S.
    • Journal of Power System Engineering
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    • v.13 no.6
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    • pp.35-42
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    • 2009
  • The piping systems in the steam-driven power engines lie under the cyclic condition of thermal expansion and contraction by superheated steam. These phenomena might cause some severe damages on the pipes and the accessory devices. To avoid these damages, the calculation of the proper strength and the consideration of the reduced resultant forces on the materials are needed. In the present study, numerical investigations on the effects of the thermal deformation of the industrial piping system were performed with comparison of the design data. Commercial software, ABAQUS with the thermal-fluidic loadings based on the design conditions was used for the thermal stress analysis of the piping system. From the analysis of the initially-designed pipe supporters, the rearrangement was suggested to improve the piping design.

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A Study on the Sintering and Mechanism of Crystallization Prevention of Alumina Filled Borosilicate Glass (알루미나를 충전재로 첨가한 붕규산염 유리의 소결 및 결정화 방지기구에 대한 연구)

  • 박정현;이상진;성재석
    • Journal of the Korean Ceramic Society
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    • v.29 no.12
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    • pp.956-962
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    • 1992
  • The predominant sintering mechanisms of low firing temperature ceramic substrate which consists of borosilicate glass containing alumina as a filler are the rearrangement of alumina particles and the viscous flow of glass powders. In this system, sintering condition depends on the volume ratio of alumina to glass and on the particle size. When the substrate contains about 35 vol% alumina filler and the average alumina particle size is 4 $\mu\textrm{m}$, the best firing condition is obtained at the temperature range of 900∼1000$^{\circ}C$. The extensive rearrangement behavior occurs at these conditions, and the optimum sintering condition is attained by smaller size of glass particles, too. The formation of cristobalite during sintering causes the difference of thermal expansion coefficient between the substrate and Si chip. This phenomenon degradates the capacity of Si chip. Therefore, the crystallization should be prevented. In the alumina filled borosilicate glass system, the crystallization does not occur. This effect may have some relation with aluminum ions in alumina. For aluminum ions diffuse into glass matrix during sintering, functiong as network former.

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Thermally Induced Mesophase Development in Ethanesilica Films via Macromolecular Templating Approach

  • Cho, Whirang;Char, Kook-Heon;Kwon, Su-Yong
    • Macromolecular Research
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    • v.17 no.9
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    • pp.697-702
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    • 2009
  • Mesoporous ethanesilica thin film was prepared using PEO-PLGA-PEO triblock copolymers as structure-directing agents and (1,2-bis(triethoxysilyl) ethane BTESE; bridged organosilicates) as inorganic precursors via one-step sol-gel condensation of ethanesilica precursors. The mesostructure of ethanesilica films is critically dependent on the processing experimental parameters after the hydrolyzed silica sol mixture was spin-cast. This study examined the effects of the block copolymer template/organosilica precursor ratio in the casting solution and aging period before calcination of the mesostructure. It was further demonstrated that mesoscopic ordering of organosilicate thin films is induced by the rearrangement of block copolymer template/organosilica hybrid during thermal decomposition of the PEO-PLGA-PEO triblock copolymer. The mesoporous structure and morphology were characterized by SAXS, TEM and solid-state NMR measurement.

Hydroxy-Substituted Polyenaminonitrile as a Soluble Precursor for Rigid-Rod Polybenzoxazole

  • Kim, Ji Heung;Lee, Jae Gwan
    • Bulletin of the Korean Chemical Society
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    • v.22 no.9
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    • pp.999-1004
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    • 2001
  • (1-Chloro-2,2-dicyanovinyl)benzene or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene was reacted with 2-amino-phenol to give the model compound, hydroxy enaminonitrile, which was found to undergo thermal cyclization reaction to form the corresponding benzoxazole. This intramolecular cyclization reaction is expected to occur through nucleophilic attack to electropositive enamine carbon by ortho-hydroxy group on the phenyl ring, which is accompanied by the release of neutral malononitrile through rearrangement. From each bifunctional monomer, o-hydroxy substituted polyenaminonitrile was prepared and characterized as a new precursor polymer for well-known aromatic polybenzoxazole. Also the unusual macrocyclic dimer formation from the 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane polymerization reaction system was discussed. The thermal cyclization reactions and the properties of polymers were investigated using FT-IR and thermal analysis (DSC & TGA).

Thermal Rearrangement of 1,1-Disubstituted 2-Vinylcyclopropanes to 4,4-Disubstituted Cyclopentenes (두 치환체를 가진 비닐시클로프로판의 시클로펜텐으로의 열적자리 옮김반응)

  • Iwhan Cho;Kwang-Duk Ahn
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.158-163
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    • 1978
  • The four 1,1-disubstituted 2-vinylcyclopropanes, 1,1-diphenyl-2-vinylcyclopropane (1a), 1,1-dicyano-2-vinylcyclopropane(1b), ethyl 1-cyano-2-vinylcyclopropanecarboxylate(1c), and diethyl 2-vinylcyclopropane-1,1-dicarboxylate(1d) rearranged below $300{\circ}C$ to the corresponding 4,4-disubstituted cyclopentenes, 4,4-diphenylcyclopentene(2a), 3-cyclopentene-1,1-dicarboxylate(2d). Diphenpyl derivative 1a rearranged almost quantitatively to 4,4-diphenylcyclopentene(2a) at the temperature of $250{\circ}C$. Although dicyano derivative 1b in solution underwent the thermal rearrangement at rather low temperature of $170{\circ}C$, the other vinylcyclopropanes, 1c and 1d, in solution rearranged thermally above $220{\circ}C$. In the thermal reaction of 1b, 1c, and 1d considerable amounts of polymers 3 were also produced. Also detected product was the ring-opened diene, ethyl 2-cyano-2,4-hexadienoate(4), in case of the pyrolysis of 1c. The observed facile rearrangement of disubstituted vinylcyclopropanes was explained by the radical stabilization effect of substituents on the diradical intermediates 5.

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