• Title/Summary/Keyword: Substitution reaction

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자연환경 변화와 광물의 역할

  • 김수진
    • Proceedings of the Petrological Society of Korea Conference
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    • 2000.05a
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    • pp.3-11
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    • 2000
  • The earth environment consists of four spheres : geosphere, hydrosphere, atmosphere and biosphere. The geosphere consists mostly of minerals. It, however, contains some water and air in its shallow depth. Although hydrosphere and atmosphere consist predominantly of water and air, respectively, both contain some minerals. The biosphere consisting of various organisms is present in the interfaces of geosphere, hydrosphere and atmosphere. The natural environment of the earth is continuously changing by the interaction of four spheres. It suggests that out relevant environmental problems can not be revolved without understanding the natural relationship of these four spheres. Minerals in our environment are very important because they are the main constituent materials of the earth and they control our environment. The roles of minerals in our environment have not been understood even in the scientific society. Thus their roles have been neglected. Review of studies on the environmental mineralogy so far made at our laboratory and others show that minerals control the environment in various ways. Minerals neutralize the acid water as well as acid rain. Minerals in soils and rocks are major neutralizer of the acid rain. Salinization of sea water is attributed to the ionic substitution between minerals and sea water. Some minerals control the humidity of the air. Corals, the products of biomineralization, are the main carbon controller of the air. Minerals also adsorb heavy metals, organic pollutants and radioactive nuclides. Such remarkable functions for controlling the environment come from the mineral-water reaction and biomineralization. All these phenomena are subjects of the environmental mineralogy, a new field of earth science.

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Kinetics and Mechanism of the Pyridinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.270-274
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    • 2012
  • The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1c) with X-pyridines are investigated kinetically in acetonitrile at $-25.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 1c with a cyclic five-membered ring is $2.70{\times}10^5$ times faster than its acyclic counterpart (1a: phenyl ethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}$ = +26 eu) compared to negative value of 1a (${\Delta}S^{\neq}$= -24 eu) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=20.5kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=12.7kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater selectivity parameters (${\rho}_X$ = -1.99 and ${\beta}_X$ = 0.41) with the strongly basic pyridines compared to those (${\rho}_X$ = -0.42 and ${\beta}_X$ = 0.07) with the weakly basic pyridines.

Nucleophilic Substitution at a Carbonyl Carbon Atom (Ⅷ). Kinetics and Mechanism of the Reactions of Chloroformates with Substituted Anilines and Halides (카르보닐 탄소원자의 친핵성 치환반응 (제8보). 염화포름산물과 치환아닐린 및 할라이드와의 반응에 관한 속도론적 연구)

  • Cho Won-Jei;Kim Jack C.;Lee Euk-Suk;Lee Ikchoon
    • Journal of the Korean Chemical Society
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    • v.20 no.6
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    • pp.453-459
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    • 1976
  • Rate constants for the reaction of methyl chloroformate with substituted anilines, and for the halogen exchanges in phenyl chloroformate have been determined in acetone. Although the rate data can be interpreted equally well with the addition-elimination mechanism($S_AN$) involving an intermediate, results of MO and isotope effect studies strongly favor the synchronous ($S_N2$) mechanism for the reactions studied. It was concluded that for the fast reacting nucleophiles the transition state is of "late" type while for the slow reacting nucleophiles it is of "early" type.

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Nucleophilic Substitution at a Carbonyl Carbon Atom (V). Kinetic Studies on Halogen Exchange Reactions of N,N-Dialkylcarbamoyl Chlorides in Dry Acetone (카르보닐 탄소원자의 친핵치환 반응 (제5보). 아세톤 용매속에서의 Dialkylcarbamoyl Chloride의 할로겐 교환반응에 관한 속도론적 연구)

  • Kim Shi Choon;Lee, Ik Choon
    • Journal of the Korean Chemical Society
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    • v.19 no.1
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    • pp.11-15
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    • 1975
  • Kinetic study of halogen exchange for N,N-dimethylcarbamoyl chloride and N,N-diethylcarbamoyl chloride in acetone by using radioisotopic halide ions has been carried out at two temperatures as a part of studying the reactivity of carbonyl carbon atom. The order of nucleophilicity showed a similar tendency as that for alkyl chloroformate, but reaction rate is much slower than that for solvolysis and alkyl chloroformate. The activation parameters,${\Delta}H^*$and${\Delta}S^*$ were found to decrease in sequence $Cl^{\rightarrow}Br^{\rightarrow}I^-$ for N,N-dialkylcarbamoyl chlorides. The results are interpreted in terms of solvation effect, degree of bond-breaking and bond-formation and electronic requirements.

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Kinetics and Mechanism of Pyridinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.483-488
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    • 2014
  • The nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $35.0^{\circ}C$. The Hammett and Bronsted plots with X in the nucleophiles for both substrates exhibit biphasic concave upwards with a break region between X = 3-Me and H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are negative with 8 while positive with 10 despite the same free energy correlations with X for both substrates. A stepwise mechanism with a rate-limiting bond formation is proposed with 8, whereas a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed with 10 based on the sign of ${\rho}_{XY}$, negative and positive with 8 and 10, respectively. A frontside nucleophilic attack is proposed with strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values while a backside attack is proposed with weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$ for both substrates.

Comparison of Photocyclization Reactions of Fluoro- vs Nonfluoro-Substituted Polymethyleneoxy Donor Linked Phthalimides

  • Park, Hea Jung;Ryu, Young Ju;Kim, Kyung Mok;Yoon, Ung Chan;Kim, Eunae;Sohn, Youngku;Cho, Dae Won;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1108-1114
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    • 2013
  • Photochemical reactions of fluoro- vs. nonfluoro-substituted polymethylenoxy chain linked phthalimide were carried out to explore how electronegative fluorine atoms inside the donor chain influence photocyclization reaction efficiencies and to briefly determine the alkali metal binding properties of the photoproducts. The results of this study show that the fluorine-substituted donor chain linked phthalimide undergoes inefficient photocyclization via single electron transfer (SET)-induced excited state pathways to generate 14-membered cyclic amidol compared to nonfluoro-analog due to low electron donor ability of the terminal oxygen donor site. These results show that photoinduced intramolecular SET processes arising from ${\alpha}$-silyl ether electron donors to phthalimides are largely dependent on the kinds of substituents inside donor chain. Finally, a preliminary study with the cyclic amidols generated in this effort showed that they have weak alkali metal cation binding properties regardless of absence/presence of fluoro-substituents.

The substitution effect of Langasite $(La_3Ga$_5SiO_{14})$-type compound, $Ca_3TaGa_3Si_2O_{14}$ crystals on their synthesis and crystal growth (Langasite$(La_{3}Ga$_{5}SiO_{14})$-type 인 $Ca_{3}TaGa_{3}Si_{2}O_{14}$ 결정의 합성과 경정성장에서의 치환효과)

  • Young Suk Kim;Keun Ho Auh
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.11 no.6
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    • pp.285-289
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    • 2001
  • We investigated that each site was substituted by new chemical components in Langasite ($La_3Ga_5/SiO_{14}$)-type structure with superior piezoelectric characteristics than $La_3Ga_5/SiO_{14}$. In this study $Ca_3TaGa_5Si_{2}O_{14}$ was synthesized by soilid-state reaction and grown by the $\mu$-PD(micro-pilling-down)and Cz technique. Lattice parameter and chemical composition was investigated by XRD and EPMA respectively.

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Synthesis and Characterization of Di and Triblock Copolymers Containing a Naphthalene Unit for Polymer Electrolyte Membranes (고분자전해질 막을 위한 나프탈렌 단위를 포함하는 디 및 트리 블록공중합체의 합성 및 특성분석)

  • KIM, AERHAN
    • Transactions of the Korean hydrogen and new energy society
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    • v.27 no.6
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    • pp.660-669
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    • 2016
  • A fluorinated-sulfonated, hydrophobic-hydrophilic copolymer was planed subsequently synthesized using typical nucleophilic substitution polycondensation reaction. A novel AB and ABA (or BAB) block copolymers were synthesized using sBCPSBP (sulfonated 4,4'-bis[4-chlorophenyl)sulfonyl]-1,1'-biphenyl), DHN (1,5-dihydroxynaphthalene), DFBP (decafluorobiphenyl) and HFIP (4,4'-hexafluoroisopropylidenediphenol). All block copolymers were easily cast and made into clear films. The structure and synthesized copolymers and corresponding membranes were analyzed using GPC (gel permeation chromatography), $^1H$-NMR ($^1H$ nuclear magnetic resonance) and FT-IR (Fourier transform infrared). TGA (Thermogravimetric analysis) and DSC (differential scanning calorimetry) analysis showed that the prepared membranes were thermally stable, so that elevated temperature fuel cell operation would be possible. Hydrophobic/hydrophilic phase separation and clear ionic aggregate block morpology was confirmed in both triblock and diblock copolymer in AFM (atomic force microscopy), which may be highly related to their proton transport ability. A sulfonated BAB triblock copolymer membrane with an ion-exchange capacity (IEC) of 0.6 meq/g has a maximum ion conductivity of 40.3 mS/cm at $90^{\circ}C$ and 100% relative humidity.

Phase criterion of the feedback cycle of edgetones (쐐기소리의 되먹임 사이클의 위상조건)

  • Gwon, Yeong-Pil
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.20 no.3
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    • pp.1106-1113
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    • 1996
  • The phase criterion of the feedback cycle of low-speed edgetones has been obtained using the jet-edge interaction model which is based on the substitution of an array of dipoles for the reaction of the wedge to the impinging jet. The edgetone is produced by the feedback loop between the downstream-convected sinuous disturbance and upstream-propagating waves generated by the impingement of the disturbance on the wedge. By estimation of the phase difference between the downstream and the upstream disturbances, the relationship between the edge distance and the wavelength is obtained according to the phase-locking condition at the nozzle lip. With a little variation depending on the characteristics of jet-edge interaction, the criterion can be approximated as follows: h/.LAMBDA. + h/.lambda. = n - 1/4, where h is the stand-off distance between the nozzle lip and the edge tip, .LAMBDA. is the wavelength of downstream-convected wave, .lambda. is the wavelength of the upstream-propagating acoustic wave and n is the stage number for the ladder-like characteristics of frequency. The present criterion has been confirmed by estimating wavelengths from available experimental data and investigating their appropriateness. The above criterion has been found to be effective up to 90.deg. of wedge angle corresponding to the cavitytones.

High Yielding [18F]Fluorination Method by Fine Control of the Base

  • Lee, Sang-Ju;Oh, Seung-Jun;Chi, Dae-Yoon;Moon, Dae-Hyuk;Ryu, Jin-Sook
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2177-2180
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    • 2012
  • New [$^{18}F$]F-fluorination methods using a minimized amount of precursor has been developed by controlling the base concentration. In the first method, pre-conditioning of the anion exchange cartridge with $K_2CO_3$ solution or water was carried out. The trapped [$^{18}F$]fluoride on the cartridge was then eluted by KOMs or KOTf solution. [$^{18}F$]F-Fluorination could be performed without additional base. In the second method, the QMA cartridge was preconditioned with KOMs solutions. Trapped [$^{18}F$]fluoride on the QMA was then eluted with KOMs and additional base, such as KOH, $K_2CO_3$, and $KHCO_3$, was added into the reaction vessel. Method 1 showed a [$^{18}F$]F-incorporation yield of 20.9% for [$^{18}F$]FLT synthesis with 5 mg of precursor. Unlike method 1, a [$^{18}F$]F-incorporation yield of 91.4% was achieved from the same amount of precursor in method 2.