Reações de inserção intramolecular de diazo compostos polifuncionais catalisadas por ródio(II): síntese de oxetan-3-ona-2-carboxilato e outros heterociclos funcionalizados

gamma-Hydroxy-alpha-diazo-beta-ketoesters are key intermediates in the chemistry of penicilin-based antibiotics and natural products. The method developed here for the synthesis of ethyl 2-diazo-4-hydroxy-3-oxo-butanoate 17 (in two steps from the diazo mercurial 2) compares very favorably with those reported in the literature for similar compounds. The Rh2(OAc)4-mediated intramolecular OH-insertion reaction of the diazo hydroxy ester 17 was investigated, furnishing the oxetan-3-one-2-carboxilate 18 in good yield. When the diazo ester lacks a free hydroxyl group as in the case of the phenoxy diazo ester 11 an intramolecular CH-insertion takes place, affording the 2H-chromene 20 in almost quantitative yield. The behavior of other functionalized diazo esters towards Rh2(OAc)4 was also investigated.

Componentes voláteis do café torrado. Parte II. Compostos alifáticos, alicíclicos e aromáticos

This review is about the aliphatic, alicyclic and aromatic compounds (non-heterocyclic compounds) that are present in the volatile fractions of roasted coffees. Herein, the contents, aroma precursors and the sensorial properties of volatile phenols, aldehydes, ketones, alcohols, ethers, hydrocarbons, carboxylic acids, anhydrides, esters, lactones, amines and sulphur compounds are discussed. Special attention is given to the compounds of these groups that are actually important to the final aroma of roasted coffees.

The interaction between mercury(II) and sulfathiazole

The interaction of mercury(II) with sulfathiazole has been analyzed. IR and NMR spectral studies suggest a coordination of Hg(II) with the Nthiazolic atom, unlike related Hg-sulfadrugs compounds. The complex was screened for its activity against Escherichia coli, showing an appreciable antimicrobial activity compared with the ligand.

Emprego de compostos organometálicos mononucleares de paládio(II) na ativação de macrófagos peritoneais de camundongos

The immune responses are mediated by a variety of cells that, when activated, produce a number of molecules. Macrophages are the first cells to take part in the immune response releasing many compounds in the extracellular environment such as H2O2. Taking into account this aspect we evaluated the activation of an immunological system, in vitro, by determining the H2O2 released in cultures of peritoneal macrophage cells from Swiss mice in the presence of organopalladated compounds of the type [Pd(dmba)(X)(dppp)], dmba = N,N-dimethylbenzylamine, dppp = 1,3-bis(diphenylphosphine)propane, X = Cl, N3, NCO, NCS. An excellent activation of macrophages by the [Pd(dmba)(X)(dppp)] compounds was observed and the influence of the X ligand on the immune response could be verified.

Síntese e caracterização de novos complexos de platina (II) com ligantes derivados do furano e nitrofurano

Platinum (II) complexes, for example, cisplatin and carboplatin, have been used as chemotherapeutic agents for the treatment of various types of cancer. Several other complexes of this metallic ion are also under clinical evaluation. This work describes the synthesis of five new platinum (II) complexes having furan and 5-nitrofuran derivatives and chloride as ligands. The compounds were characterized by NMR, IR and elemental analysis.

Building complexity in O2-binding copper complexes : site-selective metalation and intermolecular O2-binding at dicopper and heterometallic complexes derived from an unsymmetric ligand

A novel unsymmetric dinucleating ligand (LN3N4) combining a tridentate and a tetradentate binding sites linked through a m-xylyl spacer was synthesized as ligand scaffold for preparing homo- and dimetallic complexes, where the two metal ions are bound in two different coordination environments. Site-selective binding of different metal ions is demonstrated. LN3N4 is able to discriminate between CuI and a complementary metal (M′ = CuI, ZnII, FeII, CuII, or GaIII) so that pure heterodimetallic complexes with a general formula [CuIM′(LN3N4)]n+ are synthesized. Reaction of the dicopper(I) complex [CuI 2(LN3N4)]2+ with O2 leads to the formation of two different copper-dioxygen (Cu2O2) intermolecular species (O and TP) between two copper atoms located in the same site from different complex molecules. Taking advantage of this feature, reaction of the heterodimetallic complexes [CuM′(LN3N4)]n+ with O2 at low temperature is used as a tool to determine the final position of the CuI center in the system because only one of the two Cu2O2 species is formed

Selective Ortho-Hydroxylation–Defluorination of 2-Fluorophenolates with a Bis(m-oxo)dicopper(III) Species

The bis(mu-oxo) dicopper(III) species [Cu-III 2(mu-O)(2)(m-XYLMeAN)](2+) (1) promotes the electrophilic ortho-hydroxylation-defluorination of 2-fluorophenolates to give the corresponding catechols, a reaction that is not accomplishable with a (eta(2) : eta(2)-O-2) dicopper(II) complex. Isotopic labeling studies show that the incoming oxygen atom originates from the bis(mu-oxo) unit. Ortho-hydroxylation-defluorination occurs selectively in intramolecular competition with other ortho-substituents such as chlorine or bromine

Síntese e caracterização de um novo complexo de platina (IV) a partir de seu análogo de platina (II) utilizando iodo molecular como agente oxidante: uma rota sintética interessante para obtenção de novos complexos de platina

In an attempt to reduce toxicity and widen the spectrum of activity of cisplatin and its analogues, much attention has been focused on designing new platinum complexes. This work reports the synthesis and characterization of novel compounds of the platinum (II) and platinum (IV) containing 2-furoic hydrazide acid and iodide as ligands. Although the prepared compounds do not present the classical structure of biologically active platinum analogues, they could be potentially active or useful as precursors to prepare antitumor platinum complexes. The reported compounds were characterized by ¹H NMR, 13C NMR, 195Pt NMR, IR and elemental analyses.

Titulações potenciométricas de cátions metálicos tendo como eletrodo indicador o sistema Cu/Cu(II)-EDTA

In potentiometric titrations of metal cations with EDTA the Hg/HgY2- system is usually used to detect the end point. However, the use of mercury has been discouraged in analytical procedures due to its toxicity. In this work the Cu/CuY2- system was used as indicator electrode for potentiometric titrations of some metal cations with EDTA. The solutions of Cu2+, Cd2+, Mn2+, Co2+ and Zn2+ were titrated with Na2EDTA solution in the presence of a small concentration of the CuY2- complex using a copper wire as indicator electrode. The potentiometric titrations with the Cu/CuY2- system showed good correlation when compared with an Hg/HgY2- system.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.

Synthesis, structure and physicochemical properties of zinc and copper complexes based on sulfonamides containing 8-aminoquinoline ligands

Sulfonamides obtained by reaction of 8-aminoquinoline with 4-nitrobenzenesulfonylchloride and 2,4,6-triisopropylbenzenesulfonyl chloride were used to synthesize coordination compounds with CuII and ZnII with a ML2 composition. Determination of the crystal structures of the resulting zinc and copper complexes by X-ray diffraction show a distorted tetrahedral environment for the [Cu(qnbsa)2], [Cu(qibsa)2] and [Zn(qibsa)2] complexes in which the sulfonamide group acts as a bidentate ligand through the nitrogen atoms from the sulfonamidate and quinoline groups. The complex [Zn(qnbsa)2] crystallizes with a water molecule from the solvent and the Zn is five-coordinated and shows a bipyramidal-trigonal geometry. The electrochemical and electronic spectroscopy properties of the copper complexes are also discussed.

Teores de carbamato de etila em aguardentes de cana e mandioca: parte II

Herein, we report the concentration of ethyl carbamate (EC) and copper in 380 samples of sugar-cane spirit and 45 samples of manioc spirit as determined by GC-MS and FAAS respectively. The cyanide content determined spectrophotometrically is reported for the manioc spirit. Sugar cane spirit produced by alembic distillation (70,0 µg L-1) shown a lower content of EC than samples produced by column distillation (270 µg L-1). No simple correlation between the content of EC and copper for sugar cane spirit as well among the concentration of EC, copper, and cyanide for manioc spirit could be observed.

Caracterização de escamas do peixe piau (Leporinus elongatus) e sua aplicação na remoção de Cu(II) de meio aquoso

Characterization of fish scales of Leporinus elongatus and their application in the removal of Cu(II) from aqueous solutions are described. It was observed that the scales are mainly formed by hydroxyapatite and type I collagen. Adsorption of Cu(II) was performed using batch experiments at 25 0C. The ANOVA statistical results have shown that the Langmuir model was successful applied to determine the maximum adsorption capacity of 2.686 x10-4 mol g-1 and the Langmuir equilibrium parameter (b) of 168.8 L mol-1. The Langmuir separation parameter, R L, has shown favorable adsorption of Cu(II) on the scales.

Estudo do comportamento eletroquímico de substâncias complexantes utilizando eletrodo de cobre

Copper electrode can be used for determination of complexing compounds through complexation reactions between Cu(II) and the analites. In this work some studies with three compounds were performed: glycine (precursor of glyphosate synthesis), herbicide glyphosate and aminomethylphosphonic acid (main metabolite of glyphosate). These compounds are complexing agents for Cu electrodes. Through simple experiments (cyclic voltammetry and corrosion studies) the applicability of the copper electrode as electrochemical sensor for complexing compounds in flow systems was presented.

Síntese e caracterização estrutural do ligante isatina-3-(N4-benziltiossemicarbazona) e do seu complexo de mercúrio(II)

The reaction of 4-(phenyl)thiosemicarbazide with isatin yielded a new ligand, isatin-3-(N4-benzylthiosemicarbazone). Isatin-3-(N4-benzylthiosemicarbazone) deprotonated in ethanol/KOH reacts with an ethanolic solution of Hg(NO3)2 to give a mercury complex. The compounds were characterized by IR and X-ray single crystal structure determination. The X-ray studies revealed that the complex possesses a tetrahedral geometry with two deprotonated thiosemicarbazone ligands coordenated. The ligand and its mercury complex crystallize in the monoclinic (P2(1)/c) and triclinic (P-1) crystal system, respectively.