• Title/Summary/Keyword: dioxane

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Hydrolysis Mechanism of Phenyl-N-benzoylchlorothioformimidate Derivatives (Phenyl-N-benzoylchlorothioformimidate 誘導體의 加水分解 反應메카니즘)

  • Ki-Sung Kwon;Chon-Suk Kim;Yong-Gu Lee;Nack-Do Sung
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.589-597
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    • 1992
  • The rate constants of hydrolysis of phenyl-N-benzoylchlorothioformimidates were determined by UV spectrophotometry in 30% (v/v) aqueous dioxane at $25^{\circ}C$. On the basis of rate equation, general base catalysis, solvent effect, substituent effect, thermodynamic parameters, frontier orbital interaction and hydrolysis product analysis, it may be concluded that the hydrolysis of phenyl-N-benzoylchlorothioformimidates proceeds through $S_N1$ mechanism via azocarbocation intermidiate below pH 10.0, while above pH 10.00 the hydrolysis proceeds through nucleophilic addition-elimination ($Ad_{N-E}$) mechanism. In the range of pH from 10.0 to 11.0 these two reaction occur competitively.

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Preparation and Properties of Cellulose Triacetate Membranes for Reverse Osmosis (역삼투용 Cellulose Triacetate 막의 제조와 특성)

  • Nam, Sang-Yong;Hwang, Hae-Young;Koh, Hyung-Chul
    • Membrane Journal
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    • v.17 no.4
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    • pp.277-286
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    • 2007
  • The technology of seawater desalination has been received much attentions to solve the problem of water shortage through all over the world. In this study, it attempts to confirm the use-possibility of cellulose triacetate (CTA) for preparation of reverse osmosis membranes which have been highlighted as high efficiency and low energy consumption process for seawater desalination. The effects of casting dope parameters like an acetyl content, solvent, additives on the membrane performance were investigated. It was possible to produce the membranes which have high water flow rate and salt rejection with the increase of acetyl content and dioxane content among various dioxane/acetone ratios. Acetic acid and maleic acid were preferred for additives to produce high performance membranes. It was verified that $HOLLOSEP^{(R)}$ module which is commercialized CTA membrane by TOYOBO Co. can produce stable water production and high-quality water for long-term operation in the practice plants without any chemical treatments.

Donor Number of Mixed MeOH Solvents Using a Solvatochromic Cu(Ⅱ)-Complex (분광용매화 구리(II) 착물에 의한 메탄올 이성분 혼합용매들의 Donor Number)

  • Seoung-Kyo Yoo;Jin Sung Kim;Yeol Sakong
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.796-801
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    • 1992
  • An empirical Lewis basicity, DN, for eight mixed methanol solvents has been measured by the solvatochromic behavior of the [Cu(tmen)(acac)]$CIO_4$. The change of DN in mixed methanol solvents is not correlated with composition of the mixtures and divided into three groups: (1) dipolar aprotic solvents contribute mainly to the solvation of solute (MeOH-DMSO, MeOH-PY, MeOH-DMF), (2) two components of mixture contribute equally to the solvation of solute (MeOH-MeCN, MeOH-dioxane, MeOH-AC) and (3) methanol contributes entirely to the solvation of solute (MeOH-DCE, MeOH-TCE). The relationship between DN and Kamlet-Taft's $B_{KT}$ for mixed methanol solvents was found to agree well. These DN values also were a useful factor to analysis of reactivity for mixed methanol solvents.

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Kinetics and Mechanism of the Hydrolysis of Phenyl N-Benzenesulfonylchloroformimidate Derivatives (Phenyl N-Benzenesulfonylchloroformimidate 誘導體의 加水分解 反應메카니즘과 反應速度論的 硏究)

  • Nack-Do Sung;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.28 no.5
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    • pp.328-334
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    • 1984
  • A series of phenyl N-benzenesulfonylchloroformimidate derivatives (p-H, p-Cl, p-CH3 & p-OCH3) were prepared and the hydrolysis of these compounds were studied kinetically at various pH by UV spectrophotometry in 1 ; 4 dioxane-water at $25^{\circ}C$. Hammett ${\rho}$ values measured at pH 5.0 (${\rho}$ = -0.45) and pH 10.0 (${\rho}$ = 0.40) indicate that the reaction proceeds via an azocarbonium ion intermediate in the acidic medium, whereas, it involves direct attack by hydroxide ion on the azomethine carbon atom occurs under the basic medium. The formation of stabilized azocarbonium ion species at pH 5.0 is also consistent with the large solvent effect(m = 1.3-1.5 & n = 5.0-5.5). On the basis of these findings, we may concluded that the hydrolysis of phenyl N-benzenesulfonylchloroformimidate derivatives proceeds by $SN_1$ below pH 8.0, however, above pH 10.0, the hydrolysis proceeds through $SN_2$ and in the range of pH 8.0-10.0, these two reactions occur competitively.

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Kinetics for Mononuclear Heterocyclic Rearrangement of N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N'-arylformamidine (I) (N-(5-phenyl-1,2,4-Oxadiazol-3-yl)-N'-arylformamidine의 Mononuclear Heterocyclic Rearrangement반응에 대한 반응속도론 (제1보))

  • Jung Ui Hwang;Jong Jae Chung;Young Zoo Youn
    • Journal of the Korean Chemical Society
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    • v.32 no.4
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    • pp.301-310
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    • 1988
  • Reaction rates for mononuclear heterocyclic rearrangement of N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N'-arylformamidines into 3-acylamino-1-aryl-1,2,4-triazoles were determined spectrophotometrically in dioxane/water (50 : 50, v/v). There are two different reaction paths according to pH. One is pH-independent path, the other is pH-dependent one. In pH-independent path, the result of substituent effect by IYT equation show that N-H bond breaking as well as new N-N bond formation controls the reaction rate. In pH-dependent path, concave-upward Hammett plot was observed. It can be concluded that new N-N bond formation is more advanced than N-H bond breaking in transition state for electron-donating substituents, but N-H bond breaking is more advanced than new N-N bond formation for electron-withdrawing substituents.

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Flavonoid Analysis from the Leaves of Eucommia ulmoides (두충나무잎의 생리활성 Flavonoid 분석)

  • 박종철;김성환
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.24 no.6
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    • pp.901-905
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    • 1995
  • Three flavonoid compounds, astragalin(1), isoquercitrin(2) and quercetin $3-O-{\beta}-D-xylopyranosyl(1-2)-{\beta}-D-glucopyranoside(3)$ isolated from the leaves of Eucommia ulmoides were identified and quantified by HPLC. All flavonoids were well separated on a ${\mu}-Bondapak\;C_{18}$ column with a mobile phase composed of THF-dioxane-MeOH-HOAc-5% $H_3PO_4-H_2O$(145 : 125 : 50 : 20 : 2 : 658). The contents of compound 1 in the methanol extract and n-butanol fraction were 0.09%(w/w) and 0.46%(w/w), of compound 2 were 0.08%(w/w) and 0.48%(w/w), and of compound 3 were 0.40%(w/w) and 1.22%(w/w), respectively.

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Kinetics and hydrolysis mechanism of insecticide O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)phosphorothioate (Flupyrazofos) (살충제 O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)-phosphorothioate(Flupyrazofos)의 가수분해 반응 메커니즘)

  • Sung, Nack-Do
    • The Korean Journal of Pesticide Science
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    • v.6 no.3
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    • pp.218-223
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    • 2002
  • The rate of hydrolysis of insecticide, O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)phosphorothioate (Flupyrazofos) have been investigated in 25% (v/v) aqueous dioxane (${\mu}=0.1M$) at $45^{\circ}C$. The hydrolysis mechanism of flupyrazofos proceeds through the specific acid ($A_{AC}2$) catalysis below pH 4.0, specific base ($B_{AC}2$) catalysis above pH 11.0 and general acid & base ($B_{AC}2$) catalysis between pH 5.0 and pH 10.0 via trigonal-bipyramidal ($d^2sp^3$) intermediate as evidence by solvent effect ($|m|{\ll}|{\ell}|$), rate equation ($kt=ko+k_H+ [H_3O^+]+k_{OH}[OH^-]$) and product analysis. The half-life ($T\frac{1}{2}$) of hydrolytic degradation in neutral media at $45^{\circ}C$ was ca. 3 months.

Application of Daphnia magna Monitoring System for Real-time Ecotoxicity Assessment (실시간 생태독성 평가를 위한 물벼룩 감시장치 적용성 검토)

  • Lee, Jang-Hoon;Ko, Woong-Tae
    • Journal of Digital Convergence
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    • v.17 no.10
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    • pp.1-12
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    • 2019
  • In this study, TI(Toxic Index) of Daphnia toximeter corresponded to ecological toxicity standard 1 TU(Toxic Unit) was set up using Daphnia toximeter and when operating NOEC(water quality standards for drinking water) and $EC_{50}$ Daphnia toximeter alarm was issued appropriately, which enables real time ecological toxicity evaluation. I studied to get a good shot and the research was conducted by investigating domestic and international related data and conducting a preliminary study. 6 of 59 hazardous substances (As, Hg, Cr, Diazinon, Dioxane, and Phenol) recommended by the water quality monitoring items for artificial river water were selected and static, dynamic and quality management test, TI was shown to be good in other materials except Diazinon, and as a result of $EC_{50}$ spiking test, TI was matched to TU by distinguishing between 1 TU and 1 TU. in suggesting the complementary point of ecological toxicity management system and the future of research on water Daphnia toximeter.

Stoichiometric Effects. Correlation of the Rates of Solvolysis of Isopropenyl Chloroformate

  • Ryu, Zoon-Ha;Lee, Young-Ho;Oh, Yung-Hee
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1761-1766
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    • 2005
  • Solvolysis rates of isopropenyl chloroformate (3) in water, $D_2O$, $CH_3OD$ and in aqueous methanol, ethanol, 2,2,2-trifluoroethanol (TFE), acetone, 1,4-dioxane as well as TFE-ethanol at 10 ${^{\circ}C}$ are reported. Additional kinetic data for pure water, pure ethanol and 80%(w/w) 2,2,2-trifuoroethanol (T)-water (W) at various temperatures are also reported. These rates show the phenomena of maximum rates in specific solvents (30% (v/v) methanol-water and 20% (v/v) ethanol-water) and, variations in relative rates are small in aqueous alcohols. The kinetic data are analyzed in terms of GW correlations, steric effect, kinetic solvent isotope effects (KSIE), and a third order model based on general base catalysis (GBC). Solvolyses based on predominately stoichiometric solvation effect relative to medium solvation are proceeding in 3 and the results are remarkably similar to those for p-nitrobenzoyl chloride (4) in mechanism and reactivity.

The Synthesis and Micelle Formation for ${\alpha}-Sulfo$ Fatty Acid Polyol Esters (알파 술폰지방산 다가알코올 에스테르류의 합성 및 미셀형성거동)

  • Jeong, No-Hee
    • Journal of the Korean Applied Science and Technology
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    • v.15 no.3
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    • pp.39-45
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    • 1998
  • In recent years, there has been considerable interest in the development of new functional surfactant including new type of anionic surfactants. Anionic surfactants, ${\alpha}-sulfo$ fatty acids that straight long chain alkyl group having from 12 to 18 carbon atoms, were synthesized with sulfur trioxide-dioxane complex to good yield. Xylitol ${\alpha}-sulfo$ fatty acid esters were obtained by reaction that the acetification and esterification of xylitol, by addition reaction with sodium chloride and hydrolysis respectively. These compounds were a new group of destructible surfactants which readily hydrolyzed and oxidized in natural water reservoirs. Physical properties of these new compounds involved surface tension, critical micelle concentration(cmc), foaming power, emulsion power, and hydrolysis properties, were measured. The cmc values of the compounds by ring method were assumed to $7.0{\times}10^{-3}{\sim}3.0{\times}10^{-2}mol/{\ell}$ range and surface tensions at cmc were $25{\sim}31dyne/cm$ respectively.