• Title/Summary/Keyword: Ring hydrogenation

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Hydrogenation of Arenes with Metallic Iridium and Rhodium Powders Prepared from Iridium(Ⅰ) and Phodium(Ⅰ)-COD Complexes under Mild Conditions

  • 진종식;이병노;문지중;송중호;박용선
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.528-533
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    • 1995
  • Metallic iridium and rhodium powders prepared from the reactions of [M(COD)(PhCN)2]ClO4 (M=Ir(1), Rh(2); COD=1,5-cyclooctadiene) with hydrogen at room temperature in methylene chloride show catalytic activities for hydrogenation of arenes at room temperature under atmospheric pressure of hydrogen. Most substituents (CH3, COOH, NO2, CH2OH, CHO, OPh, OCH3, C=C, halogens and CH2Cl) on aromatic ring suppress the rate of the hydrogenation of the aromatic ring while the aromatic ring hydrogenation of phenol and 1,4-dihydroxobenzene is faster than that of benzene over these metallic powders. Hydrogenation of benzoic acid occurs only at the aromatic ring leaving the COOH group intact over iridium metal powders while benzoic acid is not hydrogenated at all over rhodium metal powders. Carbonyl, nitro, acetylenic and olefinic groups on an aromatic ring are hydrogenated prior to the aromatic ring hydrogenation. Hydrogenolysis of OH groups of phenol, benzyl alcohol and 1,4-dihydroxobenzene, and hydrodehalogenation of halobenzenes, benzyl halides and cinnamyl chloride also occur along with the hydrogenation of aromatic ring.

Ring-Opening Metathesis Polymerization and Hydrogenation of Ethyl-substituted Tetracyclododecene

  • Kwon, Oh-Joon;Vo, Huyen Thanh;Lee, Sul-Bee;Kim, Tae-Kyung;Kim, Hoon-Sik;Lee, Hyun-Joo
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2737-2742
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    • 2011
  • Ring-opening metathesis polymerization (ROMP) of an ethyl-substituted tetracyclododecene (8-ethyltetracyclo[$4.4.0.1^{2,5}.1^{7,10}$] dodec-3-ene, Et-TCD) was carried out in the presence of a ternary catalyst system consisting of $WCl_6$, triisobutyl aluminium (iso$Bu_3Al$), and ethanol. The optimal molar ratio of Et-TCD/$WCl_3$/iso-$Bu_3Al$/ethanol was found as 500/1/3/2 at which the yield of ring-opened polymer was 100%. 1-Hexene was shown to be an effective molecular weight controlling agent for ROMP reaction of Et-TCD. The hydrogenation of the ring opened polymer (p-Et-TCD) was conducted successfully using Pd(5 wt %)/${\gamma}$-$Al_2O_3$ at $80^{\circ}C$ for 1 h. Chemical structures of p-Et-TCD and its hydrogenated product($H_2$-p-Et-TCD) were characterized using 2D NMR techniques ($^1H-^1H$ COSY and $^1H-^{13}C$ HSQC). The changes of physical properties such as thermal stability, glass transition temperature and light transmittance after the hydrogenation were also investigated using TGA, DSC, and UV.

Effect of Alkali Metal Nitrates on the Ru/C-catalyzed Ring Hydrogenation of m-Xylylenediamine to 1,3-Cyclohexanebis(methylamine)

  • Kim, Young Jin;Lee, Jae Hyeok;Widyaya, Vania Tanda;Kim, Hoon Sik;Lee, Hyunjoo
    • Bulletin of the Korean Chemical Society
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    • v.35 no.4
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    • pp.1117-1120
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    • 2014
  • Ru/C-catalyzed hydrogenation of m-xylylene diamine into 1,3-cyclohexanebis(methylamine) was greatly accelerated by the presence of $LiNO_3$, $NaNO_2$, or $NaNO_3$. It was found that the effect of the nitrate salt was significantly affected by the size of cation. The promoting effect of the nitrate salt increased with the decrease of the cation size: $LiNO_3$ ~ $NaNO_2$ > $KNO_3$ > $CsNO_3$ >> [1-butyl-3-methylimidazolium]$NO_3$. XRD analysis of the recovered catalysts after the hydrogenation reactions showed that $LiNO_3$ and $NaNO_2$ were completely transformed into LiOH and NaOH, respectively, along with the evolution of $NH_3$, while $KNO_3$ and $CsNO_3$ remained unchanged.

Synthesis of Perhydroisoquinoline Ring Systems by N-Acyliminium Cyclization$^\sharp$

  • Choi, Joong-Kwon;Jung, Young-Shik;Park, No-Sang
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.129-132
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    • 1988
  • The stereochemistry of N-acyliminium cyclizations to form decahydropyrrolo[2,1-a]isoquinolin-3(2H)-ones was studied. Particular attention was paid to the stereocontrol by an acetoxy group present on pyrrolidone ring. Two of the three new chiral centers were formed stereospecifically, and the third was controlled by elimination-hydrogenation sequence.

Facile Synthesis of Pyranoxanthones, Dihydropyranoxanthones, and Their Analogues

  • Hari, Gala Sri;Lee, Yong-Rok
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.2949-2954
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    • 2011
  • This paper describes a concise and efficient synthetic route for the biologically interesting pyranoxanthones, dihydropyranoxanthones, and their derivatives. The key strategies involve pyranyl ring formation, methylation, catalytic hydrogenation, and catalytic dihydroxylation starting from 1,3-dihydroxyxanthen-9-one.

Hydrogenation of Polycyclic Aromatic Hydrocarbons Over Pt/Kieselguhr Catalysts in a Trickle Bed Reactor (Trickle Bed Reactor에서 Pt/Kieselguhr 촉매를 이용한 다환방향족 탄화수소 수소화 반응)

  • Seung Kyo, Oh;Seohyeon, Oh;Gi Bo, Han;Byunghun, Jeong;Jong-Ki, Jeon
    • Clean Technology
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    • v.28 no.4
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    • pp.331-338
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    • 2022
  • The objective of this study is to prepare bead-type and pellet-type Pt (1 wt%)/Kieselguhr catalysts as hydrogenation catalysts for the polycyclic aromatic hydrocarbons (PAHs) included in pyrolysis fuel oil (PFO). The optimal reaction temperature to maximize the yield of saturated cyclic hydrocarbons during the PFO-cut hydrogenation reaction in a trickle bed reactor was determined to be 250 ℃. A hydrogen/PFO-cut flow rate ratio of 1800 was found to maximize 1-ring saturated cyclic compounds. The yield of saturated cyclic compound increased as the space velocity (LHSV) of PFO-cut decreased. The difference in hydrogenation reaction performance between the pellet catalyst and the bead catalyst was negligible. However, the catalyst impregnated by Pt after molding the Kieselguhr support (AI catalyst) showed higher hydrogenation activity than the catalyst molded after Pt impregnation on the Kieselguhr powder (BI catalyst), which was a common phenomenon in both the pellet catalysts and bead catalysts. This may be due to a higher number of active sites over the AI catalyst compared to the BI catalyst. It was confirmed that the pellet catalyst prepared by the AI method had the best reaction activity of the prepared catalysts in this study. The majority of the PFO-cut hydrogenation products were cyclic hydrocarbons ranging from C8 to C15, and C11 cyclic hydrocarbons had the highest distribution. It was confirmed that both a cracking reaction and hydrogenation occurred, which shifted the carbon number distribution towards light hydrocarbons.

A Study on the Synthesis of Alkyl Naphthenic Oil by the Catalytic Hydrogenation Reactions of Alkyl Aromatic Compound (알킬 방향족 화합물의 촉매 수소화 반응에 의한 알킬 나프텐 기유의 제조에 관한 연구)

  • 최주환;한흥구;최웅수;권오관
    • Tribology and Lubricants
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    • v.8 no.1
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    • pp.56-62
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    • 1992
  • The naphthenic base oil has been formulated to insulating and refrigerating oils. In the views of decreasing of the naphthenic crtide oil, new sources as its replacement have been needed. To solve this situation, the synthesis of naphthenic oil has been carried under hydrogenation reactions of alkyl aromatic compounds using various catalysts. The sturcture of reaction products has been investigated using spectroscopic methods such as NMR, UV, IR and HPLC. On the basis of the experimental results, it was convinced that unsaturated aromatic ring was saturated to saturated rings, and also optimum cond~tions established. Throughout this study, new resource as the replacement of conventional naphthenic oil has introduced.

Synthesis of Pyrazoloquinolines as Gastric $H^+/K^+$-ATPase Inhibitors

  • G. D. Kalayanov;Kang, S. K.;Cheon, H.G.;Lee, S.G.;Yum, E. K.;Kim, S. S.;Choi, J.-K.
    • Bulletin of the Korean Chemical Society
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    • v.19 no.6
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    • pp.667-671
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    • 1998
  • A series of 1-aryl-lH-pyrazolo[4,3-c]quinolines and 2-aryl-2H-pyrazolo[4,3-c]quinolines are prepared by reacting 3-acyl-4-chloroquinolines in ethanol or 3-acyl-4(lH)-quinolone in acetic acid with appropriate hydrazines as possible anti-ulcer agents. A regiospecific synthesis of 1-aryl-lH-pyrazolo[4,3-c]quinolines is also achieved. The central pyridine ring could be easily reduced by catalytic hydrogenation.

Impact of thermal and chemical treatment on the mechanical properties of E110 and E110G cladding tubes

  • Kiraly, M.;Hozer, Z.;Horvath, M.;Novotny, T.;Perez-Fero, E.;Ver, N.
    • Nuclear Engineering and Technology
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    • v.51 no.2
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    • pp.518-525
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    • 2019
  • The mechanical and corrosion behavior of the Russian zirconium fuel cladding alloy E110, predominantly used in VVERs, has been investigated for many decades. The recent commercialization of a new, optimized E110 alloy, produced on a sponge zirconium basis, gave the opportunity to compare the mechanical properties of the old and the new E110 fuel claddings. Axial and tangential tensile test experiments were performed with samples from both claddings in the MTA EK. Due to the anisotropy of the cladding tubes, the axial tensile strength was 10-15% higher than the tangential (measured by ring tensile tests). The tensile strength of the new E110G alloy was 11% higher than that of the E110 cladding at room temperature. Some samples underwent chemical treatment - slight oxidation in steam or hydrogenation - or heat treatment - in argon atmosphere at temperatures between 600 and $1000^{\circ}C$. The heat treatment during the oxidation had more significant effect on the tensile strength of the claddings than the oxidation itself, which lowered the tensile strength as the thickness of the metal decreased. The hydrogenation of the cladding samples slightly lowered the tensile strength and the samples but they remained ductile even at room temperature.