• Title/Summary/Keyword: halogen-halogen exchange

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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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Kinetic Studies on Halogen Exchange of Substituted Benzenesulfonylbromides

  • Kim, Jaerok
    • Nuclear Engineering and Technology
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    • v.5 no.4
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    • pp.321-333
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    • 1973
  • The rates and activation parameters for the halide exchange reactions of substituted benzenesulfonylbromides (R-C$_{6}$H$_4$SO$_2$Br, R=p-MeO, p-$CH_3$, p-H, p-NO$_2$) in dry acetone at two temperatures were determined. It was found that the nucleophilicity order of Cl->I-$\geq$Br- for strong electron withdrawing-, and mild electron donating group, and of I-$\geq$Cl->Br- for strong electron donating group, Hammett plots showed slightly convoked characteristics which is similar to the plots of substituted benzenesulfonylchlorides, but contrary to the concaved nature for the halide exchange reactions of substituted benzyl chlorides. The rate of halogen exchange between benzenesulfonylbromide and lithium bromide decreased in the order of solvent : ($CH_3$)$_2$CO>$CH_3$CN》MeOH. The rates and activation parameters were also compared with those already known in the substituted benzenesulfonylchlorides. Theses were explained in terms of the structural properties of the transition state, and discussed the reaction mechanisms.s.

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Synthesis and Characterization on Acetonitrile and DMAP Complexes of Indium(III) compounds (Indium(III) 화합물의 Acetonitrile 과 DMAP 착물의 합성 및 특성)

  • Choi, Zel Ho
    • Journal of the Korean Chemical Society
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    • v.42 no.2
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    • pp.184-189
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    • 1998
  • Tris(pentafluorophenyl)indium acetonitrile complexes have been prepared from the reaction of Indium trihalides (halogen=Cl, Br) and bis(pentafluorophenyl)cadmium in acetonitrile, and characterized by elementary analysis, $^13C{^1H}-,\; ^1H-\;and\; ^{19}F-NMR$ spectroscopy and mass spectrometry. The Indium (III) compounds were formed stable 1:1 adducts with acetonitrile. $In(C_6F_5)_3{\cdot}DMAP$ has been prepared from the ligand exchange reaction of In$(C_6F_5)_3 {\cdot} CH_3CN$ with DMAP in $CH_2Cl_2 {\cdot} DMAP$ has higher donating character and replaced the $CH_3CN$ through the ligand transfer reaction.

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Atom Transfer Radical Polymerization of [Poly(ethylene glycol)methyl ether] Methacrylate Using an Amide-Based Initiator (아미드기를 가지는 개시제를 이용한 [Poly(ethylene glycol)Methyl Ether] Methacrylate의 원자 이동 라디칼 중합)

  • Lee, Hyo-Kyung;Lee, Sun-Gu;Paik, Hyun-Jong
    • Polymer(Korea)
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    • v.31 no.6
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    • pp.550-554
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    • 2007
  • Atom transfer radical polymerization (ATRP) has been widely used in bioconjugation as it is an efficient and facile method to prepare polymers with pre-designed structures. Quite often, bioconjugation with proteins employs primary amines in proteins as a functional group to attach an initiator. When 2-bromoisobutryl bromide, the most widely used precursor for ATRP initiator, is used, ${\alpha}-halo$ amide initiating groups are formed in the proteins, which are known to exhibit slow initiation behavior in the ATRP process. Here we studied the ATRP of [poly(ethylene glycol)methyl ether] methacrylate (PEGMA) using amide-based initiator. PEGMA differs for both the nature and size of the polymer side branches and shows good solubility in water and a property that made it an ideal candidate for biomaterials. While normal ATRP produced ill-defined p(PEGMA) with amide based initiators, the halogen exchange method and the external additional of deactivator effectively improved the control of ATRP of PEGMA.

Kinetic Studies of Chlorine Exchange between Benzyl Chloride and Radioactive Chloride Ion (Benzyl Chloride의 Chlorine 交換反應)

  • Park, Yong-Ja;Lee, Ik-Choon
    • Journal of the Korean Chemical Society
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    • v.9 no.1
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    • pp.23-28
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    • 1965
  • Halogen exchanges between benzyl chloride and chloride ion have been studied in 90% ethanol-water mixture, and activation parameters in the exchange reaction have been determined; ${\Delta}H^{\neq}$ = 18. 50 Kcal and ${\Delta}S^{\neq}$ = -22. 09 e. u. Results indicated that the reaction proceeded via a typical bimolecular mechanism. The importance of nucleophilic ability of attacking anion in $S_N2$ process has been stressed giving some experimental evidence. The order of reactivity of halides in the exchange reaction is better explained with the Swain's nucleophilic parameter than with the bond dissociation energies.

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Preparation and Gas Characterization of Poly(phenylene oxide) Containing Imidazolium (이미다졸륨을 포함하는 폴리페닐렌옥사이드 고분자 제조 및 기체 특성평가)

  • Son, Tae Yang;Jo, Jin Woo;Kim, Ji Hyeon;Kim, Tae Hyun;Tocci, Elena;Nam, Sang Yong
    • Membrane Journal
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    • v.27 no.6
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    • pp.528-535
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    • 2017
  • In this study, halogen element was introduced into polyphenylene oxide polymer using bromination reaction, and then halogen element was replaced with imidazolium. Imidazolium corporated polyphenylene oxide polymer was synthesized and the synthesis was confirmed by various instrumental characterization. In addition, gas permeation properties of $O_2$, $N_2$, $CO_2$ were studied with different imidazolium contents. As the content of imidazolium increased, the ion exchange capacity increased and the mechanical strength decreased. The gas permeance showed a tendency to decrease slightly with increaing imidazolium contents. Whereas, it was confirmed that the tendency of $CO_2/N_2$ ideal selectivity increased as the imidazolium contents increased.

Halogen Exchange Reactions of Benzyl Halides Part Ⅱ-Kinetics of Reactions of Iodide Ion with Benzyl Chloride and Bromide in 90% Ethanol-water (벤질 할라이드의 할로겐 교환반응 (제Ⅱ보) 90% 에탄올 용액에서의 염화 및 브롬화 벤질과 요오드화 이온 간의 교환반응 속도)

  • Lee Bon-su;Whangbo Myung Hwan;Lee Ik Choon
    • Journal of the Korean Chemical Society
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    • v.13 no.2
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    • pp.103-108
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    • 1969
  • 전보에 이어 90% 에탄올 용액에서의 염화 벤질 및 브롬화 벤질과 요오드화 이온 간의 교환반응을 연구하였다. HSAB이론을 도입하여 할로겐화 이온의 pb혼합 궤도가 서로 겹치는 전이 상태로서 실험 결과를 설명하였다.

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Kinetic Studies on Halogen Exchange of 1-Naphthyl Methyl Halides (1-나프틸메틸 할라이드의 할로겐 교환반응)

  • Lee Kae-Soo
    • Journal of the Korean Chemical Society
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    • v.13 no.2
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    • pp.115-120
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    • 1969
  • Kinetics of reactions of halide ions with 1-naphthyl methyl halide have been investigated in anhydrous acetone. Semi-quantitative analysis of the results shows that if the softness of the substrate increases remarkably, the nucleophilicity order of halide ions is $I^- > Br^- > Cl^-$ even in dipolar aprotic solvent. But for 1-naphthyl methyl bromide, though the reaction center which was made soft by symbiosis of bromine atom raises the reactivity of soft nucleophile, nucleophilicity order indicates that soft-soft interaction is interfered by perihydrogen.

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Analysis of Temperature Distribution of the Glass Panel in the Infrared Heating Chamber (적외선 가열로에서 가열되는 유리 패널의 온도분포 해석)

  • Lee, Kong-Hoon;Kim, Ook-Joong;Ha, Su-Seok;Kang, Sae-Byul;Lee, Joon-Sik
    • Proceedings of the KSME Conference
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    • 2003.11a
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    • pp.278-283
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    • 2003
  • Analysis has been carried out to investigate the temperature variation and the uniformity of the temperature distribution of the glass panel by infrared radiant heating. Halogen lamps are used to heat the panel and located near the top and bottom of the rectangular chamber. The thermal energy is transfered only by radiation and the radiation exchange occurs only on the solid surfaces and is considered by using the view factor. The results show that the uniformity of the temperature distribution of the panel is improved but the time for heating increases as the wall reflectivity is large. The temperature difference reaches a maximum in the early stage of the heating process and then decreases until it reaches the uniform steady-state value.

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Copper(II) Oxyanion Complexes Derived from Sparteine Copper(II) Dinitrate: Synthesis and Characterization of 4- and 5-Coordinate Copper(II) Complexes

  • Lee, Yong-Min;Kim, Yong-Kyu;Jung, Hee-Cheul;Kim, Young-Inn;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.23 no.3
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    • pp.404-412
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    • 2002
  • Nine copper(Ⅱ) oxyanion, and mixed oxyanion complexes that have four- or five-coordinate geometries around copper(Ⅱ) centers were derived from sparteine copper(Ⅱ) dinitrate precursor [Cu($C_{15}$$H_{26}$N2)(NO3)2]. The precursor complex undergoes an anion exchange with various oxyanions, and an interchange reaction with other sparteine copper(Ⅱ) complexes. The [Cu($C_{15}$$H_{26}$N2)(CH3CO2)2] also undergoes "halogen atom abstraction" reaction with CCl4 to produce the mixed anion complex [Cu($C_{15}$$H_{26}$N2)(CH3CO2)Cl]. The whole set of prepared complexes has been used for the comparative electrochemical and spectroscopic studies.