• Title/Summary/Keyword: 1,4-dioxane

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New Synthetic Route to 1, 4-Dihydropyridine Monoacid Derivatives (1, 4-디히드로피리딘산 유도체의 새로운 제조방법에 관한 연구)

  • Shim, Young-Key;Lee, Sang-Hee;Kang, Jae-Sung;Kim, Wan-Joo
    • Journal of the Korean Chemical Society
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    • v.32 no.2
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    • pp.144-148
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    • 1988
  • A novel synthetic route to 1,4-dihydropyridine mono carboxylic acid derivatives is described. Allyl methyl 2,6-dimethyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-3, 5-dicarboxylate (IV) was treated with $Pd(OAc)_2$ in dioxane for 30 min at 110$^{\circ}C$ with reflux to give the mono acid compound(V) in 94% yield. The mono acid intermediate was converted to 2-(N-benzyl-N-methylamino)ethyl methyl 2,6-dimethyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-3, 5-dicarboxylate (VII) (Nicardipine) and their derivatives in 70~85% yield.

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Kinetics and Mechanism of Hydrolysis of Insecticidal Imidacloprid (살충성 Imidacloprid의 가수분해 반응 메카니즘)

  • Yu, Sung-Jae;Kang, Moon-Sung;Sung, Nack-Doo
    • Applied Biological Chemistry
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    • v.40 no.1
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    • pp.53-57
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    • 1997
  • The rate of hydrolysis of insecticidal 1-(6-chloro-3-pyridylmethyl) -2-nitro-iminoimidazolidine (common name; imidacloprid) have been investigated in 15%(v/v) aqueous dioxane at $45^{\circ}C$. From the kinetics and non-kinetics data such as pH-effect, solvent effect(m=0.04, n=0.30 IT m<${\Delta}H^{\neq}=16.14kcal{\cdot}mol^{-1}\;&\;{\Delta}S^{\neq}=-0.03e.u.$), rate equation ($k_{obs.}=4.56{\times}10^{-3}[OH^-]$) and analysis of hydrolysis product, 1-(6-chloro-3-pyridylmethyl-2)-imidazolidinon, the hydrolysis mechanism of imidacloprid is proposed that the specific base catalyzed hydrolysis($K_{OH^-}$) through nucleophilic addition-elimination ($Ad_N-E$) mechanism proceed via intermediate, 1-(6-chloro-3- pyridylmethyl)-2-hydroxy-2-imidazolidinylisonitraminate (I) and ${\beta}$-3-(6-chloro-3-pyridylmethyl)aminoethyl-1-nitrourea(III). And the half-life(t1/2) of hydrolytic degradation at pH 8.0 and $45^{\circ}C$ was about 4.5 months.

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A Study on the Hydrolysis and Analysis of o-Chlorobezylidenemalononitrile (o-Chlorobenzylidenemalononitrile의 가수분해 및 분석에 관한 연구)

  • Park, Sung-Woo;Kim, Nam-Yee;Kim, Dong-Hwan;Hong, Sung-Work;Sung, Nack-Do;Kim, Il-Kwang;Oh, In-Kio
    • Analytical Science and Technology
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    • v.5 no.4
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    • pp.443-454
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    • 1992
  • The analysis, hydrolysis mechanism, oxidation, reduction, thermal decomposition and metabolism of irritant materials such as chloroacetophenone isomers, bromophenylacetonitrile isomers, o-chlorobenzylidenemalononitrile(CS), and ethylisothiocyanate, etc. are interested in forensic science. We had studied hydrolysis of CS in 10% MeOH-$H_2O$ and 10% dioxane-$H_2O$ at pH 1.0~11.0 and various temperatures. As a result, we identified o-chlorobenzaldehyde and malononitrile that were formed by hydrolysis of CS by using gas chromatography/mass spectrometry, UV/Vis spectrometry, and polarographic method.

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Studies on the Polymeric Surface Active Agent(V) -The Synthesis of Anionic Oligomer Surfactant with α-Sulfo Alkanoic Acid- (고분자 계면활성제에 관한 연구(제5보) -알파 술폰 지방산 음이온성 올리고머 계면활성제의 합성-)

  • Jeong, N.H.;Park, S.S.;Jeong, H.K.;Cho, K.H.;Nam, K.D.
    • Applied Chemistry for Engineering
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    • v.4 no.2
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    • pp.381-392
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    • 1993
  • Anionic oligomer surfactants, dodecyl polyoxyethylene ${\alpha}-sulfa$ alkanoates, had been synthesized through the esterification of dodecyl polyoxyethylene glycol and ${\alpha}-sulfa$ alkanoic acid with straight chain alkyl group having from 10 to 18 carbon atoms to good yield. ${\alpha}-sulfa$ alkanoic acids were obtained by reaction with long chain alkanoic acids and sulfur trioxide-dioxane complex, and dodecyl polyoxyethylene glycols, by addition reaction with dodecyl alcohol and ethylene oxide(addition, 5, 10, 20mol) respectively. All the synthetic products could be separated by means of the thin layer and column chromatography, and their structure has characterized with IR, $^1HNMR$ and elemental analysis, respectively.

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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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Determination of hazardous semi-volatile organic compounds in industrial wastewater using disk-type solid-phase extraction and GC-MS (디스크형 고상 추출법과 GC/MS를 이용한 공장폐수 중 반휘발성유기화합물질 분석)

  • Lee, In-Jung;Lim, Tae-Hyo;Heo, Seong-Nam;Nam, Su-Gyeong;Lee, Jae-Gwan;Cheon, Se-Uk
    • Analytical Science and Technology
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    • v.25 no.4
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    • pp.236-241
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    • 2012
  • There are many industrial factories in the central Nakdong river basin and have been occurred water pollution accidents by hazardous chemicals such as phenol, 1,4-dioxane and perchlorate. In this study, ten compounds of semi-volatile organic compounds (SVOCs) (dichlorvos, toluene-2,4-diisocyanate, 4,4'-methylenedianiline, 4,4'-methylenebis (2-chloroaniline), diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthaltate, bis (2-ethylhexyl) adipate, benzophenone, 4,4'-bisphenol A) of hazardous chemicals which may be potentially discharged into the Nakdong river, were determined by gas chromatography-mass spectrometry (GC-MS) with disk-type solid-phase extraction. Accuracy and precision were in the range of 75.6~110.5%, and 4.6~12.7%, respectively and recovery was in the range of 72.4~127.9%. Three compounds (bis (2-ethylhexyl)adipate, benzophenone, 4,4'-bisphenol A) were detected in industrial wastewater such as wastewater treatment plants (WWTPs) and wastewater discharge facilities in the Nakdong River basin.

Application of a New Scaling Parameter to Chain Expansion in the Systems of Polystyrene/Mixed Solvents (폴리스티렌/혼합용매 계에서 사슬의 팽창에 대한 새로운 스케일링 파라미터의 적용)

  • Park, Il-Hyun;Lee, Dong-Il;Hwang, Mi-Ok;Yu, Young-Chol;Park, Ki-Sang
    • Polymer(Korea)
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    • v.31 no.2
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    • pp.98-104
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    • 2007
  • The expansion behavior of polystyrene (PS) chains with various molecular weights has been investigated above Flory $\Theta$temperature by viscometry after dissolving in the three different mixed solvents systems such as benzene/n-heptane, 1,4-dioxane/isopropanol, and 1,4-dioxane/n-heptane. Two different regimes are observed as increasing temperature: one regime is for the expansion of chain and the other is for the contraction. For the higher molecular weight sample of PS, the higher peak temperature showing its maximum expansion is obtained. Within a certain system of Ps/mixed solvents, the $\tau/\tau_c$ parameter shows universality for the variation of molecular weight. But while each system of Ps/mixed solvents has shown its own different slope, the universality breaks down in the overall system of mixed solvents. However after introducing a new empirical $b^{2/3}\tau/\tau_c$ parameter, all data points of three different systems have dropt on one master curve and the universality of chain expansion has recovered again. Here $\tau$ and $\tau_c$ are defined as $(T-\Theta)/\Theta$ and $(\Theta-T_c)/T_c$, respectively and $T_c$ is the critical solution temperature, and b of Schultz-Flory equation is corresponding to the effective slope in the plot of $1/T_c$ against $1/M_w^{1/2}$.

O$_3$/H$_2$O$_2$와 O$_3$/Catalyst 고급산화공정에서 1,4-dioxane의 제거 특성 연구

  • Park, Jin-Do;Seo, Jung-Ho;Lee, Hak-Sung
    • Proceedings of the Korean Environmental Sciences Society Conference
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    • 2005.11a
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    • pp.192-194
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    • 2005
  • O$_3$/H$_2$O$_2$ 고급산화공정에서 1,4-D의 제거는 반응시간에 따라 완만하게 감소하였으나, O$_3$/catalyst 고급산화공정에서는 전체 제거량의 약 50${\sim}$75%가 반응 초기 5분 내에 제거되어 O$_3$/H$_2$O$_2$ 공정에 비해 초기 반응속도가 현저히 빠른 것을 알 수 있었다. O$_3$/H$_2$O$_2$ 고급산화공정은 ${\Delta}$TOC/${\Delta}$ThOC의 비는 0.09${\sim}$0.40으로 나타났으며, O$_3$/catalyst 고급산화공정에서는 ${\Delta}$TOC/${\Delta}$ThOC의 비가 0.68${\sim}$0.98로 나타나 O$_3$/catalyst 고급산화공정이 O$_3$/H$_2$O$_2$ 고급산화공정에 비해 유기물의 산화력이 우수한 것으로 확인되었다.

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Effect of Genotoxicity or Carcinogenecity Chemicals on the ROS Production (유전독성, 발암성 화학물질이 ROS 생성에 미치는 영향)

  • Go, Seo-Youn;Sheen, Yhun-Yhong
    • Environmental Analysis Health and Toxicology
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    • v.23 no.1
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    • pp.23-32
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    • 2008
  • In the present study, ROS detection of L5178Y cells that were treated with twenty test compounds in order to find out hydrogen peroxide ($H_2O_2$) induction for genotoxicity and carcinogenic toxicity. Twenty test compounds were consist of four classes, such as genotoxic carcinogens, genotoxic noncarcinogens, nongenotoxic carcinogens, and nongenotoxic noncarcinogens. Genotoxic carcinogens are 1,2-dibromoethane, glycidol, melphalan, diethylstilbestrol and urethane. Genotoxic noncarcinogens are 8-hydroxyquinoline, emodin, acetonitrile and diallylphthalate, L-ascorbic acid. Nongenotoxic carcinogens are methyl carbamate, O-nitrotoluene, 1,4-dioxane, tetrachloroethylene and 2,3,7,8-tetrachlorodibenzo-p-dioxin. And nongenotoxic noncarcinogens are D-mannitol, 1,2-dichlorobenzene, caprolactam, bisphenol A and chlorpheniramine maleate.

Extraction of Water-Soluble Porphyrin and Metalloporphyrins into Acetonitrile by Salting-out

  • Tabata, Masaaki;Kumamoto, Midori
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.511-517
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    • 1995
  • A cationic water soluble porphyrin (5,10,15,20-tetrakis (l-methyl-pyridinium-4-yl)porphyrin, $H_2tmpyp^{4+}$) and its metalloporphyrins (MP) were easily extracted into acetonitrile separated by addition of sodium chloride ($4mol\;dm^{-3}$) in the presence of sodium perchlorate, where M denotes $Zn^{2+}$, $Cu^{2+}$, $Co^{3+}$, $Fe^{3+}$, and $Mn^{3+}$ and $P^{2-}$ is porphyrinate ion. The extracted ion-pair complexes were completely dissociated to $[MP(ClO_4)_3]^+$, and $[MP(ClO_4)_2]^{2+}$. The extraction and the dissociation constants were determined by taking into account of the partition constant of sodium perchlorate ($K_D=1.82{\pm}0.01$). The chemical properties of the separated acetonitrile phase as $E_{T(30)}$ and $D_{II,I}$ were determined and compared with other water miscible solvents (acetone, actonitrile, 1,4-dioxane, tetrahydrofuran, 1-propanol and 2-propanol). Furthermore, a sensitive and selective method was proposed for the determination of a subnanogram amount of copper(II) in natural water samples by using the present salting-out method and the porphyrins.

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