Diastereosseletividade na redução de enonas bicíclicas com hidretos volumosos

Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride®) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring.

Uma metodologia simples e eficiente para a cloração de compostos aromáticos ativados utilizando o ácido tricloro-isocianúrico

The chlorination of activated aromatic rings is efficiently achieved under mild conditions by reaction of aromatic compounds with trichloroisocyanuric acid in acetonitrile, at room temperature, leading to products in 60-95% isolated yields and good regioselectivity.

4-(hidroximetil)-benzenossulfonato de potássio: metabólito inédito isolado da alga marinha Bostrychia tenella (Rhodomelaceae, ceramiales)

Chemical investigation of the dichloromethane/methanol extract of the marine alga Bostrychia tenella has led to the isolation of two aromatic compounds, the new sulfate metabolite potassium 4-(hydroxymethyl)-benzenosulfonate (1) and the compound 1-methoxyphenethyl alcohol (2), described previously as a synthetic product. Their structures were determined by spectroscopic methods including NMR, MS, IR and by comparison with literature data.

Métodos simples de formação de monocristal de substância orgânica para estudo estrutural por difração de raios X

This work presents three operationally simple laboratory protocols for monocrystal growth of small-molecule organic compounds, which have been applied with success in the last ten years for the formation of single crystals for X-ray structural studies. In addition, five structure hints were formulated as general guidelines for selecting a small-molecule organic compound as a candidate for monocrystal growth: molecular weight >200 D, melting point >100 ºC, two or more aromatic rings in the structure, at least two sites for intermolecular hydrogen bond formation, and a halogen or other heavy atom in the structure.

Avaliação do destino e bioacumulação de benzo(a)pireno através de simulação computacional

The objective of this work was to evaluate the environmental distribution of benzo(a)pirene, a polycyclic aromatic hydrocarbon, by the EQC model. The modeling of the contaminant distribution was accomplished by means of the fugacity model applied to a hypothetical scenario constituted by air, water, soil and sediment. The modeling and simulations revealed that the soil is the preferential compartment. We also discuss the implications of the results about fate and ecological risks associated with benzo(a)pirene. We concluded that the emissions of HPAs can not be ignored and bioaccumulation among others risks can be induced.

Caracterización de la reactividad intrínseca de los halobencenos en el modelo conceptual de la teoría de funcionales de la densidad (TFD)

The aim of this paper is to study the family of halobenzenes for characterizing their intrinsic reactivity and in this way to establish a rational order of the intrinsic reactivity of this family of molecules in the electrophilic aromatic substitution. This study was carried out in the framework of Density Functional Theory which provides a global and local index that can be used in the characterization of the reactivity. This index is related to some concept derivatives of experimental chemistry, being a good approach to the characterization of halobenzenes.

Caracterización y clasificación geoquímica de asfaltitas cubanas

Traditional biomarker parameters and aromatic compounds were applied to characterize and classify ten Cuban asphaltites (asphaltene-rich petroleum occurring as seeps or filling veins, joints, cavities and fissures). Genetic molecular parameters were compared in order to establish oil-oil correlations between samples. Thermal evolution was investigated using saturated biomarker and aromatic maturity parameters. All samples seem to represent petroleum in the early catagenetic stage. Statistical procedures used as auxiliary techniques show that they represent oils of Family II (marine anoxic carbonate sourced oils), except for 2 samples interpreted as belonging to Family III oils (normal marine siliciclastic suboxic sourced oils).

Técnicas de extrações e procedimentos de clean-up para a determinação de hidrocarbonetos policílicos aromáticos (HPA) em sedimentos da costa do Ceará

Extraction and clean-up are essential points in polycyclic aromatic hydrocarbon (PAHs) analysis in a solid matrix. This work compares extraction techniques and clean-up procedures for PAH analysis. PAH levels, their toxicological significance and source were also evaluated in the waters of the Cocó and Ceará rivers. The efficiency of PAH recovery was higher for the soxhlet and ultrasonic techniques. PAH recovery varied from 69.3 to 99.3%. Total PAH concentration (ΣHPA) varied from 720.73 to 2234.76 µg kg-1 (Cocó river) and 96.4 to 1859.21 µg kg-1 (Ceará river). The main PAH sources are pyrolytic processes and the levels were classified as medium so that adverse effects are possible.

Preparação de N-alquil derivados do 1-bromo-2,4-dinitrobenzeno e do 1-cloro-2-nitrobenzeno: Uma alternativa às aulas práticas de substituição nucleofílica aromática

Preparation of the title compounds are described as an alternative nucleophilic aromatic substitution for practices in the graduate laboratory. The low toxicity and disponibility of the reagents make a suitable procedure approach to experiments regarding this aromatic reaction.

Experimento didático sobre cromatografia gasosa: uma abordagem analítica e ambiental

This paper describes an experiment to teach the principles of gas chromatography exploring the boiling points and polarities to explain the elution order of a series of alcohols, benzene and n-propanone, as well as to teach the response factor concept and the internal standard addition method. Retention times and response factors are used for qualitative identification and quantitative analysis of a hypothetical contamination source in a simulated water sample. The internal standard n-propanol is further used for quantification of benzene and n-butanol in the water sample. This experiment has been taught in the instrumental analysis course offered to chemistry and oceanography students.

Cloração do anisol, tolueno e nitrobenzeno com ácido tricloroisocianúrico (ATCI): aspectos computacionais sobre a reatividade e regiosseletividade

We present in this educational article a theoretical analysis based on DFT/B3LYP 6-311++G (d,p) and ab initio MP2/6-311++G(d,p) computational calculation about the reactivity and the regioselectivity on the chlorination reaction of anisole, toluene and nitrobenzene, using trichloroisocyanuric acid (TICA) as donor of Cl+. The H.O.M.O. / L.U.M.O. energy and N.B.O. atomic charges of various aromatic systems were calculated in ab initio level. The energies of the reagents and intermediaries were calculated using D.F.T.. These results have been presented as a quantitative example for the S E A mechanism, in the undergraduate organic chemistry disciplines.

Fontes vegetais naturais de antioxidantes

Growing knowledge on the health-promoting impact of antioxidants in everyday foods, combined with the assumption that a number of common synthetic preservatives may have hazardous side effects has led to increased investigations in the field of natural antioxidants, principally those found in plants. Food industries normally discard plant residues that could benefit the human health and diminish undesirable environmental impact. Once estimated the content of antioxidants in these residues, advantageous economical and social alternatives to the discard are possible, for example, their use for preparation of nutraceuticals to be offered to low-income populations. We present here a broad, although not complete, account of the continuously growing knowledge on the antioxidant capacity of whole fruits, seeds and peels, cereals, vegetal oils and aromatic plants, at several physical forms, as well as a description of the usual methods for evaluating their antioxidant capacity and examples of agroindustrial processes that could be harnessed for the production of antioxidant supplement food, along with research perspectives in the area.

Efeito de substâncias empregadas para remoção de cobre sobre o teor de compostos secundários da cachaça

High copper content is of great concern among producers of sugar-cane spirits who frequently use filters instead of cleaning the stills. This study compared the efficiency of activated carbon, ion-exchange-polymeric resin, and activated-carbon/iron-oxide magnetic composite for copper reduction without removing excessive organic compounds that are important for the beverage's quality. Resin was the most efficient copper adsorbent, removing fewer organic compounds. The composite also removed copper; however, it also removed large amounts of organic compounds. Activated carbon didn't remove sufficient copper to reduce its concentration to less than 5 g L-1, and it removed large amounts of higher alcohols and esters.

Validation of an analytical methodology for the quantitative analysis of petroleum hydrocarbons in marine sediment samples

This work describes a validation of an analytical procedure for the analysis of petroleum hydrocarbons in marine sediment samples. The proposed protocol is able to measure n-alkanes and polycyclic aromatic hydrocarbons (PAH) in samples at concentrations as low as 30 ng/g, with a precision better than 15% for most of analytes. The extraction efficiency of fortified sediments varied from 65.1 to 105.6% and 59.7 to 97.8%, for n-alkanes and PAH in the ranges: C16 - C32 and fluoranthene - benzo(a)pyrene, respectively. The analytical protocol was applied to determine petroleum hydrocarbons in sediments collected from a marine coastal zone.

Heterogeneidade de álcoois secundários em aguardentes brasileiras de diversas origens e processos de fabricação

Secondary alcohol concentrations in sugar cane spirits from different origins were determined by gas chromatography. A great variation in the concentration of the secondary alcohols was found in these spirits. Of the 33 brands analyzed, 8 of them were found to be out of conformity with the legislation. Sec butanol, for which the maximum allowed concentration level is 100 mg.L-1 in absolute ethanol, was found within a concentration range between 5 mg.L-1, the limit of quantitation (LQ) and 408 mg.L-1 in absolute ethanol. Sugar cane samples from Salinas, MG, were the only ones that exhibited self similarity because of the low concentrations of n-butanol and n-amylic alcohol (< limit of detection LD).