6 resultados para Diels-Alderase

em Scielo Saúde Pública - SP


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The Diels-Alder reaction continues to be the premier method for the construction of complex organic molecules. In the last 10 years many developments have been introduced, and have led to increased utility of this reaction. In this review we present some of these novelties, which are of fundamental importance in organic synthesis.

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We review herewith the use of solids such as activated alumina and other modern Lewis acid catalysts, as well as the influence of different solvents, including water, on the title reactions, described in the last seven years.

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A computational quantum chemistry experiment is described of Diels-Alder reactions between 2-cycloenones and cyclopentadiene. The effects of FMO-Frontier Molecular Orbitals (HOMO-LUMO) and of the withdrawing nature of substituents at the C=C bond of cycloenones were evaluated. The calculations were made using HF/STO-3G and B3LYP/6-31+G(d,p) methods. The FMO based indexes are in agreement with the experimentally observed reactivity order. NBO - Natural Bond Orbitals - analysis was used to ascertain the effect of C=C substituents on the dienophile reactivity.

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O estudo de Marlierea Cambess. na Amazônia Brasileira tem como principal objetivo atualizar os dados sobre a morfologia e taxonomia das espécies da região, bem como fornecer subsídios para esclarecer a separação de Marlierea de Myrcia DC. ex Guill., conforme sugerem alguns autores. Na Amazônia Brasileira, Marlierea está representada por 11 espécies (Marlierea bipennis (O. Berg) McVaugh, M. caudata McVaugh, M. ensiformis McVaugh, M. ferruginea (Poir.) McVaugh, M. mcvaughii B. Holst, M. scytophylla Diels, M. spruceana O. Berg, M. subulata McVaugh, M. summa McVaugh, M. umbraticola (Kunth) O. Berg e M. velutina McVaugh) e uma mal conhecida (M. obumbrans (O. Berg) Nied.), habitando principalmente áreas de formações florestais. O gênero se caracteriza pelo hábito arbóreo ou arbustivo; folhas opostas (exceto em M. velutina que pode apresentar folhas opostas e/ou alternas); as inflorescências em panículas (de fascículos), racemos, cimeiras ou dicásios; botões florais geralmente fechados, abertura irregular do cálice, em 4-5 lobos, pétalas freqüentemente ausentes. Os Estados do Amazonas e Pará representam os dois principais centros de distribuição dessas espécies, sendo M. spruceana e M. umbraticola as espécies mais comuns. Marlierea obumbrans será melhor estudada posteriormente, devido apresentar sua delimitação taxonômica confusa entre Myrcia e Marlierea.

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The use of water as solvent in organic reactions has been uncommon for several reasons, among them the low solubility of the reactants, the incompatibility of the intermediates with water, and the competition between the desired reaction and hydrolysis. Breslow in 1980, demonstrated that the hydrophobic effect accelerates Diels-Alder reactions and gives a high endo/exo selectivity. Since then, many other reactions were studied in this medium, and below we show the principal results. Besides the academic interest, human and economic aspects are included in this study. Water as a solvent minimizes environmental impact, costs and increases operational safety.

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The lianas observed in this study, Abuta convexa (Vell.) Diels, Abuta imene (Mart.) Eichler, and Chondrodendron platiphyllum (A. St.-Hil.) Miers, all have successive cambia in their stems. The terminology applied to stem histology in species with successive cambia is as diverse as the interpretations of the origins of this cambial variant. Therefore, this study specifically investigates the origin of successive cambia through a developmental analysis of the above-mentioned species, including an analysis of the terminology used to describe this cambial variation. For the first time, we have identified several developmental stages giving rise to the origins of successive cambia in this family. First, the pericycle originates in 1-3 layers of conjunctive tissue. After the differentiation of the first ring, the conjunctive tissue undergoes new divisions, developing approximately 10 rows of parenchyma cells. In the middle portion, a layer of sclereids is formed, again subdividing the conjunctive tissue into two parts: internal and external. New cambia originate in the internal part, from which new secondary vascular strands will originate, giving rise to the second successive vascular ring of the stem. The external part remains parenchymatous during the installation of the second ring and will undergo new periclinal division, repeating the entire process. New cambia will originate from the neoformed strands, which will form only rays. In the literature, successive cambia are formed by a meristem called "diffuse lateral meristem."However, based on the species of Menispermaceae studied in this report, it is demonstrated that the diffuse lateral meristem is the pericycle itself.