• Title/Summary/Keyword: Chemical reactions

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Thermal and Photoinduced Silylallylation Reactions of Organic Halides with 3-Stannyl-2-(silylmethyl)propene

  • 강경태;황성심;곽우영;윤웅찬
    • Bulletin of the Korean Chemical Society
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    • v.20 no.7
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    • pp.801-804
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    • 1999
  • Thermal and photoinduced silylallylation reactions of organic halides with 3-stannyl-2-(silylmethyl)propene are explored. Silylallylations occur in moderate to high yields, producing various functionalized allylsilane products in which halide carbon is bonded to the terminal alkenic carbon of allylsilane with the removal of tributyltin group. The reactions, which tolerate functional groups such as carbonyl, ester, nitrile, acetal, and ketal, hold synthetic potential for the construction of functionalized allylsilanes.

The Effect of Gas Thermochemical Model on the Flowfield of Supersonic Rocket in Propulsive Flight (기체 열화학 모델이 연소 비행하는 초음속 로켓 유동장에 미치는 영향)

  • 최환석
    • Journal of the Korean Society of Propulsion Engineers
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    • v.6 no.1
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    • pp.12-20
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    • 2002
  • An integrated analysis of kerosine/LOX based KSR-III rocket body/plume flowfield has been performed. The analysis has been executed employing three kind of gas thermo-chemical models including calorically perfect gas, multiple species chemically reacting gas, and chemically frozen gas models and their effect on rocket flowfield has been accessed to provide the most appropriate gas thermo-chemical model which meets a specific purpose of performing rocket body and plume analysis. The finite-rate chemically reacting flow solution exhibited higher temperature throughout the flowfield than other gas models due to the increased combustion gas temperature caused by the chemical reactions within the nozzle. All the reactions were dominated only in the shear layer and behind the barrel shock reflection region where the gas temperature is high and the effect of finite-rate chemical reactions on the flowfield was found to be minor. However, the present plume computation including finite-rate chemical reactions revealed major reactions occurring in the plume and their reaction mechanisms and as well.

Efficient Synthesis of Biologically Interesting Natural Pyranochalcones from Mallotus Philippensis and Their Unnatural Derivatives

  • Xia, Likai;Lee, Yong-Rok
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.2921-2927
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    • 2011
  • This paper describes efficient synthetic approaches for isolating biologically interesting natural pyranochalcones and their unnatural derivatives from Mallotus Philippensis. The key strategies involve ethylenediamine diacetate-catalyzed benzopyran formation reactions and base-catalyzed aldol reactions.

Efficient Synthesis of Bibenzyl Derivatives Bearing Pyranyl Moieties: First Total Synthesis of Bauhinol D

  • Park, Byung-Ho;Lee, Yong-Rok;Kim, Sung-Hong
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.566-570
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    • 2011
  • An efficient and general synthesis of bibenzyl derivatives bearing pyranyl rings was achieved by ethylenediamine diacetate-catalyzed reactions of 3,5-dihydroxybibenzyl with ${\alpha},{\beta}$-unsaturated aldehydes in moderate yields. These reactions provided naturally occurring compounds 1 and 2 in single step reaction. As an application of this methodology, biologically interesting natural bauhinol D (8) was synthesized by a convergent sequence from readily available benzaldehyde and benzyl phosphonate.

Efficient Synthesis of β-Acetamido Ketones by Silver(I) Triflate-Catalyzed Multicomponent Reactions

  • Pandit, Rameshwar Prasad;Lee, Yong Rok
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3559-3564
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    • 2012
  • An efficient one-pot synthesis of ${\beta}$-acetamido ketones was accomplished by AgOTf-catalyzed multicomponent reactions of substituted acetophenones with aromatic aldehydes and acid chloride in acetonitrile in high yields. The methods offer several significant advantages of easy handling, mild reaction conditions, and use of effective and non-toxic catalyst.

Pd-Catalyzed Substitution Reactions with Organoindium Reagents in situ Generated from Indium and Allyl or Propargyl Halides

  • Lee, Phil-Ho;Shim, Eun-Kyong;Lee, Koo-Yeon;SeoMoon, Dong;Kim, Sun-Dae
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.157-160
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    • 2005
  • Allylindium and propargylindium reagents in situ generated from the reactions of indium with allyl halides and propargyl halides could participate as nucleophiles in Pd-catalyzed substitution reactions of allyl carbonates to produce 1,5-dienes and 1,5-enynes in good yields. $\beta$-Hydride elimination products were produced in case of carbonates having $\beta$-hydrogens. Because organoindium reagents obtained from allyl or propargyl halides and indium have previously not been used to Pd-catalyzed allylic and propargylic substitution reactions, these results should provide more opportunities for the development of new C-C bond forming reactions.

The Measurement of Tranfer Enthalpy in Mixed Solvent (Part 2) Solvent Effects on Nucleophilic Substitution Reactions of Ethyl and 2-Phenylethyl Benzenesulfonates

  • Heo, Cheol;Lee, Hae Hwang;Lee, Ik Chun
    • Bulletin of the Korean Chemical Society
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    • v.16 no.1
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    • pp.53-58
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    • 1995
  • Heats of solution of aniline (AN), benzylamine (BA), ethyl-(EBS) and 2-phenylethyl benzenesulfonates (PEB) are calorimetrically measured in acetonitrile-methanol mixtures at 25.0 $^{\circ}C$. The activation parameters, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$, are determined for the reactions of EBS and PEB with AN and BA using the kinetic data at three temperatures. Calorimetric transfer enthalpies of initial state, ${\delta}H_t^{0{\rightarrow}x})$(IS), and kinetically derived activation enthalpies, ${\delta}\;{\Delta}H^{\neq}$, in the MeCN-MeOH mixtures are combined to determine the transfer enthalpies of transition state, ${\delta}H_t^{0{\rightarrow}x})$(TS); ${\delta}H_t^{0{\rightarrow}x})$(IS) = ${\delta}{\Delta}H^{\neq}\;+\;{\delta}H_t^{0{\rightarrow}x}$(IS) The preferential solvation of anionic charge in the TS predicts a loose TS with a greater degree of bond cleavage for the reactions of PEB than for EBS, and also for the reactions with BA compared to the reactions with AN.

Theoretical Studies of Solvent Effects on Gas Phase Reactions of Methoxide Ion with Substituted Ethylenes$^\dag$

  • Lee, Ik-Choon;Lee, Bon-Su;Won Jong-Ok
    • Bulletin of the Korean Chemical Society
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    • v.8 no.6
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    • pp.444-449
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    • 1987
  • Solvent effects on gas phase reactions of methoxide ion with substituted ethylenes, $CH_2$ = CHR where R = CN, CHO and $NO_2$, are investigated theoretically using the AM1 method. Results show that the methoxide approaches in-plane in all reactions, but subsequently rotate out-of-plane to form tetrahedral complexes in additon reactions. All reactions of a bare methoxide are found to be exothermic, the exothermicity being the greatest in the ${\beta}$-addition, in which the excess energy is forced to be contained within the ${\beta}$-adduct rendering extreme instability. However a part of the excess energy can be removed by a solvate molecule giving a stable complex prior to the product formation. The hydride transfer processes were found to be unfavorable due to the high activation barriers. The ${\alpha}-H^+$ abstraction process from acrylonitrile becomes endothermic as a result of monosolvation of the methoxide, in agreement with experimental results.

Kinetic Studies on the Reactions of NADH Analogs : Effects of 3-Substituents of 1-benzyl-1,4-Dihydropyridines

  • Park, Kwang-Hee;Kim, Hong-Gie;Park, Joon-Woo
    • Bulletin of the Korean Chemical Society
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    • v.10 no.5
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    • pp.448-452
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    • 1989
  • NADH analogs, 1-benzyl-3-substituted (X)-1,4-dihydropyridines 1-4 (1: X = $CONH_2$; 2: X = $CSNH_2$; 3: X = $COOCH_3$; 4: X = $COCH_3$) were synthesized. The second order rate constants for hydration reaction and oxidation reactions by $Cu^{2+}$, $Fe(CN)_6^{3-}$ or methylacridinium iodide (MAI) of the compounds were determined. For all reactions investigated, the rate constants increased with decreasing electronegative character of the 3-substituents of 1,4-dihydropyridines : the decreasing order of the reaction rates was 2>1>3>4. However, the sensitivity of the reaction rates on the 3-substituents differed among the reactions. This was explained in view of mechanisms of the reactions.

Theoretical Researches of Kinetics and Anharmonic Effect for the Reactions Related to NO in the Ozone Denitration Process

  • Yu, Hongjing;Xia, Wenwen;Liu, Yancheng;Yao, Li
    • Journal of the Korean Chemical Society
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    • v.65 no.3
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    • pp.185-196
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    • 2021
  • For studying the reaction mechanism of the reactions related to NO in the ozone denitration reactions, the harmonic and anharmonic rate constants were calculated by the transition state (TS) theory and Yao and Lin (YL) method. According to above calculations, the reactions of NO with O3 and NO3 play an essential role, and the kinetic parameters considering anharmonic effect were fitted. Furthermore, the rate constants were up as temperature increasing, and the tendencies of high temperature were more gradual than the low temperature. The research will provide theoretical basis for the ozone denitration reactions.