Vinte e cinco anos de reações, estratégias e metodologias em Química Orgânica

An overview of the developments that occurred in the field of organic chemistry in Brazil in the last 25 years is presented. These developments are briefly compared to those observed worldwide, including some modern trends. The main source of information was the annual meeting of the Brazilian Chemical Society (RASBQ) covering the period 1979-2001 and the biennial Brazilian Meeting on Organic Synthesis (BMOS). All the contributions presented at these two meetings were classified according to six main indicatives, to permit a discussion about the past, present and future activities of Organic Chemistry in Brazil.

Síntese do isobutileno e seu emprego em reações de esterificação: propostas de aulas práticas de química orgânica para a graduação

An experiment for the synthesis of isobutylene from tert-butanol dehydratation using oxalic acid as catalyst, followed by preparations of tert-butyl benzoate and tert-butyl cinnamate is described. The synthesis are simple, requiring two periods of 4 hours and are suitable for undergraduate organic chemistry experimental courses.

Reações aldólicas assimétricas catalíticas

This review describes the use of catalytic asymmetric aldol reactions of silyl enol ethers and silyl (thio)ketene acetals with aldehydes (the Mukaiyama aldol reaction) in order to illustrate its synthetic utility. A variety of Lewis acid and basic reagents were employed for catalytic aldol reactions with high diastereo- and enantioselectivities. The origins of the selectivity of these reactions are discussed and some representative examples of their application in the synthesis of natural products are presented. New developments in chiral heterobimettalic lanthanoid catalysis and enantioselective aldol reactions in aqueous media are also included.

Transferência de energia entre corantes catiônicos em sistemas homogêneos

In this work, the energy transfer by dipole-dipole interaction between cationic dyes in n-alcohols (methanol, ethanol, 1-propanol and 1-butanol) is studied by time resolved and steady state fluorescence measurements. The critical radii of energy transfer were determined by three independent methods; the spectral overlap, fluorescence decay profiles, and relative intensity measurements. In all solvents, R0 values of the dye pairs obtained from spectral overlap were between 40 to 90 Å. Steady state and time resolved fluorescence measurements resulted in values of R0 in the range of 50 - 80 Å, with good correlation of values.

Efeitos da beta-polinitração na eficiência catalítica de rutenioporfirinas em reações de oxidação de cicloexano

Rutheniumporphyrins, especially with several nitro groups in b-positions, were used in the cyclohexane oxidation in the presence of iodosylbenzene, hydrogen peroxide and sodium hypochlorite as oxygen donors, under mild conditions. The beta-polynitrated complexes were able to promote the catalytic cyclohexane oxidation. They show an exceptionally high catalytic efficiency and resistance to attack by strong oxidizing agents. The cyclohexane oxidation was monitored by gas chromatography and the results showed that the beta-polynitrated rutheniumporphyrins are better catalysts when compared to other complexes not beta-polynitrated. In all cases, the 2-phenylsubstituted complexes were more efficient than 4-phenylsubstituted complexes. The importance of the ortho effect to oxidation was shown.

Um experimento de análise em fluxo envolvendo reações enzimáticas e quimiluminescência

An experiment is proposed to introduce some fundamentals of flow analysis, chemiluminescence and kinetic monitoring of enzymatic reactions in undergraduate courses. Chemiluminescence detection is performed with a simple spectrophotometer equipped with a lab-made spiral flow cell constructed from a polyethylene tube. The hydrogen peroxide produced by the glucose oxidation in the presence of glucose oxidase is continuously monitored by the reaction with luminol in alkaline media in a flow injection system. The exercise allows also the discussion of important analytical features and the comparison with different optical methods of analysis.

Produção de etilenoglicóis e derivados por reações catalíticas do óxido de eteno

Products resulting from the ethoxylation of hydroxylated compounds, especially water and ethanol, are of great commercial importance. This work presents several aspects concerning the catalytic reactions of ethylene oxide, a chemical substance used in the production of a wide variety of products. Mechanisms of ethoxylation, distribution of products, formation of undesired by-products and perspectives for new processes using heterogeneous catalysis are also reviewed and discussed.

Evidências da formação de monocamada de óxido de alumínio sobre sílica, através de reações de enxerto

Aluminum oxide was dispersed on a commercial silica gel surface, using successive grafting reactions. The reaction products were characterized by N2 adsorption-desorption isotherms, scanning electron microscopy and infrared spectroscopy. The progressive incorporation of aluminum, up to 5.5% (w/w), does not produce agglomeration of alumina, since changes in the original pore size distribution of the silica matrix were not observed. The aluminum oxide covers homogeneously the silica surface.

Eletrocatálise das reações de oxidação de hidrogênio e de redução de oxigênio

This work discusses the electrocatalytic processes taking place in the polymer electrolyte fuel cell electrodes, specifically the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR), because these are clear examples of electrochemical reactions favored by the use of electrocatalysts. Since the gaseous reactants are very little soluble in the electrolyte, the use of special electrodes, named gas diffusion electrodes, is required to promote easy and continuous access of reactant gases to the electrocatalytic sites. Besides this, other important aspects such as the use of spectroscopic techniques and of theoretical models to improve the knowledge of the electrocatalytic systems are shortly discussed.

Utilização de reações foto-Fenton na prevenção de contaminações agrícolas

In this work the application of the photo-Fenton process for the treatment of washing water of herbicide containers using solar energy was studied. The influence of the H2O2 concentration and the iron source on the degradation of tebuthiuron and diuron was investigated. The degradation efficiency was strongly affected by the iron source. Using ferrioxalate, total mineralization of diuron and tebuthiuron was obtained either for the individual compounds or for a mixture containing both herbicides, while when using Fe(NO3)3, the maximum mineralization reached for both herbicides was only 50%.

Reações de carbociclização radicalar de orto-iodoaliloxibenzoatos derivados de d-glicose e d-galactose e comparação com as reações de seus análogos benzamidas

Two ortho-iodoallyloxybenzoates, methyl 4-O-allyl-2,3-di-O-benzyl-6-O-(2-iodobenzoyl)- alpha-D-glucopyranoside (3) and methyl 4-O-allyl-2,3-di-O-benzyl-6-O-(2-iodobenzoyl)- alpha-D-galactopyranoside (4) were synthesized in seven conventional steps from methyl alpha-D-glucopyranoside and methyl alpha-D-galactopyranoside, respectively. Bu3SnH-mediated aryl radical cyclization of 3 provided exclusively the hydrogenolysis product 12. The reaction of 4 gave the reduced uncyclized product 13 and only traces of 4A, resulting from 11-endo aryl radical cyclization. In previous papers we described that in similar Bu3SnH-mediated radical reaction of ortho-iodoallyloxybenzamides, analogs of 3 and 4, we obtained macrolactams resulting from 11-endo cyclization. An hypothesis to explain the differences is presented. It was assumed that in the aryl radical formed from iodobenzamides there is a suitable conformation to cyclization, which is stabilized by an intramolecular hydrogen bond.

Adaptação de forno de microondas doméstico para realização de reações de transesterificação sob refluxo e catálise por argilas

The microwave oven became an important source of heating for many laboratory procedures including accelerating organic reactions. Reactions that require long reflux times can sometimes be carried out in a few hours or minutes in a conventional microwave oven. However, longer reflux times can be troublesome since domestic microwave ovens are not prepared for these harsh conditions. This technical note presents our finding on heterogeneous catalysis transesterification reactions between b-keto-esters and carbohydrate derivatives under heating or microwave irradiation using an adapted domestic microwave oven.

Espectroscopia de impedância eletroquímica aplicada ao estudo das reações heterogêneas em ânodos dimensionalmente estáveis

This paper discusses different aspects related to the application of electrochemical impedance spectroscopy (EIS) in the study of heterogeneous electrochemical reactions occurring on Dimensionally Stable anodes (DSA®). The most relevant aspects of the semiconductor/electrolyte interface, the application of the EIS classical equivalent circuit approach and the ac porous model in DSA are presented. The paper shows that DSA type electrodes can be consistently investigated by using the ac porous model and an analysis is presented showing the advantage of applying this kind of approach to study heterogeneous reactions on DSA electrodes. Furthermore, some preliminary results on Ti/Ru0,3Ti(0,7-x)Sn x O2 based electrodes are presented to exemplify the use of the ac porous model analysis.

Um aparato para monitorar reações rápidas: um "stopped-flow" artesanal de baixo custo

The modern stopped-flow reaction analyzer has shown high efficiency and flexibility, which provides outstanding sample economy with a dead-time of less than 1 ms. However the cost of the equipment imposes a serious restriction to many Brazilian scientists and teachers. In this work we describe the construction of a low-cost stopped-flow system coupled to a UV-Vis spectrophotometer. The performance of the system was checked by monitoring the kinetics of two reactions: the fading of phenolphthalein in aqueous alkaline solution and the chlorophyll a demetallation in acid medium. The apparatus showed reasonable efficiency with a dead-time of 0.3 to 0.5 s. The very good results obtained in these two illustrative processes show that the system is satisfactory for determining rate constants with mean reaction times ranging from seconds to minutes.