Estudo experimental e teórico da redução de bases de Schiff derivadas da 3,3-difenilpropilamina

A series of seven Schiff bases have been synthesized from 3,3-diphenylpropilamine and substituted benzaldehydes. These imines were treated with NaBH4 in ethanol affording the corresponding amines in 98-55% yields. A molecular modeling study was performed with the Schiff bases in order to compare the theoretical parameters with the experimental results. The theoretical parameters were obtained by AM1 and PM3 semi-empirical methods. The analysis of charge, electron densities and LUMO coefficients suggested that the most favorable interactions should occur with Schiff bases containing electron-donating groups, in accordance with experimental yields, showing that the higher reactivity is due to higher electrophilic character of imine carbons.

Química de complexos de (etilenodiaminatetraacetato)rutenato(III/II)

This paper provides a survey of general aspects involved in the coordination chemistry of low-valent (mainly +III,+II), low-spin (d p5,d p6) ruthenium ions with ethylenediamine-N,N,N',N'-tetraacetate (edta) and their substituted derivatives. The topics covered herein include structure, reactivity, kinetics, thermodynamics, electrochemistry and spectroscopy. The contributions from either our research group or the literature over the last three decades are focused in this review.

Anéis aromáticos condensados e relação E4/E6: estudo de ácidos húmicos de gleissolos por RMN de 13C no estado sólido utilizando a técnica CP/MAS desacoplamento defasado

In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS 13C techniques, did not show significant correlation between the E4/E6 ratio and the degree of aromaticity. However, dipolar dephasing (DD) measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS 13C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity) of the humic substances. The results indicated that the E4/E6 ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS), underestimates aromatic rings in condensed structures.

Mercury in soils and sediments from gold mining liabilities in Southern Amazonia

The 1980-1990 Amazonian gold rush left an enormous liability that increasingly has been substituted by developing fish aquaculture. This work aimed at the identification of the mercury levels in the environment, associated with fish farms located in the North of Mato Grosso State, Southern Amazon. Sediment and soil samples were analyzed for total organic carbon and total mercury. Results indicate that the chemical characteristics of the sediment largely depend on the management procedures of the fish pond (liming, fish food used and fish population). The soils presented relatively low concentrations when compared with other data from the literature.

Síntese e propriedades catalíticas em reações de oxidação de goethitas contendo nióbio

Nb-substituted goethites have been prepared and characterized by Mössbauer spectroscopy, XRD, SEM and BET surface area measurements. Mössbauer and XRD analyses suggested that Nb replaces Fe3+ in the structure with duplet formation. The insertion of Nb into the goethite structure caused a significant increase in the BET surface area of the material. The prepared alpha-Fe1-xNb xOOH was investigated for the H2O2 decomposition to O2 and for the Fenton reaction to oxidize the dye methylene blue. It was observed that the introduction of Nb in to goethite produced a strong increase in the activity of oxidation of the dye contaminant by H2O2.

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.

Purificação e caracterização de uma gentioexaose obtida de botriosferana por hidrólise ácida parcial

A hexa-oligosaccharide was obtained by partial acid hydrolysis from botryosphaeran, an exopolysaccharide (EPS) β(1→3; 1→6)-D-glucan type, produced by the ascomyceteous fungus Botryosphaeria rhodina. The oligosaccharide was purified by gel filtration and charcoal-Celite column chromatography and the analysis was followed by HPAEC/PAD. The structure was determined by NMR spectroscopy and mass spectrometry, which showed that the oligosaccharide consists of six β-D-glucopiranosyl units O-6 substituted (gentiohexaose).

Estudo teórico de propriedades ópticas não-lineares de nanotubos de carbono de parede única quimicamente modificados

Structure and first hyperpolarizability for a series of armchair a(5,5) chemically modified carbon nanotubes (CNT) were calculated at semiempirical and density functional levels of theory. The 4,4´-substituted stilbenes were selected as chromophore with substituents at position 4´ set to X=NO2, H, Cl, OH and NH2. The calculated values for static first hyperpolarizability (β) were almost linearly dependent on the electronic effect of the group X, increasing from NO2 to NH2. At DFT level the effect of inserting the chromophore in the CNT surface was to enhance the β value up to 70% relative to the free 4,4´-substituted stilbene.

Efficient synthesis of benzothiazine and acrylamide compounds

This article describes the synthesis of the new (2Z)-2-(4-methoxybenzylidene)-6-nitro-4H -benzo[1,4]thiazin-3-one, (2Z)-2-(4-methoxybenzylidene)-4-methyl-6-nitro-4H-benzo[1,4]thiazin-3-one, (2Z)-6-amino-2-(4-methoxybenzylidene)-4H -benzo[1,4]thiazin-3-one, (2Z)-6-butylamino-2-(4-methoxybenzylidene)-4-methyl-4H-benzo[1,4]-thiazin-3-one and (2E)-N-alkyl-N-(2-hydroxy-5-nitrophenyl)-3-phenylacrylamides and the spectroscopic data. The arylidenebenzothiazine compounds were prepared using the Knoevenagel condensation with substituted benzaldehydes in the presence of sodium methoxide in DMF. The presence of a nitro substituent in the 4-position, water and a slightly acid reaction medium in this condensation caused the rupture of the benzothiazine ring and subsequent formation of the phenylacrylamide compounds. A crystallographic data was presented for (2E)-3-(4-bromophenyl)-N-dodecyl-N -(2-hydroxy-5-nitrophenyl) acrylamide.

Gas-phase solvolysis type reactions of SiCl3+ cations

Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.

Luz: um raro produto de reação

The production of visible light by chemical reactions constitutes interesting and fascinating phenomena and several reaction mechanisms are discussed to rationalize excited state formation. Most efficient chemiluminescence reactions are thought to involve one or more electron transfer steps and chemiexcitation is believed to occur by radical annihilation. A brief introduction to the general principles of light production and the main known chemiexcitation mechanisms will be given here. Subsequently, recent results on the mechanistic elucidation of efficient chemiluminescence systems, as the peroxyoxalate reaction, the induced decomposition of phenoxy-substituted 1,2-dioxetanes and the catalyzed decomposition of new a-peroxylactones will be discussed.

Uso da FTIR na obtenção de resinas e na síntese de peptídeos em fase sólida

Despite the increase in peptide chain aggregation, which decreases the rate of coupling reactions, the synthesis and use of very highly substituted resins still remains as a controversial point in the SPPS, due to its clear economical advantages (lesser solvent consumption and higher amount of peptide per synthesis). In order to better investigate the synthesis and the use of very highly substituted resins, the FTIR, NMR and EPR were compared. By FTIR techniques it was possible to follow all the steps of resin synthesis and the factors affecting the aggregation of the chains inside the peptidil-BHAR and MBHAR.

Synthesis of 2-azetidinone derivatives of 6-nitro-1H-indazole and their biological importance

A new series of 3-chloro-1-{[2-(6-nitro-1H-indazol-1-yl)ethyl]amino}-4-(substituted phenyl)-2-azetidinones (4a-j) was synthesized in four steps from 6-nitro-1H-indazole and characterized by IR, ¹H NMR, 13C NMR, FAB-mass spectrometry and chemical methods. Compounds 4(a-j) were screened in vitro for their antibacterial, antifungal and antitubercular activities against some selected microorganism and for their antiinflammatory activity (in vivo) against albino rats (either sex). All above activities of compounds 4(a-j) showed acceptable results.

Synthesis and biological activity of sulfur compounds showing structural analogy with combretastatin A-4

We extended our previous exploration of sulfur bridges as bioisosteric replacements for atoms forming the bridge between the aromatic rings of combretastatin A-4. Employing coupling reactions between 5-iodo-1,2,3-trimethoxybenzene and substituted thiols, followed by oxidation to sulfones with m-CPBA, different locations for attaching the sulfur atom to ring A through the synthesis of nine compounds were examined. Antitubulin activity was performed with electrophoretically homogenous bovine brain tubulin, and activity occurred with the 1,2,3-trimethoxy-4-[(4-methoxyphenyl)thio]benzene (12), while the other compounds were inactive. The compounds were also tested for leishmanicidal activity using promastigote forms of Leishmania braziliensis (MHOM/BR175/M2904), and the greatest activity was observed with 1,2,3-trimethoxy-4-(phenylthio)benzene (10) and 1,2,3-trimethoxy-4-[(4-methoxyphenyl) sulfinyl]benzene (15).

Synthesis, characterization, and biological activity of a new class of dialkylphosphorylhydrazone derivatives of isatin

Sixteen dialkylphosphorylhydrazones were synthesized by condensation of phosphorylhydrazines with substituted isatins. Products were characterized by FTIR, ¹H-NMR, 13C-NMR, and 31P-NMR. Fungicidal activities of these compounds against Rhizoctonia solani and Fusarium oxysporum were also evaluated. Some compounds inhibited the growth of Rhizoctonia solani and Fusarium oxysporum by 43% and 51%, respectively. These compounds exhibited no effects on germination of lettuce seeds (Lactuca sativa L).