• Title/Summary/Keyword: $S_N2$ reaction

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Morita-Baylis-Hillman Route to Dimethyl 2,3-Dihydrobenzo[b]oxepine-2,4-dicarboxylates and Methyl 2-(2-Carbomethoxybenzo[b]furan-3-yl)propanoates from Salicylaldehydes

  • Ahn, Sang-Hyun;Jang, Seung-Soon;Kim, Young-Keun;Lee, Kee-Jung
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.233-242
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    • 2012
  • A new synthetic method for dimethyl 2,3-dihydrobenzo[b]oxepine-2,4-dicarboxylates and methyl 2-(2-carbomethoxybenzo[b]furan-3-yl)propanoates by an intramolecular conjugate displacement reaction or an $S_N2$ reaction of acetates of Morita-Baylis-Hillman adducts of methyl (2-formylphenoxy)acetates has been described.

A Simple Synthesis of 3-Substituted 1-Amino-2-thioxo-4-imidazolidinones, Isolation of the Intermediates, N-Amino-N-ethoxycarbonylmethyl-N'-aralkyl-thioureas

  • Soon Kyung Kwon;Myoung Suk Park
    • Bulletin of the Korean Chemical Society
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    • v.13 no.5
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    • pp.526-528
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    • 1992
  • 1-Aminothiohydantoin derivatives were prepared in good yields by the reaction of alkyl or arylisothiocyanates with ethyl hydrazinoacetate hydrochloride in presence of triethylamine. The intermediates, N-amino-N-ethoxycarbonylmethyl-N'-aralkylthioure as, which were formed during the reaction and could be transformed into the appropriate 1-aminothiohydantoins, were isolated and characterized.

Serial Degradation of Perchloroethylene by Delftia sp. N6 after Dechlorination Using Fenton's Reagent

  • Lee, Wan-Seok;Kim, Jang-Eok;Kim, Hee-Sik;Ahn, Chi-Yong;Oh, Hee-Mock
    • Journal of Microbiology and Biotechnology
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    • v.16 no.11
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    • pp.1734-1739
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    • 2006
  • The degradation of perchloroethylene (PCE) was investigated with the serial treatment of biological reaction after dechlorination using Fenton's reagent. The dechlorination of PCE was expressed using $D_m$ (dechlorination value), calculated from ${\Delta}Cl^-mol/{\Delta}PCE$ mol, and was 2.58 with 5 mM of $H_2O_2$ and $Fe^{3+}$. The $150{\mu}M$ of PCE was transformed to $37{\mu}M$ of dichloroacetic acid (DCAA). Biological treatment with Delftia sp. N6 was applied after degradation of PCE by the Fenton reaction. The optical densities indicating cell growth were 0.53/0.10 with/without the Fenton reaction after one day, respectively. The N6 strain degraded 95% of the DCAA produced from PCE by the Fenton reaction within one day. Consequently, it seemed that the serial treatment of a Fenton reaction and biological reaction was effective in the removal of not only PCE, but also DCAA, one of the major metabolites of PCE.

Molecular Orbital Studies on the Reaction Path and Reactivity of $S_N2$ Reactions. Determination of Reactivity by MO Theory (Part 69) (SN2 반응의 반응경로 및 반응성에 관한 분자궤도함수 이론적 연구)

  • Lee, Ik Choon;Cho, Jeoung Ki;Lee, Hae Hwang;O, Hyeok Geun
    • Journal of the Korean Chemical Society
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    • v.34 no.3
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    • pp.239-247
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    • 1990
  • The gas-phase S_N2$ reactions can be classified into neutral bimolecular, solvated, and ionic reactions; the neutral bimolecular reaction proceeds via retention mechanism whereas the ionic reaction produces inversion products. In the reaction of solvated nucleophile with one solvent molecule, a six-center transition state (TS) is formed and the two processes i.e., retention and inversion, are found to compete with a favored path depending on the electronic effect of the nucleophile and substituents in the substrate and on the steric requirement. In the ionic reaction, the difference in the energy barrier between the two processes reduces to a small value when the substrate methyl group is made bulky, leaving ability of the leaving group is improved and at the same time the negative charge of the nucleophile is dispersed. When the reaction center atom in the $S_N2$ reaction is changed to a larger sized second row elements, the activation barrier decreases since the steric crowding in the penta-coordinated TS is relieved. However within the same row, the barrier was found to increase as the atomic size decreased. For the boron, B, the barrier height was the least since in addition to the relatively large atomic size compared to C and N, it forms tetra-coordinated TS so that the steric crowding becomes nearly negligible.

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Synthesis of Pyrimidopyrimidine by Ring Transformation of s-Triazine (s-Triazine의 Ring Transfromation에 의한 Pyrimidopyrimidine의 합성)

  • 정원근;김상기;천문우;김득준
    • YAKHAK HOEJI
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    • v.28 no.2
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    • pp.97-100
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    • 1984
  • We have investigated the feasibility of using cyclic ambident nucleophiles in s-triazine ring transformation reaction and found that they can replace the $N_{1}-C_{2-N_{3}$ fragment of s-triazine directly in basic conditions, yielding the corresponding bicyclic products. In this paper, we described the reaction and mechanistic aspects of s-triazine to pyrimidopyrimidine transformation by 6-aminouracil derivatives. This type of ring transformation is supposed to be first attempt that deals with the successful s-triazine to bicyclic heterocycle transformation.

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A Study on the Decompressed Ammonia Stripping from Ammonia Contained Wastewater (폐수의 감압 암모니아 탈기에 관한 연구)

  • 신대윤;오유경
    • Journal of Environmental Health Sciences
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    • v.27 no.1
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    • pp.93-99
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    • 2001
  • This study aims at finding out pertinent reaction conditions for treating high concentration ammonia contained in N-chemical factory wastewater with decompressed ammonia stripping method that was designed. And it also tries to investigate adsorption capability of removed ammonia to soil. The results from experiments are as follows ; 1. The removal rate of N $H_3$-N of synthetic wastewater was under 85% at pH 10 with decompressed ammonia stripping method. The reaction time in pressure 360 mmHg at pH 11 and 12 was shorter than in 460 mmHg, and the removal rate of N $H_3$-N with decompressed ammonia stripping method at 9$0^{\circ}C$ was 11~15% higher than air stripping 2. The optimum conditions for decompressed ammonia stripping with synthetic sample were shown as pH 12, temperature 9$0^{\circ}C$, internal reaction pressure 460 mmHg and reaction time 50 minutes. These conditions were applied to treat the wastewater containing organic-N 290.5mg/$\ell$, N $H_3$-N 168.9mg/$\ell$, N $O_2$-N 23.2mg/$\ell$, N $O_3$-N 252.4mg/$\ell$, T-N 735mg/$\ell$. Organic-N turned out to be removed 60%, the removal rate of N $H_3$-N IS 94%, T-N is 50%. But N $O_2$-N and N $O_3$-N were increased with 7.8% and 14.9% respectively. 3. The CO $D_{Sr}$ removal rate in decompressed ammonia stripping reaction was 42% and S $O_4$$^{2-}$ was removed 8.2%. It was turned out caused with higher pH and thermolysis. 4. In soil adsorption of ammonia desorbed from the decompressed stripping process of wastewater, the recovery rate was 76% in wet soil.

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Rate and Product Studies on the Solvolyses of Allyl Chloroformate

  • Koh, Han Joong;Kang, Suk Jin
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4117-4121
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    • 2012
  • The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with the sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

Characteristics of $TiN/TiSi_2$ Contact Barrier Layer by Rapid Thermal Anneal in $N_2$ Ambient (질소 분위기에서 순간역처리에 의해 형성시킨 $TiN/TiSi_2$ Contact Bsrrier Lauer의 특성)

  • 이철진;허윤종;성영권
    • The Transactions of the Korean Institute of Electrical Engineers
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    • v.41 no.6
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    • pp.633-639
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    • 1992
  • The physical and electrical properties of TiN/TiSiS12T contact barrier were studied. The TiN/TiSiS12T system was formed by rapid thermal anneal in NS12T ambient after the Ti film was deposited on silicon substrate. The Ti film reacts with NS12T gas to make a TiN layer at the surface and reacts with silicon to make a TiSiS12T layer at the interface respectively. It was found that the formation of TiN/TiSiS12T system depends on RTA temperature. In this experiment, competitive reaction for TiN/TiSiS12T system occured above $600^{\circ}C$. Ti-rich TiNS1xT layer and Ti-rich TiSiS1xT layer were formed at $600^{\circ}C$. stable structure TiN layer and TiSiS1xT layer which has CS149T phase and CS154T phase were formed at $700^{\circ}C$. Both stable TiN layer and CS154T phase TiSiS12T layer were formed at 80$0^{\circ}C$. The thickness of TiN/TiSiS12T system was increased as the thickness of deposited Ti film increased.

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Synthesis of Silicon Carbide Whiskers (I) : Reaction Mechanism and Rate-Controlling Reaction (탄화규소 휘스커의 합성(I) : 반응기구의 율속반응)

  • 최헌진;이준근
    • Journal of the Korean Ceramic Society
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    • v.35 no.12
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    • pp.1336-1336
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    • 1998
  • A twt -step carbothermal reduction scheme has been employed for the synthesis of SiC whiskers in an Ar or a H2 atmosphere via vapor-solid two-stage and vapor-liquid-solid growth mechanism respectively. It has been shown that the whisker growth proceed through the following reaction mechanism in an Ar at-mosphere : SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) the third reaction appears to be the rate-controlling reaction since the overall reaction rates are dominated by the carbon which is participated in this reaction. The whisker growth proceeded through the following reaction mechaism in a H2 atmosphere : SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) The first reaction appears to be the rate-controlling reaction since the overall reaction rates are enhanced byincreasing the SiO vapor generation rate.