2-oxazolinas quirais: algumas aplicações como indutores de assimetria em reações orgânicas

This article summarizes how chiral 2-oxazolines have been employed as inducers of asymmetry in many kinds of organic reactions, including the more recent examples reported in which chiral bis(oxazolines) have been complexed in situ with transition metals and utilized to induce the stereoselectivity of some reactions.

Reações orgânicas em meio aquoso

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.

Determinação de As em amostras orgânicas de interesse ambiental por espectrometria de absorção atômica com atomização eletrotérmica após combustão em bomba de O2

The toxicity of the major As species present in the environment justifies the effort for quantifying the element in environmental organic samples, which can vary from animal and vegetal tissues to coal and industrial residues. This paper comments about the applicability of the O2 bomb digestion, as a general procedure for all environmental organic materials. A rapid and straightforward method is suggested, which consists in burning the sample in the bomb at high O2 pressure, dissolving the vapours in diluted HNO3 and determining As in the resulting solution by atomic absorption spectrometry with electrothermal atomization. The method was applied to certified materials and plant samples.

Esquema para interpretação de espectros de substâncias orgânicas na região do infravermelho

This article decribes a simple and systematic method to interpret an infrared spectrum using a flow chart to elucidate the structure of a simple organic compound. It is aimed at undergraduate courses of organic chemistry to make beginners proficient. The proposed flow chart for infrared spectrum interpretation and characterization of organic compounds is suitable for theoretical and experimental courses.

Espectrometria de massas com ionização por "electrospray": processos químicos envolvidos na formação de íons de substâncias orgânicas de baixo peso molecular

An overview of the current literature on the chemical processes involved in the ion formation from low molecular weight organic compounds by electrospray ionization mass spectrometry is given.

Esquema geral para elucidação de substâncias orgânicas usando métodos espectroscópico e espectrométrico

This work describes a systematic method to be applied in undergraduate courses of organic chemistry, correlating infrared spectra, hydrogen and carbon-13 nuclear magnetic resonance, and mass spectra. To this end, a scheme and a table were developed to conduct the elucidation of the structure of organic compounds initially using infrared spectra. Interpretation of hydrogen and carbon-13 nuclear magnetic resonance spectra and of mass spectra is used to confirm the proposed structure.

Vladimir Prelog e a estereoquímica das moléculas orgânicas: um centenário de nascimento

The Croatian chemist Vladimir Prelog shared in 1975 the Nobel Prize in chemistry with J. W. Cornforth for his research into the stereochemistry of organic molecules and reactions. His studies gave new horizons to the comprehension of steric effects on the reactivity of medium-sized rings, to conformational analysis and to the stereospecificity associated to asymmetric syntheses. Prelog made important contributions to enzyme chemistry and to the structure elucidation of alkaloids and of antibiotics from microorganisms, but probably his most famous work is the CIP system for assigning the stereochemistry of chiral centers.

Elucidação estrutural de substâncias orgânicas com auxílio de computador: evoluções recentes

The development of new tools for chemoinformatics, allied to the use of different algorithms and computer programmes for structure elucidation of organic compounds, is growing fast worldwide. Massive efforts in research and development are currently being pursued both by academia and the so-called chemistry software development companies. The demystification of this environment provoked by the availability of software packages and a vast array of publications exert a positive impact on chemistry. In this work, an overview concerning the more classical approaches as well as new strategies on computer-based tools for structure elucidation of organic compounds is presented. Historical background is also taken into account since these techniques began to develop around four decades ago. Attention will be paid to companies which develop, distribute or commercialize software as well as web-based and open access tools which are currently available to chemists.

O ensino de reações orgânicas usando química computacional: I. reações de adição eletrofílica a alquenos

Basic concepts that play an important role in some organic reactions are revisited in this paper, which reports a pedagogical experience involving undergraduate and graduate students. A systematic procedure has been applied in order to use widespread available computational tools. This paper aims to discuss the use of computers in teaching electrophilic addition reactions to alkenes. Two classical examples have been investigated: addition to non-conjugated alkenes and addition to conjugated dienes. The results were compared with those normally discussed in organic textbooks. Several important concepts, such as conformational analysis and energy control (kinetic and thermodynamic) involved in reaction mechanisms can be taught more efficiently if one connects theoretical and practical tools.

Solubilidade das substâncias orgânicas

The solubility of organic compounds is a topic of great importance in chemistry and of interest in several areas, such as materials, drugs and the environment. In this paper, the solubility of these species is discussed in terms of their properties, such as the predominant type of chemical bond, molecular structure, polarity and types of intermolecular interactions. Examples of biological processes fundamental for sustainability of life and related with the solubility of chemical species are presented and discussed.

Resgatando um método eficiente para determinação do ponto de ebulição de substâncias orgânicas: percolador versus Siwoloboff

The aim of this paper was to revive the accurate determination of the boiling point of organic compounds using the percolator technique developed in the 1960s. Although this method is simple, fast and efficient it is omitted from current textbooks. This method has several advantages over Siwoloboff such as high reproducibility and direct measurement of the boiling point of the sample obtained by observing the temperature of the vapor-liquid equilibrium. The experiments were performed in the organic chemistry laboratory but allow interdisciplinary integration with other disciplines of several academic areas.

Efeitos da rugosidade superficial nas propriedades de passivação de monocamadas orgânicas automontadas

Precise surface area is needed for accurate characterization of self-assembled monolayers (SAMs) on metallic surfaces. The aim of this manuscript was to emphasize that miscalculation of surface area is the major source of errors in SAM electrochemical characterization. Limitations are discussed and recommendations given for beginners in analyses of SAM functionalized electrodes. The electrochemical measurements and examples were based on bare gold electrode immobilized with dodecanethiol. The degree of compression of the monolayer properties of formation and reproducibility of the electrochemical response depends on roughness factor, with values closer to the unit being better.

MÉTODOS SELETIVOS DE FLUORAÇÃO DE MOLÉCULAS ORGÂNICAS

Presently, the world depends on a wide variety of new materials based on organofluorine compounds. These compounds can be used as surfactants, high resistance polymers, liquid crystals, agrochemicals, radiopharmaceuticals for positron emission tomography, and drugs. However, the selective formation of C–F bonds remains a challenge. This study reviews our knowledge of organofluorine compounds and describes conventional and modern selective fluorination methods for obtaining these compounds. Here, we highlight the most common fluorination reagents and describe the fluorination reactions. This review is organized by the type of fluorine transfer: nucleophilic, electrophilic, and enzymatic

Efeitos de fontes orgânicas de cobre e enxofre sobre os parâmetros bioquímicos no soro de ovinos

RESUMO: Minerais são componentes essenciais na dieta, exercendo diversas funções no organismo animal onde o uso de sais orgânicos visa aumentar a disponibilidade dos inerais no trato digestório. O perfil metabólico auxilia na avaliação de índices produtivos, para tanto, se faz análises de componentes bioquímicos do sangue. O objetivo foi estudar os efeitos que fontes orgânicas e inorgânicas de cobre e enxofre possuem nos parâmetros bioquímicos. O experimento foi realizado na FZEA/USP, para tanto 40 ovinos foram distribuídos em 10tratamentos: 1) dieta basal; 2) dieta contendo Mo; 3) dieta basal+ Cu inorg + S inorg; 4) dieta basal + Cu inorg + S org; 5) dieta basal + Cu org + S inorg; 6) dieta basal + Cu org + S org; 7) dieta com Mo + Cu inorg + S inorg; 8) dieta com Mo + Cu inorg + S org; 9) dieta com Mo + Cu org + S inorg; 10) dieta com Mo + Cu org + S org. De acordo com cada tratamento houve a inclusão de 10mgkg-1 de MS de Cu inorgânico ou orgânico ou 10 mg kg-1 de MS de Mo ou 0,2% de S inorgânico ou orgânico. Os animais receberam dieta única duas vezes ao dia com inclusão de volumoso num total de 3% do peso vivo. O experimento teve duração de 84 dias, com coletas a cada 28 dias para estudo de glicose, ureia, albumina, colesterol, triglicerídeos. Os parâmetros foram analisados com estrutura fatorial 2 x 2 x 2 (com e sem Mo, Cu orgânico e inorgânico e S orgânico e inorgânico) e uma dieta basal e uma basal mais molibdênio, em delineamento inteiramente casualizado, com um nível de significância de 5%. Os teores séricos de glicose, ureia, albumina e colesterol não apresentaram diferença significativa entre tratamentos e tempo, tão pouco foram influenciados (p>0.05) pelos tratamentos, sendo as médias 64,8mg dl-1; 30,0mg dl-1; 2,78mg L-1; 72,2mg dl-1respectivamente, apresentando-se dentro da normalidade. Os teores de triglicerídeos nos tratamentos (28.8; 34.8; 30.8; 36.9; 34.3; 27.0; 31.6; 32.1; 34.6; 31.1mg dl-1) foram influenciados pela interação Cu x S.

Atividade antioxidante e teor de fenólicos totais em hortaliças orgânicas e convencionais

Considerando que os consumidores estão mais conscientes com a sua saúde e mais preocupados com as condições ambientais, verifica-se uma crescente demanda por alimentos orgânicos. O objetivo deste estudo foi comparar a atividade antioxidante e o teor de fenólicos totais entre alface, rúcula e almeirão de cultivos orgânico e convencional, plantados em uma mesma horta. A atividade antioxidante dos extratos metanólicos das hortaliças foi determinada através do ensaio do DPPH. O teor de fenólicos totais foi obtido espectrofotometricamente de acordo com o método de Folin-Ciocalteu e calculado como equivalente de ácido gálico. A atividade antioxidante contra o radical livre DPPH foi: rúcula orgânica > almeirão orgânico > alface orgânica > rúcula convencional > almeirão convencional > alface convencional. O teor de fenólicos totais foi superior nos vegetais orgânicos. Os resultados deste estudo sugerem que as hortaliças orgânicas podem ser uma importante fonte de antioxidantes naturais e de compostos fenólicos e, portanto, seu consumo deve ser estimulado.