• Title/Summary/Keyword: halides

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Reaction Intermediate of Organic Sulfur Compund Ⅱ. Nucleophilic Substitution Reaction of Disulfonyl Chloride Compounds

  • Dae-Dong Sung;Dae-Il Jung;Kyu-Chul Kim;Yang-Hee Kim;Soo-Dong Yoh
    • Bulletin of the Korean Chemical Society
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    • v.11 no.1
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    • pp.65-69
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    • 1990
  • The nucleophilic substitution reactions of naphthalene-1,5-disulfonyl chloride and 4-fluorosulfonylbenzenesulfonyl chloride with p-substituted anilines and methyl substituted pyridines in methanol-acetonitrile mixtures and hydrolyses of those disulfonyl halides have been studied by means of conductometric and polarographic methods. A large difference in the selective parameter, ${\rho}_N$ between mono-sulfonyl chloride and disulfonyl halide can be taken as an evidence that the second $SO_2Cl$ grolup of naphthalene-1,5-disulfonyl chloride also takes part in the reaction in contrast to sulfonyl fluoride in 4-fluorosulfonylbenzenesulfonyl chloride, which only acts as a substituent in the nucleophilic substitution reaction.

Hydrogenation of Arenes with Metallic Iridium and Rhodium Powders Prepared from Iridium(Ⅰ) and Phodium(Ⅰ)-COD Complexes under Mild Conditions

  • 진종식;이병노;문지중;송중호;박용선
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.528-533
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    • 1995
  • Metallic iridium and rhodium powders prepared from the reactions of [M(COD)(PhCN)2]ClO4 (M=Ir(1), Rh(2); COD=1,5-cyclooctadiene) with hydrogen at room temperature in methylene chloride show catalytic activities for hydrogenation of arenes at room temperature under atmospheric pressure of hydrogen. Most substituents (CH3, COOH, NO2, CH2OH, CHO, OPh, OCH3, C=C, halogens and CH2Cl) on aromatic ring suppress the rate of the hydrogenation of the aromatic ring while the aromatic ring hydrogenation of phenol and 1,4-dihydroxobenzene is faster than that of benzene over these metallic powders. Hydrogenation of benzoic acid occurs only at the aromatic ring leaving the COOH group intact over iridium metal powders while benzoic acid is not hydrogenated at all over rhodium metal powders. Carbonyl, nitro, acetylenic and olefinic groups on an aromatic ring are hydrogenated prior to the aromatic ring hydrogenation. Hydrogenolysis of OH groups of phenol, benzyl alcohol and 1,4-dihydroxobenzene, and hydrodehalogenation of halobenzenes, benzyl halides and cinnamyl chloride also occur along with the hydrogenation of aromatic ring.

Preferential Solvation and Statistical Analysis for Solvent Polarity Parameters in MeOH Binary Mixtures

  • Sakong Yeol;Yoo Seoung-Kyo;Lee Ikchoon
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.636-642
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    • 1992
  • Preferential solvation (PS) phenomena of solutes based on solvent polarity, $E_T$ and AN, were studied by UV/vis. and NMR spectra in MeOH binary mixtures. According to the extent of solvent-solvent interaction, different solvation phenomena were found. PS concept was applied to explain the reactivity of tert-butyl halides solvolysis. The findings of solvation phenomena have been related to the rate of solvolysis and PS suggested as a reason for the solvent dependence of the rates of reaction. Moreover, we found that the results of principal components analysis using six parameters are in good accordance with the results of PS phenomena in mixed methanol systems.

Synthesis of Novel Alkyl $\alpha$-Anilinophenylacetate Derivatives Using Hydrolysis of Hydantoin Ring and Its O-Alkylation

  • Park, Hae-Sun;Park, Myung-Sook;Choi, Hee-Jeon;Kwon, Soon-Kyoung
    • Proceedings of the PSK Conference
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    • 2003.04a
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    • pp.244.2-244.2
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    • 2003
  • For the development of new synthetic method for unnatural amino acid esters, alkyl ${\alpha}$-anilinophenylacetates were synthesized through base-catalyzed hydrolysis of 1,5-diphenylhydantoins in methanol and O-alkylation of sodium ${\alpha}$-anilinophenylacetate with alkyl halides in DMF. Even though hydrolysis of hydantoin ring was undertaken under about 30-40$^{\circ}C$ in methanol, the hydantoic acid sodium salt was continuously converted to the sodium ${\alpha}$-anilinophenylacetate. (omitted)

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Binary Compound Formation upon Copper Dissolution: STM and SXPS Results

  • Hai, N.T.M.;Huemann, S.;Hunger, R.;Jaegermann, W.;Broekmann, P.;Wandelt, K.
    • Corrosion Science and Technology
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    • v.6 no.4
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    • pp.198-205
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    • 2007
  • The initial stages of electrochemical oxidative CuI film formation on Cu(111), as studied by means of Cyclic Voltammetry (CV), in-situ Scanning Tunneling Microscopy (STM) and ex-situ Synchrotron X-ray Photoemission Spectroscopy (SXPS), indicate a significant acceleration of copper oxidation in the presence of iodide anions in the electrolyte. A surface confined supersaturation with mobile CuI monomers first leads to the formation of a 2D-CuI film via nucleation and growth of a Cu/I-bilayer on-top of a pre-adsorbed iodide monolayer. Structurally, this 2D-CuI film is closely related to the (111) plane of crystalline CuI (zinc blende type). Interestingly, this film causes no significant passivation of the copper surface. In an advanced stage of copper dissolution a transition from the 2D- to a 3D-CuI growth mode can be observed.

Rate and Product Studies with 2-Methyl-2-Chloroadamantane under Solvolytic Conditions

  • Lee, Young-Hoon;Seong, Mi-Hye;Lee, Eun-Sung;Lee, Yong-Woo;Won, Ho-Shik;Kyong, Jin-Burm;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.5
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    • pp.1209-1214
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    • 2010
  • Reactions of 2-methyl-2-chloroadamantane (1) in a variety of pure and binary solvents have been studied at various temperatures and pressures up to 80 MPa. The sensitivity (m) to changes in solvent ionizing power of the Grunwald-Winstein equation, and the activation volume (${\Delta}V^{\ddag}$) are calculated from the specific rates. An excellent linear relationship (R = 0.997) for 1, log (k/$k_0$) = $0.80Y_{Cl}$ + 0.11, and the activation volume, ${\Delta}V^{\ddag}$ = -15.2 ~ -10.2 $mL{\cdot}mol^{-1}$ were observed. These values are similar to those for solvolyses of 1-adamantyl halides over the full range of solvents, suggesting that the unimolecular mechanism involving ion pairs is rate-determining. These observations are also compared with those previously reported for the corresponding 1-adamantyl derivatives and chloroformate esters.

Spectrophotometric Study of the Interaction between Tetraethylammonium Halides and Aza-15-crown-5 with I2 and ICl in Acetonitrile Solution

  • Semnani, Abolfazl;Pouretedal, Hamid Reza;Hossein Keshavarz, Mohammad
    • Bulletin of the Korean Chemical Society
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    • v.27 no.6
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    • pp.886-892
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    • 2006
  • The interaction between tetraethylammonium chloride (TEACl) with ICl and tetraethylammonium iodide (TEAI) and aza-15-crown-5 (A15C5) with $I_2$ and ICl have been examined spectrophotometrically in acetonitrile solution. The results of TEACl-ICl indicate the formation of $ICl_2$ - through equilibrium reaction. In the case of TEAI-$I_2$ and A15C5-$I_2$, the equilibrium formation of $I_3$ - is confirmed. The interaction of TEAI-ICl begins with the simultaneous production of $I_2$ and IC$I_2$ - (at TEAI/ICl < 0.5) as well as continues with the simultaneous consumption of $I_2$ and formation of I$I_3$ - (at TEAI/ICl > 0.5). Similar behavior is also observed for A15C5-ICl system. However, the changes are seen at A15C5/ICl mole ratios less and more than 0.66. Several equations have been suggested for the formation of detected species. The formation constants of various reactions were evaluated from the computer fitting of the absorbance-mole ratio data. IR spectra of A15C5 and 1:1 A15C5:ICl or A15C5:$I_2$ complexes are compared and the effect of complexation on absorption bands is discussed.

${\beta}-Ag_3SI$ Single Crystal Membrane Electrode (${\beta}-Ag_3SI$ 단결정막 전극에 관한 연구)

  • Sin Doo-Soon;Seon-Cheon Lee
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.86-94
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    • 1984
  • The single crystal ion-selective electrode,$ {\beta}-Ag_3SI/PVC-THF $membrane electrode has showed a linear potential response to the activities of iodide ion (10-1${\sim}$10-7M). The $ {\beta}-Ag_3SI$ membrane electrode was compared with AgI/PVC-THF membrane and copper metal plate membrane electrodes. In order to measure the selectivity coefficient of the electrodes toward $Cl^-$ and $Br^-$, the separation and mixed solution method were employed. The potential-time curve was obtained by the usual immersion technique and pH effect was also examined. The orders of selectivity for $Br^-$, $Cl^-$ and stability of response time are ${\beta}-Ag_3SI/PVC-THF $membrane > AgI/PVC-THF membrane > copper metal plate membrane. These electrodes could be used as indicating electrodes in the potentiometric titration of a single halide and mixed halides with the standard solution of silver nitrate.

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Flexible quantum dot solar cells with PbS-MIx/PbS-BuDT bilayers

  • Choe, Geun-Pyo;Yang, Yeong-U;Yun, Ha-Jin;Im, Sang-Gyu
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.347.2-347.2
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    • 2016
  • Recently, in order to improve the performance of the colloidal quantum dot solar cells (CQDSCs), various efforts such as the modification of the cell architecture and surface treatment for quantum dot (QD) passivation have been made. Especially, the incorporation of halides into the QD matrix was reported to improve the performances significantly via passivating QD trap states that lower the life-time of the minority-carrier. In this work, we fabricated a lead sulfide (PbS) QD bilayer treated with different ligands and utilized it as a photoactive layer of the CQDSCs. The bottom and top PbS layer was treated using metal iodide ($MI_x$ and butanedithiol (BuDT), respectively. All the depositions and ligand treatments were carried out in air using layer-by-layer spin-coating process. The fabrication of the active layers as well as the n-type zinc oxide (ZnO) layer was successfully carried out on the bendable indium-tin-oxide (ITO)-coated polyethylene terephthalate (PET) substrate, which implies that this technique can be applied to the fabrication of flexible and/or wearable solar cells. The power conversion efficiency (PCE) of the CQDSCs with the architecture of $PET/ITO/ZnO/PbS-MI_x/PbS-BuDT/MoO_x/Ag$ reached 4.2 %, which is significantly larger than that of the cells with single QD (PbS-BuDT) layer.

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Improved methods for the preparation of $(Y_{1-x}Eu_x)_2O_3$:MX and $(Y_{1-x-y}Gd_xEu_y)_2O_3$:MX as red phosphor materials

  • Lee, You-Hui;Han, Sang-Do;Kim, Jung-Duk;Chang, Mi-Yeon;Singh, Ishwar.
    • 한국정보디스플레이학회:학술대회논문집
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    • 2004.08a
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    • pp.715-718
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    • 2004
  • Substantially improved methods for the preparation of europium-doped yttrium oxide red phosphor with the inclusion of alkali metal halides having a general formula $(Y_{1-x}Eu_x)_2O_3$:MX where 0.025${\leq}$x${\leq}$0.2 and MX is alkali halide in the mole ratio 0.025 to 0.6, more preferably between 0.05 to 0.2 mole, are reported. Another series of the red phosphor materials with general formula $(Y_{1-x-y}Gd_xEu_y)_2O_3$:MX where 0.05${\leq}$x${\leq}$0.40 and 0.025${\leq}$y${\leq}$0.20 and MX is alkali halide in the mole ratio 0.025 to 0.5, more preferably between 0.1 to 0.2 mole, has also been presented. The inclusion of alkali halide greatly increase the luminance of the materials. The materials are very soft with fine particle size less than 100nm. The phosphorescent materials have good luminance in VUV region.

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