• 제목/요약/키워드: Competing Reaction

검색결과 39건 처리시간 0.023초

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

  • Ahn, Kwang-Hyun;Groves, John T.
    • Bulletin of the Korean Chemical Society
    • /
    • 제15권11호
    • /
    • pp.957-961
    • /
    • 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.

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

  • 박병각
    • 대한화학회지
    • /
    • 제21권3호
    • /
    • pp.155-160
    • /
    • 1977
  • 경쟁 1,2-와 1,4-고리화첨가반응에 대한 frontier 분자궤도와 전전자에너지의 상관도를 작도하고 이 상관도에 의해서 반응기구를 설명할 수 있었다. 고찰해서 유도된 중요 결론은 다음과 같다. 1) HO와 LU사이에 교차가 일어나지 않았다. 그러므로 반응은 열반응이다. 2) diradical을 경유하는 이단계기구가 일단계기구 보다 에너지장벽으로 미루어 보아 유리하다. 3) [2+2]와 [2+4] 고리화첨가물의 생성물분포를 예측할 수 있다.

  • PDF

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
    • /
    • 제6권5호
    • /
    • pp.291-295
    • /
    • 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
    • /
    • 제4권1호
    • /
    • pp.39-43
    • /
    • 1996
  • Large-time asymptotic behavior of the solutions of interacting population reaction-diffusion systems are considered. Polynomial stability was proved.

  • PDF

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

  • 서정현;김유석;최재훈
    • 한국정밀공학회:학술대회논문집
    • /
    • 한국정밀공학회 2006년도 춘계학술대회 논문집
    • /
    • pp.537-538
    • /
    • 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.

  • PDF

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

  • 장세희;한보섭;김인규;오세화
    • 대한화학회지
    • /
    • 제10권2호
    • /
    • pp.51-53
    • /
    • 1966
  • Sandmeyer 반응으로 5-Amino-6-methyluracil로 부터 5-iodo-, 5-chloro- 및 5-bromo-6-methyluracil을 간편하게 합성하는 방법을 새로히 마련하였다. 이 방법에 따르면 5-halo-6-methyluracil이 70% 이상의 좋은 수득률로 얻어지며 부반응을 수반하지 않으므로 생성물의 정제가 쉽고 편리하게 5-halouracil을 얻을 수 있다는 이점이 있다.

  • PDF

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

  • 장세희;김인규;박도순;한보섭
    • 대한화학회지
    • /
    • 제9권1호
    • /
    • pp.29-32
    • /
    • 1965
  • Sandmeyer 반응으로 5-aminouracil로부터 5-iodo-, 5-chloro-및 5-bromouracil을 간편하게 합성하는 방법을 세로히 마련하였다. 이 방법에 따르면 5-halouracil이 75% 이상의 좋은 수율로 얻어지며, 부반응을 수반하지 않으므로 생성물의 정제가 쉽고 편리하게 5-halouracil을 얻을 수 있다는 이점이 있다.

  • PDF

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

  • Choi, Hye-Seon
    • Journal of Microbiology
    • /
    • 제35권1호
    • /
    • pp.15-20
    • /
    • 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.

  • PDF

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

  • Lin, Shi-Ying;Park, Seung-C.
    • Bulletin of the Korean Chemical Society
    • /
    • 제23권2호
    • /
    • pp.229-240
    • /
    • 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.