• Title/Summary/Keyword: 수소 치환

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A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols using Cr(VI)-Heterocyclic Complex(Cr(VI)-Isoquinoline) (Cr(VI)-헤테로고리 착물(Cr(VI)-Isoquinoline)를 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구)

  • Park, Young-Cho;Kim, Young-Sik
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.14 no.11
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    • pp.6000-6007
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    • 2013
  • Cr(VI)-heterocyclic complex[Cr(VI)-isoquinoline] was synthesized by the reaction between of heterocyclic compound(isoquinoline) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-isoquinoline in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene$CH_3$, m-Br, m-$NO_2$). Electron- donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.69(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

A Change of Surface Properties of Carbon Black by Surface Treatment (표면처리에 의한 Carbon Black의 표면물성변화)

  • Lee, Chang-Woo;Lee, Chang-Il;Hong, Young-Ho;Hong, In-Kwon;Jang, Yun-Ho;Hahm, Yeong-Min
    • Applied Chemistry for Engineering
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    • v.7 no.4
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    • pp.768-776
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    • 1996
  • Carbon Black has various advantageous properties such as reinforcement, tinting, weathering, chemical resistance, electrical resistance, etc., but it has poor affinity in the solution. The purpose of this study is to enhance dispersion in the aqueous solution by altering the surface characteristics. Two different treatments were applied for both channel black and furnace black respectively. Channel black was treated in alkaline solution to replace hydrogen of the carboxyl group with alkaline metal, Li, Na, K. Furnace black has few functional groups, and it was treated with $HNO_3$ to increase the number of functional group on carbon black. It was seen that the substitution of alkaline metal on the surface of channel black enhances the degree of dispersion. Also the higher the acid concentration and reaction temperature, the more the number of some functional groups on the furnace black. Reaction time was not seen to be effective.

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A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using (C10H8N2H)2Cr2O7 ((C10H8N2H)2Cr2O7를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Park, Young Cho;Kim, Young Sik;Kim, Soo Jong
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.597-600
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    • 2017
  • $(C_{10}H_8N_2H)_2Cr_2O_7$ was synthesized by reacting 4,4'-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using $(C_{10}H_8N_2H)_2Cr_2O_7$ in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as $H_2SO_4$ $(C_{10}H_8N_2H)_2Cr_2O_7$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

Study of the Separation and Elution Behavior of Phenols as Priority Pollutants in Reversed Phase Liquid Chromatography (역상 액체 크로마토그래피에서 유기오염물질로서의 페놀류들의 분리 및 용리거동에 관한 연구)

  • Dai Woon Lee;Sun Kyung Lee;Keun Sung Yook;Won Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.3
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    • pp.287-294
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    • 1989
  • The optimum condition for the separation of priority pollutant phenols using isocratic elution has been determined. The elution behavior of eleven phenols has been also studied to interpret the retention. The reversed phase liquid chromatographic methods were performed on a ${\mu}$-Bondapak $C_{18}$ column with methanol-water, acetonitrile-water, and THF water mixtures as mobile phases. The COF method, where Snyder's solvent triangle concept was combined with a mixture-design statistical technique, was used to optimize the strength and selectivity of solvents for the separation of phenols. The optimum solvent composition, which gives a complete separation of eleven phenols, was found to be $MeOH:ACN:H_2O$ = 7:40:53. The plots of ln k' vs. -${\Delta}H^{\circ}$ and ${\Sigma}{\pi}$ of phenols showed relatively good linearities. Effect of van der Waals volume, pi-energy and hydrogen bonding on the retention of phenols were investigated. The following equation with the correlation coefficient of 0.9927 for ACN-water solvent system was obtained; $log^{k'}=2.515{\times}10^{-2}VWV-1.301{\times}10^{-1}E-3.674{\times}10^{-1}$

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Photochemistry of Benzanilide I Photocyclization of Benzanilides (벤즈아닐리드류의 광화학 (제1보). 벤즈아닐리드류의 광고리화 반응)

  • Yong-Tae Park;Sang-Rok Do;Kap-Duk Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.4
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    • pp.426-436
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    • 1985
  • Preparative and kinetic photochemical reactions of several benzanilides were studied. Several substituted benzanilides were synthesized by acylation of substituted anilines with substituted benzoyl chlorides. While benzanilide gave a photo-Fries type reaction product, 2-chlorobenzaniline, 2-bromobenzanilide, and 2-methoxybenzanilide gave a photocyclization reaction product, phenanthridone. Since 8-chlorophenanthridone was obtained from 2,2'-dichlorobenzanilide, the carbonyl phenyl is the excited site. Quantum yield of photocyclization of 2-chlorobenzanilide, 2'-chlorobenzanilide, and 2-methoxybenzanilide were obtained. 2-Chlorobenzanilide was photocyclized effectively and 2'-chlorobenzanilide ineffectively. Since the oxygen present in the reaction medium retarded the photocyclization reaction of 2-chlorobenzanilide, the triplet state of 2-chlorobenzanilide is involved. The mechanism of the photocyclization of 2-chlorobenzanilide is suggested: $\pi-complex$ between carbonyl phenyl and N-phenyl was formed from the triplet state of 2-chlorobenzanilide; neighbour phenyl (N-phenyl) assists for leaving of chlorine from carbonyl phenyl to make an intermediate, cyclized conjugated radical, because electron donating group on the N-phenyl ring accelerated the reaction; hydrogen detachment from the intermediate is obviously not a rate determined step because there was no isotope effect on the rate of photocyclization. The photocyclization reaction rate of 2-methoxybenzanilide was faster in the presence of oxygen than in the absence of oxygen. Thus, the singlet excited state of 2-methoxybenzanilide is involved in the reaction. Probably, the intermediate, methoxyhydro-phenanthridone is oxidized by oxygen in the medium to give phenanthridone.

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Synthesis and Magnetic Characterization of Fe-nitride for Magnetic Recording (기록매체용 Iron-nitride의 합성 및 자기특성)

  • O, Yeong-U;Kim, Mun-Seop
    • Journal of the Korean Magnetics Society
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    • v.2 no.3
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    • pp.244-250
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    • 1992
  • Iron nitride $Fe_4N$ by partial substitution of nitrogen by carbon was prepared by nitriding the iron oxalate whose thermal decomposition gives a carburating atmosphere. Iron oxalates, the precursors, were prepared by precipitation and co-precipitation. The size and shape of the carbonitride particles could be controlled by modifying the conditions of preparation of the oxalate precursor. From the results of electron micrographs, it is clear that the $Fe_4N$ pigment particle maintains the original shape(needle shape) of the starting materials and that it consists of fine unit particles which link together to form a stereo-network structure. An investigation of the $Fe^{II}_3\;Fe^I_{1-x}\;Sn_xN_{1-y}C_y$ solid solution has shown that Sn plays the role of a growth inhibitor of the elementary microcrystallites of the iron carbonitride. The coercive force and saturation magnetization of iron carbonitride obtained from co-precipitated iron oxalate were 500 Oe and 120 emu/g, respectively.

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A Study on the Rearrangement of 1,3-Thiazolidine Sulfoxides to Dihydro-1,4-thiazines (1,3-티아졸리딘술폭시드의 디히드로-1,4-티아진 유도체로의 전위에 관한 연구)

  • Wha Suk Lee;Hoh Gyu Hahn;He-Duck Mah
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.247-256
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    • 1989
  • 4-Acetyl-5,6-dihydro-2-methyl-1,4-thiazine carboxylic acid derivatives 24 were prepared by ring expansion of corresponding thiazolidine sulfoxides. Oxidation of 2-methyl-1,3-thiazolidine-2-acetic acid derivatives 12 gave a mixture of cis and trans sulfoxides, 14 and 15. Assignments of the cis and trans sulfoxides were based on the $^1HNMR$ and IR spectroscopy and regioselectivity of deuterium exchange reaction. With PTSA as acid catalyst both the cis and trans sulfoxide, 14 and 15 were transformed via sulfenic acid 18 to dihydro-1,4-thiazine 24. However, under the neutral conditions (in DMF at $100^{\circ}C$) the trans sulfoxides 15 rearranged via sulfenic acid 21 to isomeric dihydrothiazines 27. The mechanism of formations of 24 and 27 is also discussed.

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Chiral Separation of Derivatized Racemic Alcohols on Substitued Cyclodextrin Stationary Phases by Capillary Gas Chromatography (모세관 기체 크로마토그래피에 의한 치환된 Cyclodextrin 정지상을 이용한 알코올 유도체의 키랄분리)

  • Lee, Sun-Haing;Seo, Yeong-Ju;Lee, Kwang-Pill
    • Journal of the Korean Chemical Society
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    • v.39 no.2
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    • pp.94-102
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    • 1995
  • S-Hydroxypropyl(PH) ${\beta}$-cyclodextrin(hydrophilic), dialkyl(DA)-cyclodextrin(hydrophobic), trifluoroacetyl(TA) ${\gamma}$-cyclodextrin(intermediate) stationary phases were used for gas chromatographic separation of racemic alcohols and their derivatives. All the alcohols used for this experiment were derivatived by using trifluoro acetic anhydride, acetic anhydride, or trichloro acetic anhydride. It is apparent that the enantioselectivity of the enantiomeric pairs was very dependent on the type of acylation reagent. The best experimental condition of optical resolution of the alcohols and their derivatives was different on the polarity of the solute molecules. The chiral separation was also studied depending on temperature, polarity of the column, and hydrogen bonding ability and steric effect between the alchols and CD stationary phase. The chiral recognition mechanism is dependent not upon the kinds of the chiral stationay phases but upon the derivatization of the racemic alchols.

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Nucleophilic Substitution at a Carbonyl Carbon Atom (IX). Solvolysis of 2-Furoyl Chloride and 2-Thenoyl Chloride in Binary Mixtures (카르보닐탄소원자의 친핵성 치환반응 (제9보). 이성분 혼합용매에서 2-염화테노일 및 2-염화퓨로일의 가용매분해반응)

  • Son Jin-Eon;Sang-Kee Yoon;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.23 no.6
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    • pp.339-348
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    • 1979
  • The kinetics of the solvolysis of 2-furoyl chloride and 2-thenoyl chloride in $MeOH-H_2O,\;EtOH-H_2O,\;(Me)_2CO-H_2O,\;MeCN-H_2O$ and MeCN-MeOH has been investigated. The rates were faster in protic solvents than in aprotic solvents. This was caused by the bond breaking of leaving group through hydrogen-bonding solvation of protic solvents. In MeCN-M$\'{e}$OH the rate in MeOH rich solvents was faster than in MeCN rich solvents by the specific solvation of alcoholic hydrogen and there was a maximum rate of reaction at MeOH mole fraction of 0.8. The reaction rates of solvolysis were considerably slower than those of benzoyl chloride owing to the electron withdrawing effect of thienyl and furyl groups. It was concluded that solvolytic reaction proceeds via a dissociative $S_N2$ mechanism in which bond-breaking precedes bond-formation at the transition state.

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Understanding and Improvement of an Experiment Measuring Chemical Reaction Rates by Monitoring Volume Change of a Gas:On the Reaction between HCl(aq) and Mg(s) (기체 부피변화를 이용한 화학반응속도 측정 실험의 이해 및 개선 연구: HCl 수용액과 고체 Mg의 반응에 대하여)

  • Jeong, Dae-Hong;Bang, Jeong-A;Yun, Hui-Suk;Choe, Won-Ho
    • Journal of the Korean Chemical Society
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    • v.50 no.5
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    • pp.404-414
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    • 2006
  • this study we analyzed and improved an experiment measuring chemical reaction rates introduced in the high school science textbooks through an understanding of the phenomena observed in carrying out the experiment. For this purpose, the contents of textbooks related to the experiment were analyzed, and the problems observed in carrying out the experiment were addressed through experimental analysis. When the experiment was carried out by the method of aquatic transposition presented in textbooks, the observed volume change of H2 gas was delayed and chemical reaction rate was increased in the early stage of reaction period. To resolve these problems, an improved method for measuring the reaction rates was suggested. In the improved experiment the reaction rate was measured to be constant on time, which was interpreted in terms of the concentration of H+ and the surface area of magnesium.