• Title/Summary/Keyword: Anion substitution

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Synthesis of C-(2-Furyl)-N-(4-nitrophenyl)methanohydrazonyl Bromide. Reactions with Nucleophiles and Active Methylene Compounds

  • Hassaneen, Hamdi M.;Shawali, Ahmad S.;Elwan, Nehal M.;Ibrahim, Al Hossien A.
    • Archives of Pharmacal Research
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    • v.14 no.3
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    • pp.266-270
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    • 1991
  • Synthesis of C-(2-furyl)-N-(4-nitrophenyl)methanohydrazonyl bromide 2 is described. Treatment of 2 with uncleophiles affords the corresponding substitution products 3-7. Also, compound 2 reacts with selenocyanate anion and thiocyanate anion and give the corresponding selenadiazoline and thiadiazoline 8 and 9, respectively. Moreover, reaction of 2 with enolates of various active methylene compounds afforded the pyrazole derivatives 17-20.

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The Chemical Reactions of Superoxide with Halopyrimidines

  • Park Koon Ha;Lee Chang-Ok
    • Bulletin of the Korean Chemical Society
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    • v.10 no.1
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    • pp.104-106
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    • 1989
  • Halopyrimidines such as 2-chloro-, 5-bromo, and 4,6-dichloro-5-nitropyrimidine undergo substitution reactions with superoxide anion radical (superoxide) to give the corresponding hydroxypyrimidines under suitable conditions. Parallel experiments employing hydroxide instead of superoxide strongly indicate that the reactivity of superoxide is comparable to that of the hydroxide in the reaction with halopyrimidines. The results seem to provide a piece of information in favor of the nucleophilic substitution rather than electron-transfer mechanism in the title reaction.

Design and Synthesis of New 3-Allylthio-6-alkylthiopyridazine Analogs via Nucleophillic Substitution Reaction (친핵 치환반응을 이용한 새로운 3-Allylthio-6-alkylthiopyridazine 유도체의 합성과 설계)

  • Park, Hae-Sun;Park, Myung-Sook
    • YAKHAK HOEJI
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    • v.58 no.1
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    • pp.28-32
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    • 2014
  • A new series of 3-allylthio-6-alkylthiopyridazines (3)~(12) was synthesized from dichloropyridazine (1) for development of candidates to retain anticancer activity of human breast cancer. The process involves allythiolation and alkylthiolation from 3,6-dichloropyridazine. 6-Substituted allylthiopyridazines (3)~(12) were prepared from 3-allylthiopyridazinyl chloride (2) via nucleophilic substitution with alkylthiol anion as nucleophile. 3-Allylthiopyridazinyl chloride (2) could be converted to pyridazines (3)~(11) using 1 equivalent of alkyl mercaptan at reflux temperature in methanol. 3,6-Diallylthiopyridazine (12) was synthesized from 3,6-dichloropyridazine (1) using allyl mercaptan (4 equivalent) and sodium hydroxide in methanol. Synthetic compounds were fully identified using NMR, IR, GC-MS data.

An Experimental Study on the Compressive Strength of Cement Mortar mixing Anion Exchange Resin (음이온교환수지 혼입 시멘트 모르타르의 압축강도에 관한 실험적 연구)

  • Jeong, Do-Hyun;Lee, Yun-Su;Lee, Han-Seung
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2018.05a
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    • pp.54-55
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    • 2018
  • Reinforced concrete is a building material that is generally used in modern society. Securing the performance of reinforced concrete is directly connected to the durability and longevity of the building. One of the major factors that deteriorate the durability of concrete is harmful ion. Recently, the quality and improvement method of reinforced concrete for penetration of harmful ion has been studied. In this study, the bead type ion exchange resin is substituted for 0%, 3%, and 6% of the fine aggregate volume in the mortar. The speciments underwent underwater curing and were checked for compressive strengths of 3 days and 28 days. From the results of compressive strength, it can be seen that the higher the substitution ratio of the ion exchange resin, the lower the early strength and long-term strength development, especially the early strength development.

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Control of $NaAlSiO_4:Eu^{2+}$ photoluminescence properties by charge-compensated aliovalent element substitutions

  • Kim, Jihae;Kato, Hideki;Kakihana, Masato
    • Journal of Information Display
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    • v.13 no.3
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    • pp.97-100
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    • 2012
  • We have conducted two kinds of the so-called charge-compensated aliovalent element substitutions to control the photoluminescence properties of $NaAlSiO_4:Eu^{2+}$ with a special focus on the enhancement of the excitation intensity at 400 nm. The aliovalent element substitutions include cation-cation and cation-anion co-substitutions according to the general formulas $Na_{1-x}M_xAl_{1+x}Si_{1-x}O_4:Eu^{2+}$ and $Na_{1-x}M_xAlSiO_{4-x}N_x:Eu^{2+}$ (M = $Mg^{2+}$, $Ca^{2+}$, and $Sr^{2+}$), respectively. The increase in the relative excitation intensity at 400 nm has been achieved in both types of the co-substitutions. Thus, the present research has demonstrated the effectiveness of the charge-compensated element substitution.

Theoretical Studies on the Gas-Phase Nucleophilic Aromatic Substitution Reaction

  • Lee, Ik-Choon;Park, Hyoung-Yeon;Bon-Su Lee
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.658-661
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    • 1991
  • The gas-phase nucleophilic substitution reaction of pentafluoroanisole with $OH^-$ and ${NH_2}^-$ nucleophiles have been studied theoretically using the AM1 method. Three reaction channels, $S_N2$, IPSO and $S_NAr$ (scheme 1), are all very exothermic so that all are accessible despite the varying central energy barriers which are much lower than the reactants level. In the IPSO and $S_NAr$ channels, the reactants form directly a stable ,${\sigma}$-anion complex which proceeds to form a proton transfer complex via a transition barrier corresponding to a loose ${\pi}$-type complex with the F-(or ${OCH_3}^-$) leaving group. Due to a greater number of probable reaction sites available for $S_NAr$ compared to the other two processes, the $S_NAr$ channel is favored as experimentally observed.

Nucleophilic Substitution Reactions of Thiophenyl Phenylacetate with Benzylamines in Acetonitrile

  • 오혁근;김선경;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.20 no.9
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    • pp.1017-1020
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    • 1999
  • The aminolysis reactions of thiophenyl phenylacetates with benzylamines are investigated in acetonitrile at 55.0℃. Relatively large selectivity parameters, βx≒ 1.5, βz = -1.5~-1.8 and βxz = 0.92 together with the valid reactivity-selectivity principle are consistent with stepwise acyl transfer mechanism with rate limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T ± . The first order kinetics with respect to the benzylamine concentration and the realtively large secondary kinetic isotope effect (kH / kD = 1.2-1.7) involving deuterated benzylamine nucleophiles suggest a four center type transition state in which concurrent leaving group departure and proton transfer are involved.

Effects of Sulfur Substitution on Chemical Bonding Nature and Electrochemical Performance of Layered LiMn0.9Cr0.1O2-xSx

  • Lim, Seung-Tae;Park, Dae-Hoon;Lee, Sun-Hee;Hwang, Seong-Ju;Yoon, Young-Soo;Kang, Seong-Gu
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1310-1314
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    • 2006
  • Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

Theoretical Studies on the Nucleophilic Substitution Reaction of Methyl Thiocyanate (티오시안산 메틸의 친핵성치환 반응에 관한 이론적 연구)

  • Ikchoon Lee;Chang Hyun Song
    • Journal of the Korean Chemical Society
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    • v.31 no.2
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    • pp.123-132
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    • 1987
  • Nucleophilic substitution reactions of methylthiocyanate(MTC) with anion nucleophiles,$SH^-,\;CN^-$ and $OH^-$, have been investigated using MNDO method. For the three reaction centers of MTC, gas-phase and solution-phase selectivities are discussed for each nucleophile by considering potential energy profiles calculated(intrinsic term) and magnitudes of negative charge on the nucleophile at the transition state(solvation term). It was found that both components of the selectivity for $SH^-$agreed with the experimental results obtained for 4-methylbenzylthiocyanate (4-MBTC), but the selectivity order for TEX>$CN^-$ was found to agree only with that of the intrinsic term and that of $OH^-$disagreed with any theoretical selectivity order. The MNDO optimized geometries for all species at the stationary points are reported.

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A Study on the physical Property of the Bio Concrete (바이오콘크리트의 물리적 특성에 관한 연구)

  • Lee, Jong-Chan;Lee, Sea-Hyun;Park, Young-Shin;Park, Jae-Myung
    • Proceedings of the Korea Concrete Institute Conference
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    • 2006.05b
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    • pp.509-512
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    • 2006
  • We have many environmental problems by the polluted materials as a results of mechanical development these days. So people want to use building products made from natural things and take a good effect for people from those bio products. We can instance electron wave shelding, far infrared ray and anion emission, and anti-bacterial property as the latest trend of the bio building material. So we had a experiment to investigate how much bio materials affect concrete when we use in the concrete with cement substitution. We tested slump, 7days compressive strength, and air contents for physical properties of bio concrete. The result is that bio concretes with four bio ingredients have proper values comparing with target values for slump and air content but lower compressive strength than plain concrete.

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