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Ruthenium nanoparticles prepared from ruthenium dioxide precursor: Highly active catalyst for hydrogenation of arenes under mild conditions

ROSSI, Liane M.; MACHADO, Giovanna
Fonte: ELSEVIER SCIENCE BV Publicador: ELSEVIER SCIENCE BV
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
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The hydrogenation of benzene and benzene derivatives was studied using Ru(0) nanoparticles prepared by a very simple method based on the in situ reduction of the commercially available precursor ruthenium dioxide under mild conditions (75 degrees C and hydrogen pressure 4atm) in imidazolium ionic liquids. Total turnovers (TTO) of 2700 mol/mol Ru were obtained for the conversion of benzene to cyclohexane under solventless conditions and TTO of 1200 mol/mol Ru were observed under ionic liquid biphasic conditions. When corrected for exposed ruthenium atoms, TTO values of 7940 (solventless) and 3530 (biphasic) were calculated for benzene hydrogenation. These reaction rates are higher than those observed for Ru nanoparticles prepared from decomposition of an organometallic precursor in similar conditions. The presence of the partially hydrogenated product cyclohexene was also detected at low conversion rates. (C) 2008 Elsevier B.V. All rights reserved.; CENPES; CENPES; Financiadora de Estudos e Projetos (FINEP); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); CTPETRO-CNPq; FAPERGS; Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul (FAPERGS)

Selective Allylic oxidation of Cyclohexene by a Magnetically Recoverable Cobalt Oxide Catalyst

SILVA, Fernanda P.; JACINTO, Marcos J.; LANDERS, Richard; ROSSI, Liane M.
Fonte: SPRINGER Publicador: SPRINGER
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
37.301396%
In this work, we prepared a new magnetically recoverable CoO catalyst through the deposition of the catalytic active metal nanoparticles of 2-3 nm on silica-coated magnetite nanoparticles to facilitate the solid separation from liquid media. The catalyst was fully characterized and presented interesting properties in the oxidation of cyclohexene, as for example, selectivity to the allylic oxidation product. It was also observed that CoO is the most active species when compared to Co(2+), Co(3)O(4) and Fe(3)O(4) in the catalytic conditions studied.; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); FAPESP; CNPq; Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq); INCT-Catalise; INCT-Catalise

Oxidação alílica de alcenos catalisada por nanopartículas de óxido de cobalto suportadas; Allylic oxidation of alkenes catalyzed by supported cobalt oxide nanoparticles.

Silva, Fernanda Parra da
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 31/03/2011 PT
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Este trabalho compreende a síntese e caracterização de um novo catalisador magneticamente recuperável de CoO para oxidação alílica de alcenos. O catalisador foi preparado através da deposição de nanopartículas (de tamanho entre 2-3 nm) do metal cataliticamente ativo em nanopartículas de magnetita revestidas por sílica. A natureza magnética do suporte permitiu a fácil separação do catalisador do meio reacional após o termino das reações pela simples aproximação de um ímã na parede do reator. O catalisador pôde ser completamente separado da fase líquida, fazendo com que a utilização de outros métodos de separação como filtração e centrifugação, comumente utilizados em sistemas heterogêneos líquidos, fossem completamente dispensados. O catalisador foi inicialmente testado em reações de oxidação do substrato modelo cicloexeno e mostrou seletividade para a produção do produto alílico, cicloex-2-en-1-ona, que é reagente de partida de grande interesse para a síntese de diversos materiais na indústria química. As reações de oxidação foram realizadas utilizando-se apenas O2 como oxidante primário, dispensando o uso de oxidantes tóxicos como cromatos ou permanganatos, que não são recomendados do ponto de vista ambiental. O catalisador sintetizado mostrou ser reutilizável em sucessivos ciclos de oxidação...

Hidrogenação parcial do benzeno com catalisadores de Ru/A12O3 e Ru/CeO2 : efeitos do metodo de impregnação e da adição de solventes ao meio reacional em fase liquida; Partial hydrogenation of benzene on Ru/A12O3 e Ru/CeO2 catalysts : effects of the impregnation method and addition of solvents to the reaction medium in liquid phase

Raphael Soeiro Suppino
Fonte: Biblioteca Digital da Unicamp Publicador: Biblioteca Digital da Unicamp
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 12/03/2010 PT
Relevância na Pesquisa
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A reação de hidrogenação parcial do benzeno em fase líquida tem sido estudada com vistas à obtenção do cicloexeno. Este produto de alto valor agregado pode ser utilizado para a obtenção de poliamidas, como o nylon, através de uma rota industrialmente simples e ecologicamente correta. Esta reação possui ainda uma importante aplicação na proteção ambiental, face às severas restrições à presença de compostos aromáticos nos combustíveis. O presente trabalho tem por objetivo estudar o desempenho de catalisadores de Ru/Al2O3 e Ru/CeO2 preparados através dos métodos de impregnação incipiente e impregnação úmida. Objetiva-se ainda estudar os efeitos da adição de solventes orgânicos ao meio reacional, e a utilização dos solventes na separação dos produtos da reação. Os catalisadores estudados foram preparados a partir de soluções aquosas de RuCl3.xH2O. No caso da impregnação incipiente, os sólidos foram secos a 358 K por 24 h e reduzidos sob fluxo de H2 a 573 K por 3 h. No caso da impregnação úmida, os catalisadores foram reduzidos com formaldeído a 353 K, durante a impregnação. Os suportes Al2O3 e CeO2 foram caracterizados através de titulação potenciométrica e a adsorção de N2 (método de B.E.T.) foi empregada para determinar a área específica dos sólidos. As técnicas de MEV+EDX e XPS permitiram avaliar a composição dos sólidos...

Oxidação aerobica de cicloexano e cicloexeno usando carvão ativado como catalisador; Cyclohexane and cyclohexene aerobic oxidation by using activated carbon as a catalyst

Liliane Schier de Lima
Fonte: Biblioteca Digital da Unicamp Publicador: Biblioteca Digital da Unicamp
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 24/02/2006 PT
Relevância na Pesquisa
37.684963%
O interesse nas reações de oxidação do cicloexano e cicloexeno tem sido foco de muitas pesquisas nos últimos anos, objetivando a busca de reações com maiores rendimentos e seletividades. A rota sintética comercialmente utilizada oxida o cicloexano a cicloexanol e cicloexanona com rendimentos muito baixos (em torno de 4 %), fomentando ainda mais a busca por rotas alternativas de oxidação. O presente trabalho estudou a oxidação direta de cicloexano e cicloexeno a 140ºC e pressões de até 50 bar usando carvões ativados de origem mineral e vegetal como catalisadores. O carvão ativado, por se tratar de um material com uma alta área superficial e de característica hidrofóbica, é compatível com reações de hidrocarbonetos e, então, foi utilizado como catalisador para estas oxidações. As oxidações diretas do cicloexano, nas condições em que foram realizadas, apresentaram resultados de conversão abaixo de 1% e, em alguns casos, com resultados irreprodutíveis. Para as reações de oxidação do cicloexeno, além de algumas mudanças nas condições das reações, foram utilizados como catalisadores carvão ativado impregnados com Pd. As reações apresentaram boas conversões, que variaram de 5 a 90%. Os carvões minerais previamente tratados com ácido clorídrico conduziram a melhores resultados nas oxidações catalíticas do cicloexeno...

Selective Allylic oxidation of Cyclohexene by a Magnetically Recoverable Cobalt Oxide Catalyst

SILVA, Fernanda P.; JACINTO, Marcos J.; LANDERS, Richard; ROSSI, Liane M.
Fonte: SPRINGER Publicador: SPRINGER
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
37.301396%
In this work, we prepared a new magnetically recoverable CoO catalyst through the deposition of the catalytic active metal nanoparticles of 2-3 nm on silica-coated magnetite nanoparticles to facilitate the solid separation from liquid media. The catalyst was fully characterized and presented interesting properties in the oxidation of cyclohexene, as for example, selectivity to the allylic oxidation product. It was also observed that CoO is the most active species when compared to Co(2+), Co(3)O(4) and Fe(3)O(4) in the catalytic conditions studied.; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP); Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Immobilization of chromium complexes in zeolite Y obtained from biosorbents : synthesis, characterization and catalytic behaviour

Figueiredo, Hugo; Silva, Bruna Andreia Nogueira Airosa; Quintelas, C.; Raposo, M. Manuela M.; Parpot, Pier; Fonseca, A. Maurício C.; Lewandowska, A. E.; Bañares, M. A.; Neves, Isabel C.; Tavares, M. T.
Fonte: Elsevier B.V. Publicador: Elsevier B.V.
Tipo: Artigo de Revista Científica
Publicado em /02/2010 ENG
Relevância na Pesquisa
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The goal of this study is the preparation of new heterogeneous catalytic materials to be used in oxidation reactions under mild conditions through the valuation of heavy metals in wastewater. The samples used in the immobilization of chromium complexes were prepared from a dichromate solution of 100 mgCr L−1. The zeolite CrNaY was prepared from a robust biosorption system consisting of a bacterial biofilm, Arthrobacter viscosus, supported on zeolite NaY. The biofilm performs the reduction of Cr(VI) to Cr(III) and this cation is retained in the zeolite by ion exchange. The immobilization of chromium complexes with heterocyclic ligands in the supercages of Y zeolite was performed by the in situ synthesis with three different ligands, 3-methoxy-6-chloropyridazine (A), 3-piperidino-6-chloropyridazine (B) and 1-(2-pyridylazo)-2-naphthol (C). A sample loaded with Cr from a liquid solution with the same initial concentration was prepared as a reference through the traditional direct ion-exchange method and coordinated with ligand (A). The resulting catalysts were fully characterized by different techniques (FTIR, XRD, TGA, SEM, Raman, cyclic voltammetric studies and chemical analysis) and the results confirmed that the Cr complexes were immobilized in supercages of NaY. Catalytic studies were performed in liquid phase for the cyclohexene oxidation...

Oxidation of cyclohexanol and cyclohexene with triazenido complexes of chromium immobilized in biosorption FAU supports

Figueiredo, Hugo; Silva, Bruna Andreia Nogueira Airosa; Kuzniarska-Biernacka, Iwona; Fonseca, A. M.; Medina, R.; Rasmussen, Soren B.; Bañares, M. A.; Neves, I. C.; Tavares, T.
Fonte: Elsevier BV Publicador: Elsevier BV
Tipo: Artigo de Revista Científica
Publicado em 01/07/2014 ENG
Relevância na Pesquisa
27.01372%
This work presents the recovery of biosorption supports as an alternative source of benign production of heterogeneous catalysts for oxidation reactions in mild conditions. Cr-containing FAU zeolite, in sodium form (NaY) and in proton form (HY), was recovered from biosorption studies and reused as support for the preparation of heterogeneous catalysts by the flexible ligand method, using 1,3-diphenyltriazene derivatives. Results showed that the ligand play an important role in the coordination of Cr inside the zeolite. The catalysts showed good activity for the oxidation of cyclohexanol, reaching a maximum of 63.5% conversion. Cr leaching was evaluated and it was found that the Cr-FAU supports lost some of the Cr into the reaction medium, whereas immobilization of Cr-complexes reduced the referred leaching. For the cyclohexene oxidation, a maximum 72.9% conversion was achieved with a HY zeolite-based catalyst.

Immobilization of cobalt phthalocyanine and tetrasulfophthalocyanine onto MCM-41 and MCM-48: effect of immobilization method on catalytic activity

Pirouzmand,Mahtab; Amini,Mostafa M.; Safari,Nasser; Hamoule,Touba
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/11/2013 EN
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Cobalt tetrasulfophthalocyanine (CoPcS) was chemically anchored to amine-modified MCM-41 and MCM-48 surface. These mesoporous silica were prepared by hydrothermal procedure. Physical mixtures of CoPc in MCM-41 and in MCM-48 were also prepared for comparison purposes. The four prepared catalysts, 10 wt.% CoPcS/NH2-MCM-41, 10 wt.% CoPcS/NH2-MCM-48, 10 wt.% CoPc/MCM-41 and 10 wt.% CoPc/MCM-48, were characterized by X-ray diffractometry (XRD), diffuse reflectance UV-Vis spectroscopy and BET specific surface analysis. The catalytic activity of the immobilized catalysts was tested in the aerobic epoxidation of cyclohexene. CoPcS/NH2-MCM-41 and CoPcS/NH2-MCM-48 showed relatively high epoxide selectivity but low conversion of cyclohexene compared to CoPc/MCM-41 and CoPc/MCM-48. No leaching of metallophthalocyanine from the catalysts immobilized by chemical bonding into the reaction medium was observed and these catalysts could be reused four times.

Diaquabis(L-phenylalaninato)nickel(II) encapsulated in zeolite: an efficient heterogeneous catalyst system for the oxidation of cyclohexene, toluene and ethyl benzene

Ghorbanloo,Massomeh; Ghamari,Somayeh; Shahbakhsh,Nahid; Ng,Seik Weng
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/11/2014 EN
Relevância na Pesquisa
27.01372%
L-Phenylalanine reacts with nickel-exchanged zeolite Y to form diaquabis(L-phenylalaninato)nickel(II), which is encapsulated in the pores of the zeolite. In this zeolite-encapsulated form, the nickel derivative functions as an efficient catalyst when cyclohexene, toluene and ethyl benzene are oxidized by hydrogen peroxide in the presence of sodium bicarbonate (as co-catalyst). The catalyst was readily recovered from the reaction mixture, and it could be re-used for other three runs without noticeable loss of activity. The heterogeneous catalyst exhibited significantly higher activity and selectivity compared with diaquabis(L-phenylalaninato)nickel(II) itself.

Epoxidation of Cyclohexene on Heterogenized Molybdenum Compounds

Barradas,E.F.M.; Cestari,A.R.; Airoldi,C.; Buffon,R.
Fonte: Brazilian Society of Chemical Engineering Publicador: Brazilian Society of Chemical Engineering
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/06/1998 EN
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Heterogenization of molybdenum species, starting either with Mo(CO)6 or MoO2(acac)2, on the surface of functionalized silicas bearing one (Si-Et1) or two (Si-Et2) ethylenediamine ligands was studied. The resulting systems are active in the catalytic epoxidation of cyclohexene by tert-butyl hydroperoxide. Using fresh catalysts, Si-Et2 results in higher selectivity, regardless of the Mo precursor. However, MoO2(acac)2-based systems are far more active. Formation of diols was never detected. Although XPS analyses point mainly to Mo(VI) species on the surface of all systems, UV-vis spectra suggest different ligands in their coordination sphere

Breaks induced in the deoxyribonucleic acid of aerosolized Escherichia coli by ozonized cyclohexene.

De Mik, G; De Groot, I
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em /01/1978 EN
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The inactivation of aerosolized Escherichia coli by ozone, cyclohexene, and ozonized cyclohexene was studied. The parameters for damage were loss of reproduction and introduction of breaks in the deoxyribonucleic acid (DNA). Aerosolization of E. coli in clean air at 80 percent relative humidity or in air containing either ozone or cyclohexene hardly affected survival; however, some breaks per DNA molecule were induced, as shown by sucrose gradient sedimentation of the DNA. Aerosolization of E. coli in air containing ozonized cyclohexene at 80 percent relative humidity decreased the survival by a factor of 10(3) or more after 1 h of exposure and induced many breaks in the DNA.

Inhibition of human polymorphonuclear leukocyte function by 2-cyclohexene-1-one. A role for glutathione in cell activation.

Wedner, H J; Simchowitz, L; Stenson, W F; Fischman, C M
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em /08/1981 EN
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27.478428%
2-cyclohexene-1-one and diethyl maleate specifically decrease reduced glutathione (GSH) levels in human polymorphonuclear leukocytes (PMN) by direct conjugation, and by interaction with the glutathione-s-transferase system. Using these two nontoxic reagents we have examined the effect of decreased GSH levels on five parameters of PMN activation: superoxide generation, release of the lysosomal enzymes lysozyme and beta-glucuronidase, and increases in the influx of Na+ and Ca2+. When PMN pretreated with 2-cyclohexene-1-one or diethyl maleate were incubated with formyl-methionyl-leucyl-phenylalanine (FMLP) or the proteolytic fragment of the fifth component membrane of complement, C5a, agents that interact with surface membrane receptors, increases in all five parameters were inhibited in a dose-dependent manner. For O-2 generation and lysosomal enzyme release the ID50 for 2-CHX-1 was 40--90 micrometers corresponding with a 30--50% decrease in intracellular GHS. In contrast stimulation of treated PMN by the divalent cation ionophore A23187 or 5-hydroxyeicosatetraenoic acid was much less sensitive to depressed GSH; the ID50 for 2-cyclohexene-1-one was 1 mM or greater, corresponding with an 80--90% decrease in GSH. The effect of lowered GSH was not the result of decreased binding of FMLP to surface receptors because [3H]-FMLP binding studies demonstrated a two- to three-fold increase in the number of available binding sites. These data indicate that normal GSH levels are necessary for the transduction of the activation signal from the exterior to the interior of the PMN...

Location of the cyclohexene ring of the chromophore of bacteriorhodopsin by neutron diffraction with selectively deuterated retinal

Seiff, F.; Westerhausen, J.; Wallat, I.; Heyn, M. P.
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em /10/1986 EN
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We report on the location of the cyclohexene ring of the retinylidene chromophore of bacteriorhodopsin projected onto the plane of the membrane. For this purpose, partially deuterated retinal was synthesized containing 11 deuterons at the following positions of the cyclohexene ring: one at C-2, two at C-4, three at C-16, three at C-17, and two at C-18. The partially deuterated retinal was incorporated biosynthetically during growth of the bacteria by using the mutant JW5, which is deficient in the synthesis of retinal. Undeuterated samples were prepared in the same way. Characterization by x-ray diffraction and absorption spectroscopy showed that these samples are identical to native purple membranes as judged by these criteria. A Fourier difference map was calculated from the differences in in-plane diffraction intensities between the deuterated and undeuterated dark-adapted membrane samples. Model calculations showed that the observed difference density had the amplitude expected for a label containing 11 deuterons. At 8.7 Å resolution, the map shows one major peak with the center of mass of the deuterated ring in the interior of the molecule between helices 3, 4, 5, and 6. Based on this result and on our previous work on the location of the middle of the polyene chain...

Inhibition of cell-mediated cytotoxicity by 2-cyclohexene-1-one: evidence for a role for glutathione and/or glutathione-protein interactions in cytolysis.

MacDermott, R P; Bertovich, M J; Bragdon, M J; Nash, G S; Leusch, M S; Wedner, H J
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em /04/1986 EN
Relevância na Pesquisa
27.75045%
In order to explore the role of glutathione in cell-mediated cytotoxicity, we have examined the effect of the sulphydryl-reactive and glutathione-depleting agent 2-cyclohexene-1-one on antibody-dependent cellular cytotoxicity, spontaneous cell-mediated cytotoxicity, and cell-mediated lympholysis by human peripheral blood mononuclear cells. 2-Cyclohexene-1-one significantly inhibited (P less than 0.001) both antibody-dependent and spontaneous cell-mediated cytotoxicity using three different cell-line targets, at three different killer:target cell ratios (10:1, 25:1 and 50:1). Using K-562 cell-line targets, spontaneous cell-mediated cytotoxicity was inhibited by 2-cyclohexene-1-one with an ID50 of 0.71 X 10(-4) M-1.48 X 10(-4) M, while antibody-dependent cellular cytotoxicity was less sensitive to inhibition, and required slightly higher concentrations of 1.48 X 10(-4) M-3.98 X 10(-4) M to achieve 50% inhibition. Similar results were seen with human colon tumour cell-line and Chang liver cell-line cells as targets. Maximal inhibition occurred when 2-cyclohexene-1-one was added to the cytotoxicity assay 60 min prior to, at the start of, or within the first 60 min of a 4-hr assay; inhibition of cytotoxicity occurred with pretreatment of effector cells; and no inhibition of cytotoxicity was observed with pretreatment of target cells. Both the allogeneic mixed leucocyte reaction and cell-mediated lympholysis were also significantly inhibited (P less than 0.001) by 2-cyclohexene-1-one. These studies demonstrate that 2-cyclohexene-1-one is an effective inhibitor of cell-mediated cytotoxicity and suggest that glutathione...

Mechanisms of inactivation of bacteriophage phiX174 and its DNA in aerosols by ozone and ozonized cyclohexene.

de Mik, G.; de Groot, I.
Fonte: Cambridge University Press Publicador: Cambridge University Press
Tipo: Artigo de Revista Científica
Publicado em /04/1977 EN
Relevância na Pesquisa
27.8017%
The mechanisms of inactivation of aerosolized bacteriophage phiX174 in atmospheres containing ozone, cyclohexene, or ozonized cyclohexene were studied by using 32P-labelled phage. The inactivation of the aerosolized phage in clear air or in air containing cyclohexene is due to damage of the protein coat since the deoxyribonucleic acid (DNA) extracted from the inactivated phage retains its biological activity. Inactivation of the phage in air containing ozonized cyclohexene is due both to protein and DNA damage. Sucrose gradient analysis shows that aerosolized inactivated phiX174 releases unbroken DNA. In contrast, the DNA from phage phiX174 inactivated by ozonized cyclohexene is broken. The inactivation of aerosolized phage phiX174-DNA was studied in the same atmospheres using 32P-labelled DNA. phiX174-DNA aerosolized in clear air or air containing cyclohexene at 75% r.h. is inactivated by a factor of 2 in 30 min. The inactivated DNA is broken. Ozone as well as ozonized cyclohexene inactivates KNA very fast causing breaks in the molecule. This is in contrast with the intact bacteriophage in which ozone does not produce breaks in the DNA.

Enhanced Catalytic Activity and Unexpected Products from the Oxidation of Cyclohexene by Organic Nanoparticles of 5,10,15,20-Tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrinatoiron(III) in Water by Using O2

Smeureanu, Gabriela; Aggarwal, Amit; Soll, Clifford E.; Arijeloye, Julius; Malave, Erik; Drain, Charles Michael
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em 09/11/2009 EN
Relevância na Pesquisa
27.598352%
The catalytic oxidation of alkenes by most iron porphyrins using a variety of oxygen sources, but generally not dioxygen, yields the epoxide with minor quantities of other products. The turnover numbers for these catalysts are modest, ranging from a few hundred to a few thousand depending on the porphyrin structure, axial ligands, and other reaction conditions. Halogenation of substituents increases the activity of the metalloporphyrin catalyst and/or makes it more robust to oxidative degradation. Oxidation of cyclohexene by 5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorophenyl)porphyrinato iron(III), ([FeIII(tppf20)]) and H2O2 is typical of the latter: the epoxide is 99% of the product and turnover numbers are about 350.[1–4] Herein, we report that dynamic organic nanoparticles (ONPs) of [FeIII(tppf20)] with a diameter of 10 nm, formed by host–guest solvent methods, catalytically oxidize cyclohexene with O2 to yield only 2-cyclohexene-1-one and 2-cyclohexene-1-ol with approximately 10-fold greater turnover numbers compared to the non-aggregated metalloporphyrin in acetonitrile/methanol. These ONPs facilitate a greener reaction because the reaction solvent is 89% water and O2 is the oxidant in place of synthetic oxygen sources. This reactivity is unexpected because the metalloporphyrins are in close proximity and oxidative degradation of the catalyst should be enhanced...

Conformational analysis of 2,2'-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) by NMR and molecular modeling

Ferreira,Marcelle de S.; Figueroa-Villar,José D.
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/05/2014 EN
Relevância na Pesquisa
37.301396%
2,2'-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-ones) with para and ortho-R groups on the benzene ring were prepared and studied by nuclear magnetic resonance (NMR) and molecular modeling to determine their conformational exchanges. Experimental and calculated results indicated conformational interconversions in these compounds by rotation of benzene ring and slow movement of dimedone rings, leading to intramolecular hydrogen bond length variation. The presence of one R group at the ortho position on the benzene ring modifies conformational exchange, leading to disappearance of one intramolecular hydrogen bond and superposition of diverse NMR signals. The correlation of σp values with chemical shifts, angles and atomic charges confirms that para-R groups electronic properties are involved in conformational exchange and chemical shift variance. These results will be used to study the interaction of these compounds with bio-molecules and their use as starting materials for design and synthesis of new bioactive agents.

Excited electronic states of cyclohexene, 1,4-cyclohexadiene, norbornene, and norbornadiene as studied by electron-impact spectroscopy

Frueholz, Robert P.; Flicker, Wayne M.; Mosher, Oren A.; Kuppermann, Aron
Fonte: Instituto de Tecnologia da Califórnia Publicador: Instituto de Tecnologia da Califórnia
Tipo: Article; PeerReviewed Formato: application/pdf
Publicado em 15/02/1979
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The excited electronic states of cyclohexene, 1,4-cyclohexadiene, norbornene (bicyclo[2.2.1]-2-heptene), and norbornadiene (bicyclo-[2.2.1]-2,5-heptadiene) have been studied by electron impact at scattering angles from 5° to 80°, and impact energies of 30 and 50 eV. Low-lying features with intensity maxima at 4.24 eV in cyclohexene and 4.10 eV in norbornene are identified as singlet --> triplet transitions. Similar features in the spectra of 1,4-cyclohexadiene and norbornadiene extending from 3.4 to 5.4 eV and 2.9 to 4.5 eV, respectively, are believed to result from superposition of two low-lying singlet --> triplet transitions in each molecule. In norbornadiene these features have estimated intensity maxima at 3.4 and 3.9 eV, while in 1,4-cyclohexadiene they appear to be more highly overlapped, yielding a single intensity maximum at 4.29 eV. The singlet --> singlet excited state spectra of these molecules are discussed from the point of view of a model in which ethylene units interact via through-bond and through-space effects. In each of these four molecules, transitions to several superexcited states are observed.

Organometallics: (I) Synthesis of a macrocyclic complex praeseodymium and (II ) effect of wilkinson's catalyst on the cleavage of cyclohexene oxide by borane

Ruth, Carolyn
Fonte: Rochester Instituto de Tecnologia Publicador: Rochester Instituto de Tecnologia
Tipo: Tese de Doutorado
EN_US
Relevância na Pesquisa
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(I) The template synthesis and characterization of the complex of praeseodymium acetate from 2,6-diacetylpyridine and orthophenylenediamine was attempted. The attempted synthesis produced a green precipitate with a high melting point and poor solubility in organic solvents, unlikely characteristics for compound 1 seen on the page. This project was set aside due to the apparent failure to produce the desired compound. (II) The effect of Wilkinson's catalyst on the treatment of cyclohexene oxide with borane-THF at 72 for 5 1/2 hours was also investigated. Oxidation of the organoborane formed by both the catalyzed and uncatalyzed reactions produced cyclohexanol. Another significant product was one which, according to GC-MS, had a molecular weight of 172. This product was not completely identified. Studies of the progress of both the catalyzed and uncatalyzed reactions were conducted using TLC. TLC showed no evidence of the starting material, cyclohexene oxide, after 30 minutes of reflux. No change in the product mixture measured by TLC occurred after 30 minutes for the catalyzed reaction and after 60 minutes for the uncatalyzed reaction, indicating that the reactions were probably complete at that point.