• 제목/요약/키워드: $S_{N}2$ mechanism

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가스 크로마토그라피에 의한 아미노산 광학 이성질체의 분리(III) -(S)-5-isobutyl-$N^3$-phenyl-2-thiohydantoin의 광학 활성 고정상으로의 응용- (Separation of Amino Acid Enantiomers by Gas Chromatography (III) -(S)-5-isobutyl-$N^3$-phenyl-2-thiohydantoin as chiral stationary phase-)

  • 박만기;양정선;고창범
    • 약학회지
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    • 제32권2호
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    • pp.112-116
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    • 1988
  • The resolution of N-trifluoroacetyl (N-TFA) ter-isopropylesters of Ala, Ile, Leu, Val and Phe by gas chromatography on the (S)-5-isobutyl-$N^3$-phenyl-2-thiohydantoin as stationary phase was investigated. The phase was employed at several column temperatures $(140^{\circ}C{\sim}200^{\circ}C)$ and the separation factors were $1.18{\sim}1.45$ range for five amino acid enantiomers. The possible mechanism of chiral recognition was investigated by NMR technique and the association constant$(K_c)$ was calculated as 201.3(r=0.98) for alanyl derivative.

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C. I. Disperse Blue 79의 알칼리 가수분해 반응속도 및 반응메카니즘 (Kinetics and Mechanism for Alkaline Hydrolysis of C. I. Disperse Blue 79)

  • 박건용;박창혁;박병기
    • 한국염색가공학회지
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    • 제13권5호
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    • pp.312-319
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    • 2001
  • Kinetics and mechanism for alkaline hydrolysis of C. I. Disperse Blue 79(B-79) which is 4-N, N- diacetoxyethyl -2- acylamino-5-ethos y -2'-bromo-4',6'-dinitroazobenzene were investigated. The color strength of B-79 in acetone/water solutions of various NaOH concentrations decreased continuously. The hydrolysis rate of B-79 increased with increasing alkali concentration and appeared following first order reaction. The observed rate constants for various concentrations of B-79 showed similar values, and B-79 was hydrolyzed by first order reaction for dye concentration. Therefore, it was confirmed that the overall reaction follow second order kinetics and proceed via $S_N2$ reaction. From the study on kinetics and spectrometric analysis, it was proposed that the rate determining step of the hydrolysis reaction of B-79 is the nucleophilic substitution reaction - that is the reaction of the rapid attack of OH- on the carbon atom, which is in acceptor ring, adjacent to auto group to break the C-N bond. And it was also found that the final hydrolysis products of B-79 include both the acceptor ring in the form of sodium salt and the donor ring possessing 4-N,N-dihydroxyethyl group converted from 4-N, N-diacetoxyethyl group.

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熱力學函數間의 直線關係 (第 5 報) 關係式의 評價와 反應機構上의 意義 (Linear Relationships between Thermodynamic Parameters (Part V) Critical Evaluation and Mechanistic Significances of the Relationship)

  • 이익춘
    • 대한화학회지
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    • 제9권1호
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    • pp.8-15
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    • 1965
  • 一般式中의 potential energy 變數로서 ${\sigma}$ Y를 使用할 수 있음을 밝혔고 또 關係式의 反應機構上의 意義를 論하였다. Benzyl chlorides의 solvolysis反應 data를 適用함으서 物質常數 ${\alpha}'$는 2個의 뚜렷한 系列을 形成하며 置換基常數 ${\sigma}$와는 各系列마다 別途로 直線關係를 가지며 이로서 $S_N1$으로부터 $S_N2$로의 反應機構의 變化를 알 수가 있었다.

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살충성 2-Chloro-1-(2,4,5-trichlorophenyl)vinyldimethylphosphate (Gardona)$^{\(R)}$의 가수분해 반응메카니즘 (Kinetics and Mechanism of Hydrolysis of Insecticidal 2-chloro-1-(2,4,5-trichlorophenyl) vinyldimethylphosphate (Gardona)$^{\(R)}$)

  • 성락도;윤태용;권기성;김태린
    • 대한화학회지
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    • 제34권5호
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    • pp.483-489
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    • 1990
  • 25${\%}$ methanol-수용액 속에서 살충성 2-chloro-l-(2,4,5-trichlorophenyl)-vinyldimethylphosphate(Gardona)의 가수분해 반응을 관찰하였다. 다양한 pH에서의 연구결과는 용매효과(m < 0.4, n < 0.7, |m| ${\ll}$ |l|(화합 S$_N$2 형)), 열역학적 파라미터 (${\{Delta}S^{\neq}$ = -27∼-32 e.u. ${\{Delta}H^{\neq}$ = 13∼18 Kcal/mole), 반응속도(k = k$_A$+k$_B$ [OH$^-$]), 일반염기 촉매 효과 및 가수분해 생성물 분석에 의하여 Gardona의 가수분해 반응이 전이상태와 carbanion 중간체를 포함하는 2분자적(Ad$_{N-E}$) 메카니즘으로 일어남을 암시하고 있다.

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Tetramethyltin과 Iodine의 $S_F2$ 분해반응에 대한 압력의 영향 (The Effect of Pressure on the $S_F2$ Cleavage Reaction of Tetramethyltin with Iodine)

  • 권오천;경진범;이영훈
    • 대한화학회지
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    • 제37권3호
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    • pp.287-293
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    • 1993
  • n-헥산과 아세톤 용매내에서 요오드와 테트라메틸주석간의 전하이동 상호작용을 분광학적 방법으로 연구하였다. 이들의 결과로부터 일시적인 전하이동착물의 흡수 스펙트럼이 관찰되었으며, 흡수 스펙트럼의 후속적인 감소현상이 요오드에 의한 테트라메틸주석의 분해반응임을 알았다.(iododestannylation). 따라서 iododestannylation에 대한 속도상수를 온도 10, 25 및 35$^{\circ}C$, 압력을 1600 bar까지 변화시켜 가면서 측정하였으며, 이때의 반응속도상수는 온도와 압력에 따라 증가함을 알았다. 이 반응속도상수로부터 ${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$, ${\Delta}H^{\neq}$${\Delta}S^{\neq}$의 값을 얻었으며, 이들 값으로부터 전이상태의 용매구조 변화 및 메카니즘을 규명하였다. 이러한 사실로부터 본 반응은 S$_F$2 메카니즘이 지배적이며 압력이 증가함에 따라 S$_F$2의 성격이 약화됨을 알았다.

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Energy Generation Coupled to Azoreduction by Membranous Vesicles from Shewanella decolorationis S12

  • Hong, Yi-Guo;Guo, Jun;Sun, Guo-Ping
    • Journal of Microbiology and Biotechnology
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    • 제19권1호
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    • pp.37-41
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    • 2009
  • Previous studies have demonstrated that Shewanella decolorationis S12 can grow on the azo compound amaranth as the sole electron acceptor. Thus, to explore the mechanism of energy generation in this metabolism, membranous vesicles (MVs) were prepared and the mechanism of energy generation was investigated. The membrane, which was fragmentized during preparation, automatically formed vesicles ranging from 37.5-112.5 nm in diameter under electron micrograph observation. Energy was conserved when coupling the azoreduction by the MVs of an azo compound or Fe(III) as the sole electron acceptor with $H_2$, formate, or lactate as the electron donor. The amaranth reduction by the vesicles was found to be inhibited by specific respiratory inhibitors, including $Cu^{2+}$ ions, dicumarol, stigmatellin, and metyrapone, indicating that the azoreduction was indeed a respiration reaction. This finding was further confirmed by the fact that the ATP synthesis was repressed by the ATPase inhibitor N,N'-dicyclohexylcarbodiimide (DCCD). Therefore, this study offers solid evidence of a mechanism of microbial dissimilatory azoreduction on a subcell level.

Magnetron Sputtering법에 의해 증착한 MoS$_2$ 박막의 고진공하에서의 트라이볼로지적 특성 (Tribological characteristics of sputtered MoS$_2$films with Magnetron Sputtering Method in High Vacuum)

  • 안찬욱;김석삼;이상로
    • 한국윤활학회:학술대회논문집
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    • 한국윤활학회 2000년도 제32회 추계학술대회 정기총회
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    • pp.406-413
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    • 2000
  • The friction and wear behaviors of Magnetron Sputtered MoS$_2$films were investigated by using a pin on disk type tester which was designed and manufactured for this experiment. The experiment was conducted by using silicon nitride (Si$_3$N$_4$) as a pin material and Magnetron Sputtered MoS$_2$on bearing steel (STB2) as a disk material, under operating conditions that include different surface roughness (Polishing specimen, Grinding specimen)(2types), linear sliding velocities in the range of 22, 44, 66mm/sec (3types), normal loads vary from 9.8N, 19.6N, 29.4N(3types), corresponding to contact pressures of 1.9∼2.7GPa and atmospheric conditions of high vacuum( 1.3${\times}$10$\^$-4/Pa), medium vacuum( 1.3${\times}$10$\^$-l/Pa), ambient air(10$\^$5/Pa)(3types). We investigated fracture mechanism in magnetron sputtered MoS$_2$films with Magnetron Sputtering method in each experiment.

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MeOH-MeCN 혼합용매계에서 브롬화벤질 및 요오드화벤질과 아닐린 사이의 친핵성 치환반응 (Nucleophilic Substitution Reactions of Benzyl Bromides and Benzyl Iodide with Anilines in MeOH-MeCN Mixtures)

  • 이익춘;손세철;송호봉;이병춘
    • 대한화학회지
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    • 제28권3호
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    • pp.155-162
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    • 1984
  • 메탄올-아세토니트릴 혼합용매계에서 파라치환된 브롬화 벤질 및 요오드화 벤질과 아닐린 치환체 사이의 친핵성 치환반응을 35.0$^{\circ}$C에서 연구하였다. Hammett관계식, Bronsted 관계식을 이용하여 반응 선택성 파라미터인$ {\rho}_N,\;{\rho}_C$${\beta}$값을 구했으며 분광용매화 관계식의 계수 a, s 등을 구했다. 분광용매화 관계식의 계수 a, s 및 a/s값으로부터 혼합용매의 ${\pi}^{sat}$효과가 본 반응에 크게 작용함을 알았다. PES 모형을 적용하여 본 반응이 dissociative $S_N$2메카니즘으로 진행됨을 알 수 있었으며 이탈기 효과의 논의에는 PES모형이 실험결과와 잘 일치하지 않음을 알 수 있었다. 양자역학적 해석방법을 이용하여 본 반응의 전이상태 변화를 논의했으며 실험결과와 잘 일치함을 알 수 있었다.

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Kinetics and Mechanism of the Aminolysis of O-Methyl S-Aryl Thiocarbonates in Acetonitrile

  • Oh, Hyuck-Keun
    • Bulletin of the Korean Chemical Society
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    • 제32권5호
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    • pp.1539-1542
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    • 2011
  • The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0$^{\circ}C$. The ${\beta}_X$(${\beta}_{nuc}$) values are in the range 0.62-0.80 with a negative cross-interaction constant, ${\rho}_{XZ}$ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles ($XC_6H_4CH_2ND_2$) are large, $k_H/k_D$ = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

A Study of Dry Etch Mechanism of the GaN using Plasma Mass Spectrometry

  • Kim, H.S.;Lee, W.J.;Jang, J.W.;Yeom, G.Y.;Lee, J.W.;Kim, T.I.
    • 한국표면공학회지
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    • 제32권3호
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    • pp.416-422
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    • 1999
  • The characteristics of inductively coupled Cl$_2$/BCl$_3$ plasmas during the GaN etching were studied using plasma mass spectrometry by measuring the relative amounts of reactive ions, neutrals, and etch products. GaN etch rates increased with the increase of pressure and showed a maximum near 25mTorr for the pure $Cl_2$ and near 30mTorr for $Cl_2$$BCl_3$. The addition of$ BCl_3$ to $Cl_2$ also was increased GaN etch rates until 50%BCl$_3$ was mixed to $Cl_2$. The GaN etching with pure $Cl Cl_2$ appears to be related to the combination of Cl$_2^{+}$ ion bombardment and the chemical reaction of Cl radicals. In the case of the GaN etching with Cl$_2$/BCl$_3$, in addition to the combined effect of$_2^{ +}$ ions and Cl radicals, $_BCl2^{+ }$ ions appear to be responsible for some of GaN etching even though they do not have significant effect on the GaN etching compared to $Cl_2^{+}$ and Cl. $Ga^{+ }$ , $GaCl^{+}$ , $GaCl_2^{+}$ , and $N_2^{+}$ were observed as the positive ions of etch products, and the intensities of these etch products showed the same trends as those of GaN etch rate. Among the etch products, Ga and $N_2$ appear to be the main etch products.

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