• Title/Summary/Keyword: alkali catalyst

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The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Alkali Metal Ethoxides with S-p-nitrophenyl 2-thiofuroate and 2-Thiophenethiocarboxylate in Absolute Ethanol

  • 엄익환;이윤정;남정현;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.18 no.7
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    • pp.749-754
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    • 1997
  • Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides (EtOM) with S-p-nitrophenyl 2-thiofuroate (1b) and 2-thiophenethiocarboxylate (2b) in absolute ethanol at 25.0±0.1 ℃. 1b is observed to be more reactive than 2b toward all the EtOM studied. The reactivity of EtOM is in the order EtOK > EtONa > EtO- > EtOLi for both substrates, indicating that K+ and Na+ behave as a catalyst while Li+ acts as an inhibitor in the present system. Equilibrium association constants of alkali metal ions with the transition state (KaTS) have been calculated from the known equilibrium association constants of alkali metal ion with ethoxide ion (Ka) and the rate constants for the reactions of EtOM with 1b and 2b. The catalytic effect (KaTS/Ka) is larger for the reaction of 1b than 2b, and decreases with decreasing the size of the alkali metal ions. Formation of 5-membered chelation at the transition state appears to be responsible for the catalytic effect.

Optimization of Process Variables in the Hydrogenation of p-Toluidine on Ru/C Catalyst (Ru/C 촉매를 이용한 p-Toluidine의 선택적 수소화 반응에 있어서 공정변수의 최적화연구)

  • Hong, Bum-eui;Lee, Jong-min;Park, Yeung-ho
    • Applied Chemistry for Engineering
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    • v.19 no.4
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    • pp.432-438
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    • 2008
  • Hydrogenation reactions of p-toluidine over Ru/C were performed while varying reaction temperature, the hydrogen pressure, catalyst loading, solvent, and alkali additive and the effects on the reaction rates and product distribution were examined. 4-Methylcyclohexylamine was generated as a main product and bis(4-methyl cyclohexyl)amine was obtained as a resentative side-product for the hydrogenation reaction of p-toluidine. The selectivity of MCHA decreased with reaction temperature and the hydrogen pressure while increased with catalyst loading. IPA was the best solvent for MCHA. A mechanism of hydrogenation reaction of p-toluidine was suggested from the results. It was found that the presence of alkali salt increased MCHA by reducing BMCHA and rates of hydrogen reaction increased.

The Conversion of Jatropha Oil into Biodiesel Using Acid / Alkali Catalysts (산 / 알칼리 촉매를 사용한 자트로파유의 바이오디젤화)

  • Hyun, Young-Jin;Kim, Hae-Sung
    • Journal of the Korean Applied Science and Technology
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    • v.25 no.3
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    • pp.275-281
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    • 2008
  • The esterification of free fatty acid in Jatropha oil added by propylene glycol using p-TSA catalyst was done, and then the transesterification of Jatropha oil added by 1.0vol% GMS as an emulsifier using TMAH, and mixed catalyst(60wt%-TMAH+ 40wt%-KOH) respectively was followed at $60^{\circ}C$. The esterification conversion at the 1:8 molar ratio of free fatty acid to methanol using 8.0wt% p-TSA was 94.7% within 60min. The overall conversion at the 1:8 molar ratio of Jatropha oil to methanol and $60^{\circ}C$ using mixed catalyst was 95.4%. The kinematic viscosity of Biodiesel using TMAH and mixed catalyst in 24h met the ASTM D-6751 above $30^{\circ}C$, and showed a little more than its criterion.

Novel organic catalysts for nucleophilic fluorination including F-18 radiofluorination

  • Na, Hyeon Su;Kim, Dong Wook
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.3 no.2
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    • pp.116-121
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    • 2017
  • To overcome the low reactivity and solubility of alkali metal fluorides (MFs), various types of phase transfer catalysts (PTCs) have been developed over the last decades. However, since the fluoride activated by such PTC sometimes has a strong basicity, it may cause various side reactions such as elimination reaction or hydroxylation reaction in the nucleophilic fluorination reaction. Also, they may cause separation problems in the compound purification process. In recent advanced study, various PTCs have been developed to solve these problem of conventional catalyst. In this review, we would like to introduce three kinds of novel multifunctional organic catalysts such as bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA), easy separable pyrene-tagged ionic liquid (PIL) by reduced graphene oxide (rGO), and tri-tert-butanolamine organic catalyst.

Calix-Arene based phase transfer catalysts fornucleophilic fluorination

  • Minji Nam;Dong Wook Kim
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.7 no.2
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    • pp.141-146
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    • 2021
  • With increasing interest in fluorinated compounds, nucleophilic fluorination reaction has been generally used for synthesizing fluorine-containing chemicals. However, alkali metal fluorides (MFs) generally have low solubility and reactivity in organic solvent. To overcome these problems, various phase transfer catalysts (PTCs) have been investigated. Calix-arene is known as to capture the metal cation(M+), and therefore in this review, we would like to introduce several kinds of calix-arene based PTCs, such as bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA), oligo-ethylene glycol linked bis-triethyleneglycol crown-5-calix[4]arene (BTC5A), and ionic liquid functionalized calix-arene based catalyst, as well as ion-pair receptor crown-6-calix[4]arene-capped calix[4]pyrrole.

A Study on the Reaction Kinetics of Nitrogen Compounds over Bimetallic Molybdenum Catalysts (이금속성 형태 몰리브덴 촉매를 이용한 질소화합물의 반응속도 연구)

  • Ahn, Beom-Shu
    • Journal of the Korean Applied Science and Technology
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    • v.22 no.4
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    • pp.349-354
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    • 2005
  • It is interesting to discover the reaction kinetics of the newly developed molybdenum containing catalysts. The dissociation/adsorption of nitrogen on molybdenum surface is known to be structure sensitive, which is similar to that of nitrogen on iron surface. The rates over molybdenum nitride catalysts are increased with the increase of total pressure. This tendency is the same as that for iron catalyst, but is quite different from that for ruthenium catalyst. The activation energies of the molybdenum nitride catalysts are almost on the same level, although the activity is changed by the addition of the second component. The reaction rate is expressed as a function of the concentration of reactants and products. The surface nature of $CO_3Mo_3N$ is drastically changed by the addition of alkali, changing the main adsorbed species from $NH_2$ to NH on the surface. The strength of $NH_x$ adsorption is found to be changed by alkali dopping.

Synthesis of Methyl Alcohol and Alternative Gases for Petroleum by Thermochemical Gasification of Waste Lignocellulosic Materials (II) - Thermochemical Conversion of Sawdust, Ricestraw and Ricehusk Using Alkali Salts as Catalyst by Pressurized Reactor (목질(木質) 폐재(廢材)의 열(熱)-화학적(化學的) 방법에 의한 메틸알콜과 대체(代替)에너지 가스의 합성(合成) (II) - 가압하(加壓下)에 알칼리염을 촉매로 사용한 톱밥, 볏짚 그리고 왕겨의 열화학적(熱化學的) 분해(分解) -)

  • Lee, Byung-Guen
    • Journal of the Korean Wood Science and Technology
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    • v.14 no.3
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    • pp.43-46
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    • 1986
  • A stainless steel autoclave reactor, which is the property of Pacific Northwest Laboratories(PNL) and located in PNL, was acted for pyrolysis and gasification of sawdust, ricestraw, and ricehusk. The initial reaction temperature of this reactor was 300$^{\circ}C$, and up to 500$^{\circ}C$ to complete pyrolysis and gasification reaction. The maximum exerted pressure on this reactor was 800 psig. In order to examine the effect of catalyst on reaction temperature, $K_2CO_3$, and nickel/alkali carbonate catalyst mixture were also used. The experimental results obtained with this reactor indicated that good yields of methane-rich gas(exceeding 40% methane) can be produced. The product gas mixtures were also identified to be CO. $CO_2$, $C_2H_4$, and $CH_3CHO$ etc. by Gas Chromatography and Mass Spectrometer.

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The Conversion of Mixed Fat of Beef Tallow and Jatropha Oil into Biodiesel Using Acid / Alkali Catalysts (산/알칼리 촉매를 사용한 우지와 자트로파유 혼합지방의 바이오디젤화)

  • Hyun, Young-Jin
    • Journal of the Korean Applied Science and Technology
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    • v.26 no.2
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    • pp.179-185
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    • 2009
  • The esterification of the reactants of Jatropha oil and methanol added by propyleneglycol was done using p-TSA catalyst. And then the emulsification of triglyceride and methanol was conduced by 1.0vol% GMS. The emulsified reactants were transesterified at $65^{\circ}C$ using TMAH and mixed catalyst (50wt%-TMAH+50wt%-NaOH) respectively. The esterification conversion at the 1:8 molar ratio of free fatty acid to methanol using 8.0wt% p-TSA was 94.7% within 80min. The overall conversion at the 1:8 molar ratio of mixed fat(50wt% Beef Tallow) to methanol and $65^{\circ}C$ using mixed catalyst was 95.4% The cloud point of Biodiesel decreased with the addition of petroleum diesel.

The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Aryl 2-Furoates with Alkali Metal Ethoxides in Ethanol

  • Dong-Sook Kwon;Jung-Hyun Nahm;Ik-Hwan Um
    • Bulletin of the Korean Chemical Society
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    • v.15 no.8
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    • pp.654-658
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    • 1994
  • Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of p-and m-nitrophenyl 2-furoates (4 and 5, respectively) with alkali metal ethoxides ($EtO^-M^+$) in absolute ethanol at 25$^{\circ}$C. The reactivity of $EtO^-M^+$ toward 4 is in the order $EtO^-K^+$ > $EtO^-Na^+$> $EtO^-Li^+$ > $EtO^-K^+$+ 18-crown-6 ether. This is further confirmed by an ion pairing treatment method. The present result indicates that (1) ion paired $EtO^-M^+$ is more reactive than dissociated $EtO^-$ ; (2) the alkali metal ions ($K^+,\;Na^+,\;Li^+$) behave as a catalyst; (3) the catalytic effect increases with increasing the size of the metal ion. A similar result has been obtained for the reaction of 5, however, the catalytic effects shown by the metal ions are more significant in the reaction of 5 than in that of 4.