Synthesis of quinoxaline 1,4-di-N-oxide derivatives on solid support using room temperature and microwave-assisted solvent-free procedures

We describe the synthesis of 12 new ethyl and methyl quinoxaline-7-carboxylate 1,4-di-N-oxide derivatives on solid supports with room temperature and microwave-assisted solvent-free procedures. Results show that solid supports have good catalytic activity in the formation of quinoxaline 1,4-di-N-oxide derivatives. We found that florisil and montmorillonite KSF and K10 could be used as new, easily available, inexpensive alternatives of catalysts. Additionally, room temperature and microwave-irradiation solvent-free synthesis was more efficient than a conventional procedure (Beirut reaction), reducing reaction time and increasing yield.

Phenolic compounds from Sidastrum micranthum (A. St.-Hil.) fryxell and evaluation of acacetin and 7,4'-Di-O-methylisoscutellarein as motulator of bacterial drug resistence

From the aerial parts of Sidastrum micranthum (A. St.-Hil.) Fryxell (Malvaceae) were isolated m-methoxy-p-hydroxy-benzaldehyde, o-hydroxy-benzoic acid, acacetin, quercetin, 7,4′-Di-O-methylisoscutellarein, genkwanin and tiliroside. These compounds were identified by data analyses of spectroscopic methods. Although acacetin and 7,4′-Di-O-methylisoscutellarein did not display relevant antibacterial activity (MIC = 256 µg/mL), they modulated the activity of antibiotics, i.e. in combination with antibiotics at 64 µg/mL (¼ MIC), a two-fold reduction in the MIC was observed for norfloxacin and ethidium bromide; regarding tetracycline and erythromycin a two-fold reduction in the MIC was observed only with 7,4′-Di-O-methylisoscutellarein.

Determinação de deoxinivalenol e zearalenona em arroz natural e parboilizado e suas frações utilizando quEChERS e HPLC/UV-FL

The QuEChERS extraction method followed by quantification using HPLC/UV-FL was evaluated for deoxynivalenol (DON) and zearalenone (ZEA) determination in natural and parboiled rice and their fractions (bran and husk). The comparison between QuEChERS and partition with acetonitrile extraction showed that the first one was better. It presented higher recovery (91% for DON, 105% for ZEA) wih precision ranging from 1.5 to 18.6%. The limits of quantification were 22.2 µg kg-1 for DON and 4.3 µg kg-1 for ZEA. DON and ZEA showed higher levels in endosperm of parboiled rice (8 e 111.7 µg kg-1, respectively) when compared to natural rice.

Síntese e caracterização de copolímeros de cadeia lateral derivados de acrilatos de 4,5-di-hidroisoxazol e do (-)-mentol

Five monomers 5-[4-(5-cyano-4,5-dihydroisoxazol-3-yl)phenoxy]undecyl acrylate (7a); n-alkyl 3-{4-[5-(acryloyloxyundecyl)oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylate (7b,c for n-butyl and n-hexyl, respectively); 3-{4-[5-(acryloyloxyundecyl) oxyphenyl]}-4,5-dihydroisoxazole-5-carboxylic acid (7d) and (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl acrylate (9) and the corresponding copolymers 10a-d,11 and homopolymers 12 from 7a and 13 from 9 were designed and synthesized. Except for acrylate 9 which is derived from (-)-menthol, all of the monomers belong to the series containing the isoxazoline ring linked to the acrylate unit by a flexible spacer chain of eleven methylene units. They presented low glass temperature and despite birefringence behavior, these copolymers showed no mesomorphic properties.

Síntese de derivados 4-aril-3,4-di-hidrocumarínicos catalisada por NbCl5

Multicomponent reactions between phenols, β-diesters and benzaldehydes for the synthesis of 4-aryl-3,4-dihydrocoumarin derivatives were carried out under mild conditions (room temperature) and presented moderate yields (38-88%) and reasonable reaction times (2-4 days), using niobium pentachloride as a catalyst.

Coeficiente de distribuição do inseticida tiametoxam na fração mineral de solos sob efeito de ácidos orgânicos mono, di e tricarboxílicos

The aim of this study was to investigate the sorption and desorption of thiamethoxam in contrasting soils under the effect of organic acids. The results showed that MTo sorption had higher Kd. The presence of organic acids increased sorption and reduced desorption of thiamethoxam at MTo. The opposite was observed for the LVdf where the presence of 400 µmol L-1 of acid reduced the sorption of thiamethoxam in a concentration of 20 µmol L-1, not influencing desorption. The dynamics of organic acids with minerals from the soil particles were clarified by infrared analysis.

Synthesis, characterization and computational studies of (E)-2-{[(2-aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butylphenol

(E)-2-{[(2-Aminopyridin-3-yl)imino]-methyl}-4,6-di-tert-butyl-phenol ( 3: ), a ligand containing an intramolecular hydrogen bond, was prepared according to a previous literature report, with modifications, and was characterized by UV-vis, FTIR, ¹H-NMR, 13C-NMR, HHCOSY, TOCSY and cyclic voltammetry. Computational analyses at the level of DFT and TD-DFT were performed to study its electronic and molecular structures. The results of these analyses elucidated the behaviors of the UV-vis and electrochemical data. Analysis of the transitions in the computed spectrum showed that the most important band is primarily composed of a HOMO→LUMO transition, designated as an intraligand (IL) charge transfer.

DI-HIDROCUCURBITACINA B: SEMI-SÍNTESE DE NOVOS DERIVADOS GLICOSILADOS

In the last ten years, the interest in natural and semi-synthetic cucurbitacin derivatives has increased, primarily due their cytotoxic and anti-tumoral activities. However, the isolation of glycosylated cucurbitacins has been difficult due the presence of β-glucosidase enzyme. With the aim of obtaining new glycosylated derivatives, the glycosylation of dihydrocucurbitacin B under Köenigs-Knorr and imidate reaction conditions was studied. Novel glycoside derivatives 16-(1,2-orthoacetate-3,4,6-tri-O-acetyl-α-D-glucopyranosyl)-dihydrocucurbitacin B (2), 2-O-β-D-2,3,4,6-tetra-O-acetyl-galactopyranosyl dihydrocucurbitacin B (3) and 2-O-β-D-galactopyranosyl dihydrocucurbitacin B (4) were synthesized for the first time in 17% (2 and 3) and 48% (4) yields.

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Amphoteric behavior of di-2-pyridyl ketone benzoylhydrazone in ethanol-water mixtures

The ligand di-2-pyridyl ketone benzoylhydrazone (DPKBH) is widely used for the determination of transition metal ions in environmental samples. Due to its low solubility in water it is used in aqueous-ethanol (1:1) solvent and for higher sensitivity the pH must be properly adjusted. The properties of DPKBH solutions must be known at different ethanol-water percentages in order to achieve higher sensitivity and/or selectivity for metal analysis. The acid-base behavior of this reagent in aqueous-ethanol solvent and the dissociation/ionization constants (pK1 and pK2) of DPKBH have been determined in different aqueous-ethanol solvent mixtures (10, 20, 30 and 50 % V/V of ethanol) from potentiometric titrations at 25.0 ± 0.1° C. As the amount of ethanol increases from 10 to 30% the pK1 and pK2 values increased, but they decreased in 50% of the organic solvent. The results are correlated with the medium composition and its effects.

Síntese e atividade fitotóxica de amidas derivadas do ácido 6alfa,7beta-di-hidroxivouacapan-17beta-óico

O ácido 6alfa,7beta-di-hidroxivouacapan-17beta-óico foi isolado das sementes de Pterodon polygalaeflorus Benth (Leguminosae) e então dez novas amidas derivadas deste ácido foram preparadas. Os efeitos destas amidas na germinação de sementes de Sorghum bicolor L. e Cucumis sativus L. foram avaliados. Nove compostos, a uma concentração de 100 ppm, mostraram um efeito inibitório (5-21%) no crescimento radicular de C. sativus L.. A N-(t-butil)-6alfa,7beta-di-hidroxivouacapan-17beta-amida mostrou a maior ação inibitória (33%) para S. bicolor L.. Somente a N-benzil-6alfa,7beta-di-hidroxivouacapan-17beta-amida mostrou efeito estimulatório no crescimento radicular para C. sativus L. e S. bicolor L., de 16% e 34% respectivamente.

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Spectrophotometric determination of arsenic in soil samples using 2-(5-bromo-2-pyridylazo)-5-di-ethylaminophenol (Br-PADAP)

In this paper, a new, simple and sensitive method for arsenic determination in soil is proposed. This is based on the reduction of silver (I) and iron (III) ions by arsine followed by a complexation reaction of iron (II) with the spectrophotometric reagent Br-PADAP 2-(5-bromo-2-pyridylazo)-5-di-ethylaminophenol. Arsenic determination with a Sandell's sensitivity of 3.1 10-4 cm-2, linear range from 0.1 µg ml-1 to 2.0 µg ml-1 (r560 = 0.9995), molar absorptivity of 2.45 10(5) l mol-1 cm-1 and a concentration detection limit of 1.4 ng ml-1 (3s) were obtained using a 10 ml sample volume. Selectivity was increased with the use of EDTA as a masking agent. The proposed method was applied for arsenic determination in the presence of several ions amounts in digested soil samples. The results revealed that antimony (III), mercury (II), germanium (IV), platinum (IV) interferes at all analyzed proportions. The interferences can be easily removed by the use of EDTA. Precision and accuracy obtained were satisfactory with a R.S.D. < 5 %. Recovery of arsenic in soil samples varied from 95.55 to 102.70 % with a mean of 99.63 %. These results demonstrated that the proposed method is applicable for arsenic analysis in different soil samples.

Di-And Tri-Hydroxylated Kaurane Derivatives From Microbial Transformation Of Ent-Kaur-16-En-19-Ol By Cephalosporium Aphidicola And Their Allelopathic Activity On Lactuca Sativa (Lettuce)

The use of microorganisms to induce chemical modifications in organic molecules is a very useful tool in organic synthesis, to obtain biologically active substances. The fungus Cephalosporium aphidicola is known by its ability to hydroxylate several skeleton positions of many classes of organic compounds. In this work, the microbial transformation of ent-kaur-16-en-19-ol (1) by C. aphidicola, afforded two hydroxylated compounds, ent-kauran-16β,19-diol (2) and ent-kauran-16β,17,19-triol (3). Their structures were established by 1D and 2D-NMR studies. Both compounds were tested for their action on the growth of radical and shoot of Lactuca sativa.