• Title/Summary/Keyword: 반응용매

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A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using 2,4'-Bipyridinium Dichromate (2,4'-Bipyridinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Kim, Young Sik;Park, Young Cho
    • Applied Chemistry for Engineering
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    • v.22 no.6
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    • pp.718-722
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    • 2011
  • 2,4'-Bipyridinium dichromate [$(C_{10}H_8N_2H)_2Cr_2O_7$] was synthesized by the reaction of 2,4'-bipyridinie with chromium trioxide in $H_2O$. The structure was characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase in the order of the dielectric constant (${\varepsilon}$), in the order : cyclohexene < chloroform < acetone < N,N'-dimethylformamide. In the presence of hydrochloric acid, 2,4'-bipyridinium dichromate effectively oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant (${\rho}$) was -0.65 at 303 K. The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

Effect of Organic Solvents on Lipase for Interesterification of Fats and Oils (유지의 에스테르교환에 있어서 유기용매가 리파제에 미치는 영향)

  • Kwon, Dae-Y.;Rhee, Joon-S.
    • Korean Journal of Food Science and Technology
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    • v.17 no.6
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    • pp.490-494
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    • 1985
  • The effect of organic solvents on the stability and catalytic activity of the microbial lipase from Rhizopus arrhizus for interesterification of fats and oils has been examined. The reaction system used was nonaqueous solvent system (two phase system). The solvents examined were 5 hydrocarbons (n-hexane, n-heptane, n-octane, isooctane, and cyclohexane) and 3 ethers (diethylether, diisopropylether, di-n-butylether). The results revealed that diisopropylether and isooctane are superior to the other solvents examined for interesterification of fats and oils in two phase systems.

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Nucleophilic Displacement at Sulfur Center (XVII). Solvolysis of 2-Anthracenesulfonyl Chloride (황의 친핵성 치환반응 (제17보) 2-염화안트라센 술포닐의 가용매 분해반응)

  • Hyong Tae Kim;Soo Dong Yoh;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.27 no.3
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    • pp.167-177
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    • 1983
  • The kinetics of 2-anthracenesulfonyl chloride in methanol-water, ethanol-water, acetone-water and acetonitrile-water has been studied by electroconductometric method. For media in which water has the same mole fraction, the rate was greater in protic solvent than in dipolar aprotic solvent and it was greater consistently in methanol-water than in ethanol-water over the whole range of solvent composition investigated, while the two rates in acetone-water and acetonitrile-water inverted at about 0.9 of mole fraction of water. Both m value, susceptibility of rate to the ionizing power and n value, solvent participation number in the transition state were much smaller in protic solvent. These values and the activation parameters show that solvolysis of 2-anthracenesulfonyl chloride proceeds by $ S_N2$ mechanism.

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Solvation in Mixed Solvents (VII). Solvolysis of t-Butyl Halide in Isodielectric Solvents (혼합용매에서의 용매화 (제 7 보). 등유전상수 용매에서 t-Butyl Halide 의 가용매분해반응)

  • Lee, Ick-Choon;Lee, Hai-Whang;Uhm, Tae-Seop;Sung, Dae-Dong;Ryu, Zoon-Ha
    • Journal of the Korean Chemical Society
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    • v.32 no.2
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    • pp.85-93
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    • 1988
  • Solvolyses of t-butylhalides (X = Cl, Br, I) in quasi isodielectric solvent system, MeOH-nitromethane, MeOH-nitrobenzene and MeOH-ethyleneglycol have been studied kinetically. Methanolyses for t-butylhalides in MeOH-NM and MeOH-NB show rate maxima at 40~100 % (v/v) MeOH. The rate maxima observed have been interpreted as a result of cooperative enhancement of polarity-polarizability and hydrogen bonddonor ability of solvents. The influences of polarity-polarizability and hydrogen bonddonor ability on reactivities of substrates have been discussed in terms of Y value changes. The solvolysis rates for t-butylhalides in E.G. are more than 20 fold faster than those in MeOH and this was attributed to the solvent structure of E.G.

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Analysis of Thermal Imidization Kinetics of 6FDA-BAPP Polyimide in Relation with Solvent Evaporation (6FDA-BAPP 폴리이미드 열축합 반응에서의 잔류용매에 따른 이미드화거동 연구)

  • Lee, Eun-Young;Hwang, Tae-Seon;Nam, Jae-Do
    • Polymer(Korea)
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    • v.36 no.4
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    • pp.448-454
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    • 2012
  • A poly(amic acid) (PAA) was prepared by reaction of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluropropane (BAPP) in N,N-dimethylacetamide (DMAc). The cast films of the synthesized PAA were thermally treated at different temperatures to create polyimide (PI) films. The heat treatment temperature varied between 80 and $230^{\circ}C$ to investigate the imidization index in relation with the solvent evaporation rates. The progress of PAA imidization was examined using a thermogravimetric analyzer (TGA) and a Fourier transform infrared spectroscope (FTIR) at various time and temperature. The experimental results showed that the imidization index was fast at the initial stage in the presence of solvent, DMAc, reaching the final imidization. When the imidization temperature is high over $200^{\circ}C$, the imidization index decreased because the solvent was evaporated too fast.

Kinetics of the Oxidation of Substituted Benzyl Alcohols with 4-(Dimethylamino)pyridinium Dichromate (4-(Dimethylamino)pyridinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응 속도)

  • Choi, Sun do;Park, Young Cho
    • Applied Chemistry for Engineering
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    • v.16 no.1
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    • pp.153-157
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    • 2005
  • 4-(Dimethylamino)pyridinium dichromate was synthesized by the reaction of 4-(dimethylamino)pyridine with chromium(VI)trioxide in $H_2O$, and characterized by IR, EA and ICP. The oxidation of benzyl alcohol using 4-(dimethylamino)pyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexen < chloroform < acetone < N,N-dimethylformamide. In the presence of hydrochloric acid(HCl), 4-(dimethylamino)pyridinium dichromate oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) smoothly in N,N-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron-withdrawing groups retarded the reaction. The Hammett reaction constant($\rho$) was -0.70 at 303K. The observed experimental data have been rationalized as follows: the proton transfer occurs after the prior formation of a chromate ester in the rate-determining step.

Kinetics of the Oxidation of Substituted Benzyl Alcohols using 6-Methylquinolinium Dichromate (6-Methylquinolinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응 속도)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.12 no.12
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    • pp.5990-5996
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    • 2011
  • 6-Methylquinolinium dichromate[$(C_{10}H_9NH)_2Cr_2O_7$] was synthesized by the reaction of 6-methylquinoline with chromium trioxide in $H_2O$, and characterized by IR, ICP. The oxidation of benzyl alcohol using 6-methylquinolinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene < chloroform < acetone < N,N- dimethylformamide. In the presence of hydrochloric acid($H_2SO_4$ solution), 6-methylquinolinium dichromate oxidized benzyl alcohol and its derivatives(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$) smoothly in DMF. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.67(303K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

Optimization for Chia Seed Antioxidative Activity of Solvent Extraction Using the Response Surface Methodology (반응표면 분석법을 이용한 치아씨 항산화 활성 추출의 최적화 조건)

  • Han, Kee-Young;Choi, Jin-Young
    • The Korean Journal of Food And Nutrition
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    • v.29 no.2
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    • pp.228-236
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    • 2016
  • The purpose of this study was to determine the optimum conditions of solvent extraction type and solvent concentration (60, 70, 80%, v/v), extraction time (30, 80, 130 mins) and extraction temperature (10, 15, $20^{\circ}C$) in order to increase the antioxidant activity of the chia seed. The total polyphenol content and DPPH radical scavenging activity was measured by using response surface methodology (RSM) to establish the optimal conditions. Using ethanol and methanol extractions at extraction concentrations of 60%, and time and temperature of 130 mins and $20^{\circ}C$, the maximum total polyphenol content was 871.00 mg% ($R^2=0.9507$) and 557.70 mg% ($R^2=0.9784$) for ethanol and methanol extraction respectively. Using the same extraction conditions, the maximum level of DPPH radical scavenging activity was 72.14% ($R^2=0.9675$) and 52.79% ($R^2=0.9524$) for ethanol and methanol extraction respectively. The results indicate that ethanol extracts showed a higher antioxidant activity than methanol extracts. The ethanol extraction conditions of response surface analysis (RSA) were affected more by ethanol concentration than by extraction time or temperature. In contrast, the methanol extraction conditions of response surface analysis (RSA) were affected more by extraction time. Based on the RSM, the optimum ethanol extraction conditions were the following: extraction concentration, 63%: time, 100 mins: and temperature, $18^{\circ}C$. The optimum methanol extraction conditions were the following: extraction concentration, 65%; time, 120 mins; and temperature, $16^{\circ}C$.

Study of Solvent Effects on the Ionization of tert-butyl Halide in MeOH-DMSO Mixtures (MeOH-DMSO 혼합용매중에서 tert-butyl halide의 이온화에 미치는 용매효과)

  • Yeol Sakong;Shi Choon Kim;Jin Sung Kim;Bon Su Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.1
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    • pp.45-51
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    • 1985
  • Rate constants and activation parameters for the methanolysis of t-butyl halide (t-BuCl, t-BuBr, t-BuI) in various MeOH-DMSO mixtures were measured by conductometric method. Taft's solvatochromic parameters, such as polarity-polarizability(SPP's), ${\pi}^{\ast}$, hydrogen bond donor (HBD) acidity, ${\alpha}$, and hydrogen bond acceptor (HBA) basicity, ${\beta}$ of the solvents, were determined by the so called solvatochromic method using five indicators. The variation of methanolysis rate with the solvent composition was discussed on the basis of the activation parameters and the correlation of the rates with the solvatochromic parameters. It is concluded that the polarity-polarizability, HBD acidity and HBA basicity of the mixtures had an effect on the ionization of t-butyl halide cooperatively, also that the specific interaction between the leaving groups and the solvents, such as ion-dipole and hydrogen bond acceptor-donor interaction, is the most important factor of solvent effects on the stabilization of transition states.

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Solvent-tolerant Lipases and Their Potential Uses (유기용매 내성 리파아제와 그 이용가능성)

  • Joo, Woo Hong
    • Journal of Life Science
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    • v.27 no.11
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    • pp.1381-1392
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    • 2017
  • This review described solvent-tolerant lipases and their potential industrial, biotechnological and environmental impacts. Although organic solvent-tolerant lipase was first reported in organic solvent-tolerant bacterium, many organic solvent-tolerant lipases are in not only solvent-tolerant bacteria but also solvent-intolerant bacterial and fungal strains, such as the well-known Bacillus, Pseudomonas, Streptomyces and Aspergillus strains. As these lipases are not easily inactivated in organic solvents, there is no need to immobilize them in order to prevent an enzyme inactivation by solvents. Therefore, the solvent-tolerant lipases have the potential to be used in many biotechnological and biotransformation processes. With the solvent-tolerant lipases, a large number insoluble substrates become soluble, various chemical reactions that are initially impossible in water systems become practical, synthesis reactions (instead of hydrolysis) are possible, side reactions caused by water are suppressed, and the possibility of chemoselective, regioselective and enantioselective transformations in solvent and non-aqueous systems is increased. Furthermore, the recovery and reuse of enzymes is possible without immobilization, and the stabilities of the lipases improve in solvent and non-aqueous systems. Therefore, lipases with organic-solvent tolerances have attracted much attention in regards to applying them as biocatalysts to biotransformation processes using solvent and non-aqueous systems.