• Title/Summary/Keyword: $S_N2$ reaction

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Effects of Different Extraction Extraction Media and Reaction Mixtures on Photosystem II Activity of Spinach Chloroplasts (시금치 엽록체의 광계의 활성에 미치는 추출용매와 반응용액의 영향)

  • 권병규
    • Journal of Plant Biology
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    • v.19 no.4
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    • pp.95-99
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    • 1976
  • This work deals with different extraction media and reaction mixtures on photosystem II activity of Spinach chloroplasts. The photoreduction rate of ferricyanide and DPIP by intact chloroplasts which extracted with four kinds of extraction media; S-Tris-N pH 7.2, 8.0, S-Tricine-N pH 7.2, 8.0, was measured in five kinds of reaction mixtures; S-Tris-N pH 7.2, 8.0, S-Tricine-N pH 7.2, 8.0, 0.05 M-Tris pH 7.2. The extraction medium which shows the highest photoreduction rate was S-Tris-N at pH 7.2 and S-Tricine-N at pH 8.0. As to the reaciton mixture, S-Tricine-N pH 8.0 showed the highest rate. On the complex effects of extraction media and reaction mixtures, the highest photordeuction rate of Hill oxidant by intact chloroplasts was obtained by S-Tris-N pH 7.2 extraction medium and S-Tricine-N pH 8.0 reaction mixture. The second highest activity was obtained by S-Tricine-N pH 8.0 extraction medium and reaction mixture.

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Synthesis and Characterization of Square Planar Mixed-Ligand Complexes (II) : Electrophilic and Nucleophilic Reaction of M(S-S)(N-N) Type Complexes with Ni(II), Pd(II), and Pt(II) (평면사각형 혼합 리간드 착물의 합성과 그 특성 (제 2 보) : Ni(II), Pd(II) 및 Pt(II)의 M(S-S)(N-N)형 착물의 친전자성 및 친핵성 반응)

  • OH Sang Oh;Chung Duck Young
    • Journal of the Korean Chemical Society
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    • v.36 no.1
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    • pp.81-86
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    • 1992
  • The electrophilic and nucleophilic reactions of M(S-S,ph)(N-N,H) (M = Ni(II), Pd(II), Pt(II); (S-S,ph) = 1,2-diphenylethylenedithiolate; (N-N,H)=1,10-phenanthroline) complexes have been investigated. Reaction with norbornadiene depended upon the back donating ability of the central metal ion and produced 2,5-dithia-3,4-diphenyl-tricyclo[4,4,1,0]-undeca-3,8-diene. In the reaction with methyl iodide, the effect of cleavage of (N-N,H) ligand affected the yield of methylated $M(S-S,ph)_2$ product. The structure of the thermolysis product, ${\alpha},{\alpha}{\prime}$-bismethylthiostibene $(CH_3S-SCH_3,ph)$ of methylated complexes indicates that the main product of the nucleophilic reaction is $M(CH_3S-SCH_3,ph)(S-S,ph)$. We have synthesized a new mixed-ligand complex M(S-S,CN)(N-N,H)((S-S,CN) = 1,2-dicyanoethylenedithiolate) through the nucleophilic reaction of ligand.

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N,N'-Dimethylethylenediamine-N,N'-di-α-butyric Acid Cobalt(III) Complexes Utilizing Oxidation of Sulfur of S-Methyl-L-cysteine

  • Kim, Hyun-Jin;Youm, Kyoung-Tae;Yang, Jung-Sung;Jun, Moo-Jin
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.851-856
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    • 2002
  • The Reaction of S-methyl-S-cysteine(L-Smc) with racemic $s-cis-[Co(demba)Cl_2]-1$ (Hydmedba = $NN'-dimethylethylenediamine-NN'-di-\alpha-butyric$, acid) yields ${\Delta}$-s-cis-[Co(dmedba)(L-Smc)] 2 with N, O-chelation. Oxidation of sulfur of 2 with $H_2O_2$ in a 1 : 1 mole ratio gives ${\Delta}$-s-cis[Co(dmedba)(L-S(O)mc)] 3 having an uncoordinated sulfenate group. Oxidation of sulfur of L-Sm with $H_2O_2in$ a 1: 1 mole ratio produces S-methyl-L-cysteinesulfenate (L-S(O)me) 5. Direct reaction of 1 with 5 in basic medium gives an N.O-chelated ${\Delta}$s-cis[Co(dmedba)(L-S(O)mc)-N.O], which turmed out be same as obtained by oxidation of 2, while an N, S-chelated ${\Delta}$-s-cis-[Co(dmedba)(S-S(O)mc)-N,O] complex 4 is obtained in acidic medium from the reaction of 1 with 5. This is one of the rare $[$Co^{III}$(N_2O_2-type$ ligand)(amino acid)] type complex preparations, where the reaction conditions determine which mode of N, O and N, S caelation modes is favored.

Studies on the Reaction of 2-Phenylethyl Arenesulfonates with Pyridine under High Pressure (2-Phenylethyl Arenesulfonates와 피리딘과의 고압반응에 관한 연구)

  • Yoh Soo Dong;Park, Jong Hwan
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.383-388
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    • 1986
  • Kinetics of the reaction of 2-phenylethylarenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40∼60${\circ}C$. The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reactions of benzyl benzenesulfonate with pyridine in acetoneitrile were investigated by an electric conductivity method under 1 to 2,000 bars and at 40~60${\circ}C$ .The rates of these reactions were increased with raising temperatures and pressures, but less than those of the reaction of benzyl benzenesulfonate with pyridine in acetone. The activation volumes and activation entropies of 2-phenylethyl m-nosylate were more negatively large than those of benzyl benzenesulfonate. From these phenomena it can be deduced that 2-phenylethyl system has more firmly $S_N2$ character in tranistion state. The Hammett reaction constants are also estimated from the second-order reaction constants. With increasing pressures the reaction parameters $({\rho})$ were decreased, but the $S_N2$ characters were increased. From these results, the reaction mechanism can be adequately described as typical $S_N2$ process under high pressure.

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Kinetic Studies on the Reaction of Benzyl m-Nitrobenzenesulfonate with N,N-Dimethylanilines (벤질 m-술폰산니트로벤젠과 N,N-디메틸아닐린類와의 反應에 關한 反應速度論的 硏究)

  • Yoh Soo-Dong;Lee Mu-Sang
    • Journal of the Korean Chemical Society
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    • v.23 no.1
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    • pp.37-41
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    • 1979
  • The kinetics of the reaction of benzyl m-nitrobenzenesulfonate with m-and p-substituted N,N-dimethylanilines in acetone have been investigated by an electric conductivity method. The effects of substituents on the reactivity of N,N-dimethylaniline and the existence of linear free energy relationship were discussed. The rate constants k were in the range 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$ and increased with the electron donating ability of substituents. In the present reaction, the Hammett plot was correlated with ${\sigma}$ substituent constant, especially using the new ${\sigma}$ value of 0.35 in p-MeO and it's ${\rho}$ value was found to be -1.37. r value for the reaction was very large than the value obtained in the reaction of benzyl bromide. $Br{\"{o}}nsted$ linear relationship was shown between rate constant and basicites except for p-MeO resulted from solvent effect. From the Bronsted plot, this reaction was suggested that the cleavage of the C${\cdot}{\cdot}{\cdot}$O bond in the $S_N2$ transition state proceed the bond formation.

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Sn2/E2 Branching in Protic Solvents: A Mechanistic Study

  • Oh, Young-Ho;Im, Suk;Park, Sung-Woo;Lee, Sung-Yul;Chi, Dae-Yoon
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1535-1538
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    • 2009
  • We present calculations for $S_N$2/E2 reactions in protic solvents (t-butyl alcohol, ethylene glycol). We focus on the role of the hydroxyl (-OH) groups in determining the $S_N$2/E2 rate constants. We predict that the ion pair E2 mechanism is more favorable than the naked ion E2 reaction in ethylene glycol. E2 barriers are calculated to be much larger (~ 9 kcal/mol) than $S_N$2 reaction barriers in protic solvents, in agreement with the experimental observation [Kim, D. W. et al. J. Am. Chem. Soc. 2006, 128, 16394] of no E2 products in the reaction of CsF in t-butyl alcohol.

Cobalt(Ⅲ) Complexes of N₄and $N_2O_2$ System Tetradentate Ligands : Amino Acid Cobalt(Ⅲ) Complexes of 1,3-Diaminopropane-N,N'-Di-α-(β-methyl)-Pentanoic Acid

  • 함혜영;이석중;김영상;준무진
    • Bulletin of the Korean Chemical Society
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    • v.17 no.5
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    • pp.428-432
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    • 1996
  • Amino acid cobalt(Ⅲ) complexes of 1,3-diminopropane-N,N'-di-α-(β-methyl)-pentanoic acid (H2dpdmp), uns-cis-[Co(dpdmp)(aa)] (aa=glycine, S-alanine, R-aspartic acid, sarcosine) have been prepared from the reaction between the uns-cis-[Co(dpdmp)Cl2]- complex and the corresponding amino acid. In the reaction with the uns-cis-[Co(dpdmp)Cl2]- complex, glycine and S-alanine have yielded both merridional and facial isomers, while R-aspartic acid and sarcosine, only merridional isomers. The stereospecific substitution reaction of R-aspartic acid to racemic uns-cis-[Co(dpdmp)Cl2]- complex has yielded two merridional diastereomers; ΛR-uns-cis- and ΛR-uns-cis-[Co(dpdmp)(R-asp)]. It is of interest to note that this is one of the few CoⅢ(ONNO)(aa) type complex preparations, which gives only one isomer with stereospecificity. On the other hand, two merridional products obtained from the reaction of sarcosine with racemic uns-cis-[Co(dpdmp)Cl2]- are turned out to be mixtures of optical isomers.

Synthesis of TiO2 Fine Powder by Sol-Gel Process and Reaction Mechanism(II) : Hydrolysis of Titanium n-Propoxide (졸-겔법에 의한 TiO2미분말 합성과 반응메카니즘(II): Titanium n-propoxide의 가수분해)

  • Myung, Jung-Jae;Park, Jin-koo;Chung, Yong-Sun;Kyong, Jin-Bum;Kim, Ho-Kun
    • Applied Chemistry for Engineering
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    • v.8 no.5
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    • pp.777-783
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    • 1997
  • $TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.

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Effects of the thin SiO$_{2}$ film at the Ti-Si interface on the formation of TiN/TiS$i_2$ bilayer (Ti-Si 계면의 얇은 산화막이 TiN/TiS$i_2$ 이중구조막 형성에 미치는 영향)

  • 이철진;성만영;성영권
    • The Transactions of the Korean Institute of Electrical Engineers
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    • v.45 no.2
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    • pp.242-248
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    • 1996
  • The properties of TiN/TiSi$_{2}$ bilayer formed by a rapid thermal annealing is investigated when thin SiO$_{2}$ film exists at the Ti-Si interface. The competitive reaction for the TiN/TiSi_2 bilayer occurs above 600 .deg. C. The thickness of the TiSi$_{2}$ layer decreases with increasing SiO$_{2}$ film thickness and also decreases with increasing anneal temperture When the competitive reaction for the TiN/TiSi$_{2}$ bilayer is occured by rapid thermal annealing, the composition of TiN layer represents TiN$_{x}$O$_{y}$ due to the SiO$_{2}$ layer at the Ti-Si interface but the structures of the TiN and TiSi$_{2}$ layers were not changed.d.d.

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Ring Closure of N-(2-Hydroxyethyl)-N'-phenylthioureas:One-Pot Synthesis of 2-Phenylaminothiazolines

  • Kim, Taek Hyeon;Min, Jeong Gi;Lee, Gyu Jae
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.919-922
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    • 2000
  • The cyclization reaction of N-(2-hydroxyethyl)-N'-phenylthioureas 2 containingambident nucleophile was ex-amined in the combination of a variety ofbases and p-toluenesulfonyl chloride (TsCl).N-(2-Hydroxyeth-yl) thioureas 2 were readily obtained in high yields from the reaction of the corresponding 1,2-aminoalcohols with phenyl isothiocyanate, avoiding the need for O-protection.The use of a one-pot reaction (NaOH/TsCl) was found to be most effective in producing the requisite 2-phenylaminothiazolines (S-cyclization) 3 in the case ofthioureas 2a-2e derived from N-unsubstituted aminoalcohols,while in the thioureas 2f and 2g prepared from N-substituted aminoalcohols the combination of Et3N and TsCl led to the S-cyclization products.