• 제목/요약/키워드: $S_N2-S_N2'$ Reaction

검색결과 1,102건 처리시간 0.18초

Studies on the Quaternization of Tertiary Amines (Ⅳ). Kinetics and Mechanism for the Reaction of Substituted Phenacyl Tosylates with Substituted Pyridines

  • Lee, Oh-Seuk;Yoh, Soo-Dong
    • Bulletin of the Korean Chemical Society
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    • 제6권2호
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    • pp.99-102
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    • 1985
  • Substituent effects of substrate and nucleophile for the reaction of substituted phenacyl tosylates with pyridines were determined conductometrically in acetonitrile. Activation parameters for these reactions were also calculated. The substituent effects in nucleophile were increased with electron-donating power of pyridines and Br${\o}$nsted linear relationship was shown. Rate constant was increased by both electron-donating and electron-attracting groups in the substrate. It seems that dissociative S$_{N}$2 ("loose" transition state) mechanism is operating in the case of electron-donating substituents while associative S$_{N}$2 ("tight" transition state) mechanism is operative in the case of electron-attracting substituents.

$HgGa_2S_4:CO^{2+}$ 단결정의 불순물 광흡수 (Impurity optical absorption of $HgGa_2S_4:CO^{2+}$ single crystals)

  • 김형곤;김남오;김병철;최영일;김덕태;현승철;방태환;이경섭;구할본
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2004년도 춘계학술대회 논문집
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    • pp.3-7
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    • 2004
  • $HgGa_2S_4:CO^{2+}$ single crystal were grown by the chemical transport reaction(CTR) method. 1n the optical absorption spectrum of the $HgGa_2S_4:CO^{2+}$ single crystal measured at 298K, three groups of impurity optical absorption peaks consisting of three peaks, respectively, were observed at 673nm, 734nm, and 760nm, 1621nm, 1654nm, and 1734nm, and 2544nm, 2650nm, and 2678nm. At 10K, the three peaks(673nm, 734nm, and 760nm) of the first group were split to be twelve peaks. These impurity optical absorption peaks are assigned to be due to the electronic transitions between the split energy levels of $Co^{2+}$ sited in the $S_4$ symmetry point.

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XPS를 이용한 Cu/Polyimide와 Cu/TiN 계에 대한 연구

  • 이연승
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2000년도 제18회 학술발표회 논문개요집
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    • pp.169-169
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    • 2000
  • 최근 반도체 소자의 초고집적화 현상에 따라 기존의 Al-base 합금에 대한 한계에 달하면서 그에 대한 대체 물질로 Cu가 관심을 모으게 되었고 그럼으로써 Cu metallization을 위한 많은 연구가 진행되어 왔다. Cu는 Al-base 합금계보다 비저항이 낮고, 녹는점이 높으며, 또한 electromigration 특성이 뛰어난 것으로 알려져 있다. 공학적인 면에서 이미 이들 계에 대한 adhesion 및 전기적 특성에 대한 많은 연구가 있어왔지만, 이들 특성 변화에 대한 물리적 의미를 제공할 만한 기초 자료들이 부족한 상태이다. 본 연구에서는 부도체인 polyimide 박막과 diffusion barrier인 TiN 박막위에서의 Cu 박막성장에 따르는 interface chemical reaction의 변화를 XPS를 이용하여 관찰함으로서 이들 계에 있어서의 adhesion과의 관계를 조사하였다. 그리고 XPS를 이용한 modified surface accumulation method를 적용시켜 TiN diffusion barrier를 통한 Cu의 grain boundary diffusion 상수들을 측정하였다. Cu/TiN system의 경우에는 interface chemical reaction이 일어나지 않았지만 Cu/polymide system에 있어서는 boundary diffusivity는 특히 40$0^{\circ}C$에서 $650^{\circ}C$ 영역에서, Db=60$\times$10-11exp[-0.29/(kBT)]cm2/sec 이었다.

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Selective Synthesis of a New Macropolycycle Containing One N-CH2-N Linkage and Its Reaction with Cu2+ and Ni2+ Ions in Methanol

  • Kang, Shin-Geol;Kweon, Jae-Keun;Jeong, Gyeong-Rok;Lee, Uk
    • Bulletin of the Korean Chemical Society
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    • 제29권10호
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    • pp.1905-1910
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    • 2008
  • The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.0$0^{1.18}.0^{7.12}$]docosane ($L^1$) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.$1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^7$) containing one 1,3-diazacyclohexane subunit. In methanol, $L^7$ readily reacts with $Cu^{2+}$ ion to form [$CuL^7(H_2O)$]$^{2+}$ which is extremely inert against methanolysis. In the solution containing $Ni^{2+}$ ion, however, $L^7$ reacts with methanol to yield [$NiL^3$]$^{2+}$ ($L^3$ = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.$0^{1.18}.0^{7.12}$]- docosane), in which one N-$CH_2OCH_3$ pendant arm is appended. The copper(II) complex [$CuL^7(H_2O)$]- $(ClO_4)_2{\cdot}3H_2O\;(I{\cdot}3H_2O)$ has a severely distorted trigonal bipyramidal coordination geometry with a 4-5- 6-5 chelate ring sequence. The crystal structure of [$NiL^3$]$(PF_6)_2{\cdot}2H_2O$ (IIb) shows that the N-$CH_2OCH_3$ pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [$NiL^3$(S)]$^{2+}$, in which the N-$CH_2OCH_3$ group as well as S is coordinated to the metal ion, and [$NiL^3$]^{2+}.

S$_N$2 Transition State Variation in the Benzenesulfonyl Chloride Sovolysis$^*$

  • Lee, Ik-Choon;Koo, In-Sun;Kang, Han-Keun
    • Bulletin of the Korean Chemical Society
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    • 제2권2호
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    • pp.41-45
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    • 1981
  • For solvolyses of benzenesulfonylchlorides we determined transfer enthalpies of transition states, and solvent (TFE + EtOH) and substituent effects on rates. We have used the More O'Ferrall plots to show that transition states variation caused by solvent and substituent changes is consistent with an associative $S_N2$ mechanism for the nucleophilic substitution reaction of benzenesulfonylchlorides.

녹조류 Chlamydomonas reinhardtii의 (CA/GT)n Simple Sequence Repeat DNA 다형현상 ((CA/GT)n Simple Sequence Repeat DNA Polymorphism in Chlamydomonas reinhardtii)

  • 강태진;양덕춘
    • 식물조직배양학회지
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    • 제24권2호
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    • pp.113-117
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    • 1997
  • Simple sequence repeats (SSR)는 진핵생물체에 널리 산재되어 있으며, 큰 다형현상을 나타내고, polymerase chain reaction (PCR)으로 쉽게 분석된다. 이 연구의 목적은 서로 다른 Chlamydomonas reinhardtii계통간의 다형현상과 Chlamydomonas의 SSR 좌위에서의 유전양상을 결정하는데 있었다. C. reinhardtii의 genomic DNA library를 만들어 $^{32}$P로 라벨링한 (AC)$_{11}$ probe를 이용하여 (CA/GT)n 반복서열을 가지는 clone을 선택하기위해 screen하였다. 선택된 clone을 sequencing하여 (CA/GT)n sequence에 인접한 PCR primer set를 제조하였다. PCR은 여러 C. reinhardtii 계통의 SSR 좌위를 증폭하기 위하여 사용하였다. 그 좌위는 및몇 C. reinhardtii 계통에서 다형현상을 보였다. 그러나 그 좌위에서 C. reinhardtii의 6계통중 4계통만 DNA가 PCR 증폭을 하였고 2계통은 증폭을 하지 않았다. C. reinhardtii와 C. smithii의 교배로 생긴 4배체에서 2:2의 분리비를 보여주었는데, 이는 단순한 멘델의 유전양상을 나타낸다. 이러한 결과로 미루어 SSR 다형현상은 Chlamydomonas의 개체 식별, 개체군 연구, 연쇄 분석, 그리고 유전자 지도 작성을 하는데 유용할 것이다.다.

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Deep Desulfurization of Fuels by Heteropolyanion-Based Ionic Liquid

  • Li, Jinlei;Hu, Bing;Hu, Chuanqun
    • Bulletin of the Korean Chemical Society
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    • 제34권1호
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    • pp.225-230
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    • 2013
  • A new heteropolyanion-based ionic ($[Hmim]_5PMo_{10}V_2O_{40}$) was synthesized by the reaction of molybdovanadophosphoric acid ($H_5PMo_{10}O_{40}$) with N-methylimidazole. [$[Hmim]_5PMo_{10}V_2O_{40}$ showed a high catalytic activity in the oxidative desulfurization of sulfur-containing compounds in 1-methylimidazolium tetrafluoroborate ($[Hmim]BF_4$) ionic liquid using 30% aqueous $H_2O_2$ as the oxidant. The catalytic system was of high activity, simplified workup and flexible recyclability. The catalytic oxidation reactivity of sulfur-containing compounds decreased in the order dibenzothiophene (DBT) > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The influences of various parameters including reaction time (t) and temperature (T), catalyst dosage, and oxidant to sulfur molar ratio n(O)/n(S) on the desulfurization of model oil were investigated in details. 99.1% of DBT conversion in the model oil was achieved at atmospheric pressure under the optimal conditions: n(O)/n(S) = 4:1, $60^{\circ}C$, 100 min and molar ratio of catalyst to sulfur of 0.062. The ionic liquid can be recycled six times without significant decrease in activity.

Synthesis and Antitumor Activity of New Anthracycline Analogues

  • ;김완중;유동진;강현수;장순량
    • Bulletin of the Korean Chemical Society
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    • 제22권9호
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    • pp.963-968
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    • 2001
  • New anthracycline analogues 2-9 as potential anticancer agents have been synthesized from daunomycin (1a) and doxorubicin (1b). Compounds 2 and 6 were prepared by the nucleophilic displacement type esterification of 14-bromodaunomycin (1c) with N-benzoyl-(2R,3S)-phenylisoserine and L-pyroglutamic acid in triethyl-amine, respectively. Compounds 3, 7 and 4, 8 were prepared by the reaction of either daunomycin (1a) or doxorubicin (1b) with one equivalent of the corresponding acids in the presence of EDCI/PP. Compounds 5, 9 were obtained from 1b by reaction with 2.2 equivalents of the corresponding acids in the same manner. The cytotoxic activities of the analogues in comparison with adrimycin on cultured SNU-16 and MCF7 cell were described.

Density Functional Study on [3+2]-Dipolar Cycloaddition Reaction of the N-heterocyclic Carbene Boryl Azide with Olefins

  • Zhang, Xing-Hui;Wang, Ke-Tai;Niu, Teng;Li, Shan-Shan
    • Bulletin of the Korean Chemical Society
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    • 제35권5호
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    • pp.1403-1408
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    • 2014
  • The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity.

고압하에서의 이소퀴놀린과 브롬화 벤질류의 반응에 관한 속도론적인 연구 (Kinetic Study on the Reaction of para-substitued Benzylbromide with Isoquinoline under High Pressure)

  • 김영철;임종완;최성용
    • 대한화학회지
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    • 제42권2호
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    • pp.150-155
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    • 1998
  • Acetonitrile 용매내에서 isoquinoline과 치한된 benzylbromide의 반응을 압력변화(1~1000bar)에 따라 반응속도론적으로 연구하였다. 속도상수로부터 활성화파라미터들을 TEX>$\(DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq},Ea)$구하였다. 온도가 증가함에 따라 속도상수는 증가 하고, TEX>$\DeltaV^{\neq}, \Delta\beta^{\neq},및 \DeltaS^{\neq}$는 모두 음의 값으로 나타내었다. 치환기효과와 실험 결과로 부터 반응메카니즘을 고찰한 결과 전체적인 반응은 $S_{N}2$반응 메카니즘으로 진행되나, 치환체와 압력변화에 따라 전이상태 구조에 약간의 변화가 있었다.

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