• Title/Summary/Keyword: Competing Reaction

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Shape Selective Oxygen Transfer to Olefins Catalyzed by Sterically Hindered Iron Porphyrins

  • Ahn, Kwang-Hyun;Groves, John T.
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.957-961
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    • 1994
  • Epoxidation of olefins catalyzed by iron-tetraarylporphyrins were studied to see the shape selectivity in the competing reaction between cis-and trans- or internal and external olefins. Cis-olefins were more reactive than trans-olefins in the competing reaction between cis-and trans-olefins. Interestingly, in the epoxidation of $cis-{\beta}-methystyrene$ by ${\alpha}{\beta}{\alpha}{\beta}$ atropisomer of Fe(III)TNPPPCl and iodosylbenzene, 27% of total product was phenylacetone. The unusually large amount of phenylacetone may be produced by hydride rearrangement of carbocationic intermediate. Regioselectivity of the reaction was also studied by using the most sterically hindered Fe(III)TTPPPCl. In the epoxidation of limonene with Fe(III)TTPPPCl, the disubstituted double bond was more reactive than trisubstituted double bond. This is in contrast to the results obtained with other iron-tetraarylporphyrins. Similar trend was also observed in the competing reaction between mono-and di-substituted olefins.

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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Methyl Linoleate Oxidation via Electron Transfer in Competition with $^1O_2$ Formation Photosensitized N-Acetyl-L-Tryptophan 3-Methyl Indole

  • Yoon, Min-Joong;Song, Moon-Young;Cho, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.291-295
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    • 1985
  • The efficiency of photosensitization of methyl linoleate (ML) oxidation by N-acetyl-L-trypophan(NAT) and 3-methyl indole(scatole) was markedly enhanced by increased concentration of ML in ethanol solution. The fluorescence intensities of sensitizers were observed to be quenched by ML, indicating that ML interacts with the indole excited singlet state. The inhibition of photosensitization by azide demonstrated a possible role of singlet oxygen in the photosensitization. The steady state kinetic treatment of azide inhibition of photosensitization was expected to show linear increase of reciprocal yield of ML oxidation product vs. reciprocal ML concentration at constant azide concentration, but the actual slope was nonlinear. This indicates another competing reaction involved in the photosensitization, As a possible competing reaction, electron transfer from ML to the excited sensitizer was proposed, since the measured fluorescence quenching rate constant closely resembled electron transfer rate constant determined from ML concentration dependence of oxidation product formation.

ASYMPTOTIC STABILITY OF COMPETING SPECIES

  • Kim, June Gi
    • Korean Journal of Mathematics
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    • v.4 no.1
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    • pp.39-43
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    • 1996
  • Large-time asymptotic behavior of the solutions of interacting population reaction-diffusion systems are considered. Polynomial stability was proved.

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Characterization of Mixing in Reaction Modules for the Production of Chemical Materials (화학소재 생산용 반응 모듈의 혼합 성능 해석)

  • Seo J.H.;Kim Y.S.;Choe J.
    • Proceedings of the Korean Society of Precision Engineering Conference
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    • 2006.05a
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    • pp.537-538
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    • 2006
  • Split and recombine type reaction module was made by electrical discharge machining. The reaction module has special features to well mix the two reactants which have high flow ratio or high concentrations difference. It could be achieved by deviding one flow equally by two and inserting second flow in between. The mixing performance was measured by a parallel competing reaction with iodide-iodate system. The result shows that the developed three inlets micromixer has better mixing efficiency than comercialized Y type micromixer.

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Reaction of Nitrous Acid on 5-Aminopyrimidines [III] Sandmeyer Reaction of Diazotizated 5-Amino-6-Methyluracil (Aminopyrimidine 유도체에 대한 아질산의 작용 [III] Diazotizated 5-Amino-6-Methyluracil에 대한 Sandmeyer 반응)

  • Chang, Sae-Hee;Hahn, Bo-Sup;Kim, In-Kyu;Oh, Sea-Hwa
    • Journal of the Korean Chemical Society
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    • v.10 no.2
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    • pp.51-53
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    • 1966
  • A new conventional method for the preparation of 5-iodo, chloro-, and bromo-6-methyluracil by Sandmeyer reaction was described. According to this procedure, 5-halo-6-methyluracils have been prepared in high yields (up to 70%) without any difficulties to obtain highly pure products. No appreciable competing reaction was observed.

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Reaction of Nitrous Acid on 5-Aminopyrimidines (I) Sandmeyer Reaction of Diazotizated 5-Aminouracil (5-Aminopyrimidine 유도체에 대한 아질산의 작용 [I] Diazotizated 5-Aminouracil에 대한 Sandmeyer 반응)

  • Chang, Sae-Hee;Kim, In-Kyu;Park, Do-Soon;Hahn, Bo-Sup
    • Journal of the Korean Chemical Society
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    • v.9 no.1
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    • pp.29-32
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    • 1965
  • A new conventional method for the preparation of 5-iodo-, chloro-and bromouracil by Sandmeyer reaction was described. According to this procedure, 5-halouracils have been prepared in high yields(up to 75%) without any difficulties to remove of impurities. No appreciable competing reaction was observed.

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Catalytic mechanism and inhibition studies of purine nucleoside phosphorylase (PNP) in micrococcus luteus

  • Choi, Hye-Seon
    • Journal of Microbiology
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    • v.35 no.1
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    • pp.15-20
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    • 1997
  • Kinetic studies were done to elucidate the reaction mechanism of purine nucleoside phosphorylase (PNP) in Micrococcus Luteus. PNP catalyzes the reversible phosphorolysis of ribonucleosides to their respective base. The effect of alternative competing substrates suggested that a single enzyme was involved in binding to the active site for all purine nucleosides, inosine, deoxyiosine, guanosine, deoxyguanosine, adenosine and deoxyadenosine. Affinity studies showed that pentose moiety reduced the binding capacity and methylation of ring N-1 of inosine and guanosine had little effect on binding to bacterial enzyme, whereas these compounds did not bind to the mammalian enzymes. The initial velocity and product inhibition studies demonstrated that the predominant mechanism of reaction was an ordered bi, bi reaction. The nucleoside bound to the enzyme first, followed by phosphate. Ribose 1-phosphate was the first product to leave, followed by base.

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Quantum Mechanical Study of the O(1D) + HCl → OH + Cl Reaction

  • Lin, Shi-Ying;Park, Seung-C.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.229-240
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    • 2002
  • Quantum mechanical calculation is performed for the $O(^1D)$ + HCl ${\rightarrow}$OH + Cl reaction using Reactive Infinite Order Sudden Approximation. Shifting approximation is also employed for the l ${\neq}$ 0 partial wave contributions. Various dynamical quantities are calculated and compared with available experimental results and quasiclassical trajectory results. Vibrational distributions agree well with experimental results i.e. product states mostly populated at $v_f$ = 3, 4. Our results also show small peak at $v_f$ = 0, which indicates bimodal vibrational distribution. The results show two significant broad peaks in ${\gamma}_i$ dependence of the cross section, one is at ${\gamma}_i$ = $15^{\circ}-35^{\circ}$ and the another is at ${\gamma}_i$= $55^{\circ}-75^{\circ}$ which can be explained as steric effects. At smaller gi, the distribution is peaked only at higher state ($v_f$ = 3, 4) while at the larger gi, both lower state ($v_f$ = 0) and higher state ($v_f$ = 3, 4) are significantly populated. Such two competing contributions (smaller and larger ${\gamma}_i$) result in the bimodal distribution. From these points we suggest two mechanisms underlying in current reaction system: one is that reaction occurs in a direct way, while the another is that reaction occurs in a indirect way.