• Title/Summary/Keyword: Product selectivity

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New Design in Homogeneous Palladium Catalysis: Study of Transformation of Group 14 Element Compounds and Development of Nanosize Palladium Catalysts

  • Tsuji, Yasushi;Fujihara, Tetsuaki
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.1902-1909
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    • 2007
  • This account reports an overview of our findings in homogeneous Pd-catalyzed reactions. Herein we describe the new design in reactions of Group 14 element compounds and in homogeneous nanosize Pd catalysts. In the early stages of our study, we developed Pd-catalyzed transformations of allylic esters with disilanes, silylcyanides and acylsilanes to the corresponding silylation, cyanation and acylation products, respectively. We also developed a Pd-catalyzed three component coupling reaction of Group 14 element compounds involving 1,3-diene and acid chlorides to form β,γ-unsaturated ketone as a single product. Recently, we focus our attention on modifying the catalytic environment by nanosize Pd in order to improve the performance of Pd catalysts. These nanosystems realize efficient catalytic environment with remarkable enhancement in catalytic activity and unprecedented selectivity.

N-Alkylation of Primary Aromatic Amines Using Alkylhalide and Triethylamine (알킬할라이드와 Triethylamine을 이용한 일급 아로미틱 아민의 N-알킬레이션)

  • Kim, Ju-Hee;Park, Myung-Sook
    • YAKHAK HOEJI
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    • v.49 no.2
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    • pp.162-167
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    • 2005
  • Synthetic method for the selective N-monoalkylation of anilines using alkyl halides and triethylamine under room temperature was described. The corresponding N-alkyl anilines were obtained in good yields with minor quantities of dialkylated products. Anilines 2a-m and 3a-m were identified using NMR and IR. A series of 2a-m and 3a-m has been synthesized from aniline, toluidines, ethylanilines, aminoacetophenones, phenetidines. Formation of anilines was undertaken with dropping of alkylhalides at room temperature in methanol (or ethanol) for 3 hours~5 days. Selectivity on the monoalkylation was relatively high. Synthetic ratio of monoalkylated and dialkylated product was 94 : 6 in case of maximum monoalkylation.

Screening of Vietnamese Medicinal Plants for Cytotoxic Activity

  • Thu, Nguyen Bich;Trung, Trinh Nam;Ha, Do Thi;Khoi, Nguyen Minh;Hung, Tran Viet;Hien, Tran Thi;Yim, Nam-Hui;Bae, Ki-Hwan
    • Natural Product Sciences
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    • v.16 no.1
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    • pp.43-49
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    • 2010
  • Thirty-two methanol extracts of thirty-one Vietnamese medicinal plants were evaluated for the cytotoxic activity against five human cancer cell lines, including A549, MCF-7, HT 1080, Huh-7, and HepG2. Of these, the nine extracts of Acanthopanax trifoliatus (4), Acanthopanax gracilistylus (5), Siegesbeckia orientalis (10), Betula alnoides (11), Passiflora edulis (18), Zanthoxylum simulans (leaf, 23), Adenosma caeruleum (26), Solanum verbascifolium (29), and Alpinia malaccensis (31), exhibited high potent cytotoxic activity showing a certain degree of selectivity against the different cell types, with $IC_{50}$ values ranging from 2.1 to $3.8\;{\mu}g/mL$.

Carbonylation of Bromo(Bromomethyl)Benzenes to Alkyl Carboalkoxyphenylacetates Catalyzed by Cobalt Carbonyl

  • Shim, Sang-Chul;Doh, Chil-Hoon;Lee, Dong-Yub;Youn, Young-Zoo;Lee, Seung-Yub;Chae, Shin-Ae;Oh, Dae-Hee;Oh, Hun-Seung
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.45-48
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    • 1992
  • A synthetic method for bis-carbonylation of bromo(bromomethyl)benzenes was described. Alkyl carboalkoxyphenylacetates were easily prepared by the carbonylation of benzylic and arylic bromide moieties in bromo(bromomethyl)benzenes with alcohols in the presence of $K_2CO_3,\;CH_3I$, and a catalytic amount of cobalt carbonyl under the atmospheric pressure of carbon monoxide at room temperature in good to excellent yields. The base played a decisive role in the selectivity of product and $K_2CO_3$ was the best one among bases used.

Shape Selective Oxygen Transfer to Olefins Catalyzed by Sterically Hindered Iron Porphyrins

  • Ahn, Kwang-Hyun;Groves, John T.
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.957-961
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    • 1994
  • Epoxidation of olefins catalyzed by iron-tetraarylporphyrins were studied to see the shape selectivity in the competing reaction between cis-and trans- or internal and external olefins. Cis-olefins were more reactive than trans-olefins in the competing reaction between cis-and trans-olefins. Interestingly, in the epoxidation of $cis-{\beta}-methystyrene$ by ${\alpha}{\beta}{\alpha}{\beta}$ atropisomer of Fe(III)TNPPPCl and iodosylbenzene, 27% of total product was phenylacetone. The unusually large amount of phenylacetone may be produced by hydride rearrangement of carbocationic intermediate. Regioselectivity of the reaction was also studied by using the most sterically hindered Fe(III)TTPPPCl. In the epoxidation of limonene with Fe(III)TTPPPCl, the disubstituted double bond was more reactive than trisubstituted double bond. This is in contrast to the results obtained with other iron-tetraarylporphyrins. Similar trend was also observed in the competing reaction between mono-and di-substituted olefins.

A Convenient Allylation of 1,n-Dicarbonyl Compounds Using Organoindium Reagents

  • Lee, Pil Ho;DongSeo, Mun;Lee, Gu Yeon
    • Bulletin of the Korean Chemical Society
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    • v.22 no.12
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    • pp.1380-1384
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    • 2001
  • The chemoselective reactions of 1,n-dicarbonyl compounds with allyl halides using indium metal were investigated. $\alpha-Ketoesters$ such as ethyl pyruvate, ethyl 3-methyl-2-oxobutyrate and ethyl benzoylformate reacted with a variety of allyl halides i n the presence of indium to afford hydroxy unsaturated carbonyl compounds in good to excellent yields in MeOH/HCl at $25^{\circ}C.$ For the allyl bromide, the presence of various substituents at the $\alpha$ or $\gamma$ position exhibited little effects on both the reaction rates and yields. Ethyl acetoacetate or ethyl levulinate was treated with allylindium reagent to give hydroxy unsaturated carbonyl compounds in good yield. These results mean that both reactivity and selectivity are independent of the distance between carbonyl groups. 2,3-Butanedione or 1-phenyl-1,2-propanedione reacted with allylindium to produce monoallylation product as major compound.

Development of Microwave-Matrix Reformer for Applying SOFC Stack (SOFC 스택 적용 마이크로웨이브-매트릭스 개질기 개발)

  • AN, JUNE;CHUN, YOUNG NAM
    • Transactions of the Korean hydrogen and new energy society
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    • v.32 no.6
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    • pp.534-541
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    • 2021
  • In this study, a novel microwave-matrix reformer was proposed to convert CH4, which is a major component, to a high quality hydrogen energy. And to identify this performance, it was investigated for O2/C ratio, steam feed amount and reformed gas recirculation which are affected for methane conversion and product gas yield. Through the parametric screening studies, optimal operating conditions were that O2/C ratio, steam feed amount and recirculation rate were 1.1, 10 mL/min and 30 L/min. In this conditions, CH4 conversion was 68.1%, H2 selectivity 77.2 and H2/CO ratio 2.62 which are possible applying SOFC stack for RPG (residential power generator).

A study of the NF3 plasma etching reaction with cobalt oxide films grown on an inorganic compounds

  • Jae-Yong Lee;Kyung-Min Kim;Min-Seung Ko;Yong-Soo Kim
    • Nuclear Engineering and Technology
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    • v.54 no.12
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    • pp.4449-4459
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    • 2022
  • In this study, an NF3 plasma etching reaction with a cobalt oxide (Co3O4) films grown on the surface of inorganic compounds using granite was investigated. Experimental results showed that the etching rate can be up to 1.604 mm/min at 380 ℃ under 150 W of RF power. EDS and XPS analysis showed that main reaction product is CoF2, which is generated by fluorination in NF3 plasma. The etching rate of cobalt oxide films grown on inorganic compounds in this study was affected by surface roughness and etch selectivity. This study demonstrates that the plasma surface decontamination can effectively and efficiently remove contaminated nuclides such as cobalt attached to aggregate in concrete generated when decommissioning of nuclear power plants.

Synthesis of the Hydrocarbons from Methanol over ZSM-5 Zeolite Catalyst (ZSM-5 제올라이트 촉매상에서의 메탄올로부터 탄화수소 합성반응)

  • Sang Eon Park;Hak Ze Chon
    • Journal of the Korean Chemical Society
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    • v.25 no.2
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    • pp.97-102
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    • 1981
  • The conversion of methanol to hydrocarbons has been studied over synthetic ZSM-5 zeolite catalyst having high silica to alumina ratio. The conversion products were olefins, paraffins, cycloparaffins, and aromatics, and the catalyst showed especially high selectivity toward the formation of aromatics. The catalyst showed the shape-selectivity and the size of molecules in the product was limited approximately to the size of 1,3,5-trimethylbenzene. Hydrogen form(HZSM-5) was more active, indicating reactions following the dehydration of methanol seemed to be mainly catalyzed by acid sites. Comparison of the reaction characteristics and acid site distribution of the ZSM-5 catalyst with those of mordenite and faujasite type catalysts suggests that cross-linked pore channel structure and the strong acidity of the ZSM-5 catalyst are primarily responsible for the selective formation of aromatics over this catalyst.

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Solvolysis of 2-Thiophenesulfonyl Chloride (2-염화티오펜술포닐의 가용매 분해반응)

  • Jin-Chel Choi;Jieun Oh;Dae Ho Kang;In Sun Koo;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.695-701
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    • 1993
  • Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

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