• Title/Summary/Keyword: Chemical reactions

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The Synthetic Potential of SET Photochemistry of Silicon-Substituted Polydonor-Linked Phthalimides

  • Yoon, Ung Chan;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.8
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    • pp.1099-1114
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    • 2006
  • Our studies in the area of single electron transfer (SET) photochemistry have led to the discovery of efficient processes, in which regioselective formation of carbon-centered radicals takes place by nucleophile assisted desilylation of $\alpha$-trialkylsilyl substituted ether, thioether, amine and amide centered cation radicals. The rates of bimolecular desilylation of the intermediate cation radicals exceed those of other cation radical $\alpha$-fragmentation processes (e.g.,-deprotonation). This sereves as the basis for the design of highly regioselective, SET-induced photomacrocyclization reactions of polyether, polythioether, polyamide, and polypeptide linked phthalimides. Photocyclization reactions of trimethylsilyl-terminated substrates in these families are unique in that they produce polyfunctionalized macrocyclic substances in a highly efficient and regioselective manner. In addition, our studies in this area have led to important information about the factors that govern chemical and quantum efficiencies that should be applicable to a wide variety of redox processes promoted by SET from substrates containing more than one electron donor site.

Photochemical Approach to the Preparation of Lariat Crown Ethers Containing Peptide Sidearms

  • Cho, Dae-Won;Quan, Chunsheng;Park, Hea-Jung;Yoon, Ung-Chan;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.503-509
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    • 2011
  • New types of lariat type crown ethers containing peptide sidearms were prepared by using a novel strategy employing single electron transfer (SET)-induced photocyclization reactions of $\alpha$-silylether terminated phthalimides. Reactions of chiral substrates in this series produced diastereomeric mixtures of crown ether products as a result of the formation of new stereogenic center generation in the photocyclization process.

Vibration Analysis and Diagnosis for Reactor Agitator (Reactor Agitator 의 진동분석 및 진단사례)

  • Yoo, Ju-Hyung;Jung, Goo-Choong;Lee, Sun-Hwi
    • Proceedings of the Korean Society for Noise and Vibration Engineering Conference
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    • 2012.04a
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    • pp.107-112
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    • 2012
  • All chemical processes are centered in the chemical reactor. Chemical reactions are often accompanied by mixing. Mixing can influence not just reaction rate but also product distribution if more than one product is possible. So, reactor agitator is more critical in industrial reactions. High vibration was occurred on reactor agitator which is critical equipment in HDPE plant. This paper describes analysis and diagnosis for agitator vibration throughout some tests. High vibration has been occurred by misalignment and resonance. Through the correction it could be stable.

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Catalytic Activity Studies in Transesterification Reaction (에스테르 교환반응(交換反應)의 촉매활성(觸媒活性)에 관(關)한 연구(硏究))

  • Park, Keun-Ho;Kim, Dong-Shik;Jeong, Soon-Wook
    • Journal of the Korean Applied Science and Technology
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    • v.7 no.1
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    • pp.71-76
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    • 1990
  • Transesterification reactions (methyl methacrylate with monoethanolamine, methyl methacrylate with n-butyl alcohol, dimethylphthalate with ethylene glycol, dimethyl phthalate with monoethanolamine) were kinetically investigated in the presense of various metal acetate catalysts at $110^{\circ}C$. The amount of reactants was measured by gas and liquid chromatography, and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively. The overall reaction order was 2nd, Maximum reaction rates were appeared at the range of 1.4 to 1.6 in electronegativity of metal ions and maximum catalytic activities were obserbed at the range of 1.5 to 1,8 in instability constant of metal acetates.

Characteristics of the Ignition Delay for Hydrocarbon Fuels by Reduced Chemical Kinetics Modeling (축소 화학반응 모델링에 의한 탄화수소 연료의 점화지연 특성)

  • 김형욱;배상수;민경덕
    • Transactions of the Korean Society of Automotive Engineers
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    • v.9 no.4
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    • pp.44-49
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    • 2001
  • Reduced chemical kinetics mechanism has been derived, which can be applicable for autoignition model of hydrocarbon fuels, and contains 23 reactions and 18 species. The present model is validated with the experimental data, where the ignition delays of several hydrocarbon fuels, such as n-heptane, i-octane, n-decane and DME(dimethylether) are measured as equivalence ratios are varied. Especially, the effects of different fuels on ignition delays can be explained by changing the rate constants of three reactions among the present model. As a result, the proposed model can be applicable to two stage ignition model of Diesel combustion.

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Preparation of Sophorose - I. Chemical Synthesis of Sophorose from D-Glucose (Sophorose의 제조-I. D-Glucose로부터 sophorose의 화학적 합성)

  • Anufriev, Victor P.;Park, Jong-Dae;Lee, You-Hui;Kim, Shin-Il;Baek, Nam-In
    • Applied Biological Chemistry
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    • v.39 no.6
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    • pp.512-516
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    • 1996
  • Sophorose $(2-O-{\beta}-D-glucopyranosyl-D-glucopyranose)$ was chemically synthesized from D-glucopyranose through six steps of chemical reactions with the yield of 21%. The chemical structures of sophorose and some compounds obtained during reactions were confirmed by interpretations of spectral data, NMR, IR, etc.

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Application of Pseudo Molecular Complexes (II). A New Mechanism for Aromatic Substitution (유사분자 착물의 응용 (제 2 보). 새로운 방향족 치환반응 기구)

  • Park Byung-Kak
    • Journal of the Korean Chemical Society
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    • v.19 no.3
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    • pp.179-185
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    • 1975
  • A new mechanism is proposed for aromatic substitution, involving the formation of pseudo molecular complexes at the transition state. It accounts for the addition reactions of aromatic compounds with double bond reagents such as ozone, somium tetraoxide and carbene as well as all of the features of electrophilic substitution reactions. The pseudo molecular complex has been proved to be formed by quantum-chemical considerations using the simple Huckel method.

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Synthesis of Diblock Codendrimer by Double Click Chemistry

  • Lee, Jae Wook;Han, Seung Choul;Ji, Won Ho;Jin, Sung-Ho;Kim, Ji Hyeon
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4103-4108
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    • 2012
  • Efficient double click methods for the synthesis of diblock codendrimers were developed. The synthetic strategy involved the sequential click reactions between an alkyne and an azide. The short core building block, 1,4-diazidobutane, was chosen to serve as the azide functionalities for dendrimer growth via click reactions with the alkyne-functionalized PAMAM dendrons as hydrophilic dendron and alkyne-functionalized Fr$\acute{e}$chet-type dendrons as hydrophobic dendron. The structure of diblock codendrimers was confirmed by $^1H$ and $^{13}C$ NMR spectroscopy, IR spectroscopy, mass spectrometry, and GPC analysis.

Photochemical Reaction of Nalidixic Acid in Methanol

  • Park, Hyoung-Ryun;Park, Ok-Hyun;Lee, Hong-Yune;Seo Jung-Ja;Bark, Ki-Min
    • Bulletin of the Korean Chemical Society
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    • v.24 no.11
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    • pp.1618-1622
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    • 2003
  • The photochemical reactions of methanolic nalidixic acid (NAL) solution in the absence and in the presence of air have been investigated using 300 nm UV light. From the reactions, 1-ethyl-7-methyl-4-oxo-4-hydro-1,8-naphthyridine (EMDN),formic acid, and formaldehyde are produced. In the presence of air, hydrogen peroxide is also detected along with the products listed above. The presence of oxygen during the irradiation of methanolic NAL solution effects on the product yield. The initial quantum yields of the products and of the NAL decomposition are determined. Possible reaction pathways for the photochemical reaction are suggested on the basis of the products analysis.

The Chemistry of Rhodium in Polysulfone: Reactions with Various Small Gas Molecules

  • Il-Wun Shim;Jin-Si Kim;Seok-Jong Oh;Yong-Sik Yang;Hwan-Kyu Suh;Sang-Kyu Lee
    • Bulletin of the Korean Chemical Society
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    • v.15 no.2
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    • pp.126-132
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    • 1994
  • RhCl [P($C_6H_5)_3]_3$ complexes have been incorporated in polysulfone (PS) as a dispersion medium using cosolvent (THF). The interactions between Rh(Ⅰ) complexes and polysulfone polymer molecules are examined by infrared spectroscopy and thermal analysis. The chemical reactivity of Rh in PS films has been investigated by reacting Rh sites with CO, $H_2,\;D_2,\;O_2\;NO,\;C_2H_2\;and\;C_2H_4$ in the temperature range $25-200^{\circ}C$. Various Rh-carbonyl, -hydride and -nitrosyl species formed in PS films are characterized by their infrared spectra. Rh complexes in PS film show interesting catalytic reactivities in the reactions such as hydrogenation of $C_2H_2\;and\;C_2H_4$, oxidation of CO, and reduction of NO by CO or $H_2$ gas under relatively mild conditions.