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.

Constituintes químicos e atividade Leishmanicida de Gustavia elliptica (Lecythidaceae)

The phytochemical investigation of the stem bark and leaves of G. elliptica provided a mixture of the norisoprenoids blumenol B and 6-epiblumenol B along with the triterpenes friedelin, as the major constituent, friedelanol, ursa-9(11),12-dien-3-ol, a-amyrin, β-amyrin, morentenol, epifriedelanol, as well as the sesquiterpenes trans-caryophyllene, α-humulene, ethyl hydnocarpate and other fatty acid esters. The identification of the compounds was performed on basis of spectrometric methods such as GC-MS, IR, MS and 1D and 2D NMR. Stem bark extracts showed significant leishmanicidal activity against promastigote forms of Leishmania braziliensis, with the best results for the chloroform extract.

Atribuição absoluta e geral de isômeros constitucionais por espectrometria de massas: o caso das metilpiperidinas

An absolute method is described via mass spectrometry (MS) for the structural assignment of isomers within the class of methylpiperidines. The method explores both the unimolecular and bimolecular gas phase behavior of structurally diagnostic fragment ions (SDFI). For the methylpiperidnes, the isomeric 2-methyl, 3-methyl and 4-methyl 2-azabutadienyl cations are found to function as SDFI. These fragment ions are expected to be formed from all members within the class, to be stable and to retain the structural information of the precursor molecule, and to not interconvert into one another. To characterize these SDFI, both the collision induced dissociation (CID) in argon and bimolecular ion/molecule chemistry with ethyl vinyl ether were compared.

Estudo espectroscópico de compósito obtido da reação no estado sólido entre um complexo mononuclear de vanádio(IV) e caulinita

The use of probes, such as paramagnetic species diluted in diamagnetic materials in EPR spectroscopy, and mathematical tools such, as the Kubelka-Munk function in DRUV-VIS spectroscopy are strategies in the analysis of complex mixtures of solid materials. The results obtained here show that the solid state reaction between the complex, [VO(acac)(BMIMAPY)] [ClO4], BMIMAPY = [(bis(1-methylimidazole-2-yl)methyl)(2-(pyridyl-2-yl)ethyl) amine] and acac = acetilacetonate, with kaolinite turns possible to obtain anisotropic EPR spectrum of the complex with a reasonable level of resolution. The study by DRUV-VIS using the method of second derivative mode of the Kubelka-Munk function revealed new complex structural arrangements, a solid hitherto unknown.

Extraction and isolation of dictamnine, obacunone and fraxinellone from Dictamnus dasycarpus Turcz. by supercritical fluid extraction and high-speed counter-current chromatography

Supercritical fluid extraction was used to extract active compounds from the Chinese traditional medicinal D. dasycarpus under the pressure of 30 MPa and temperature of 45 ºC. Further separation and purification was established by high-speed counter-current chromatography (HSCCC) with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (1:0.8:1.3:0.9, volume ratio). The separation yielded a total of 47 mg of dictamnine, 24 mg of obacunone and 83 mg of fraxinellone from 1.0 g of the crude extract in one step separation with the purity of 99.2, 98.4 and 99.0%, respectively, as determined by HPLC. The chemical structures of these compounds were identified by ESI-MS, IR, ¹H-NMR and 13C-NMR.

Quantificação sérica de vitamina C por CLAE-UV e estudo de estabilidade

Vitamin C, an exogenous antioxidant, is essential to human health. In this study, a method was validated to serum vitamin C quantification by HPLC-UV. Its stability with and without the use of tris [2-carboxy-ethyl] phosphine hydrochloride (TCEP), at -20 and -80 °C, in serum and supernatant were also evaluated. Analysis showed r² > 0.99, precision CV% < 15% and % bias < 15%, being linear, precise and accurate. The stability test revealed that using TCEP in serum storage at -20 and -80 °C or in supernatant at -80 °C the vitamin C levels remain stable for 30 and 12 days, respectively.

High performance thin layer chromatographic determination of nifedipine in human serum after liquid-liquid extraction

A method using HPTLC for quantitation of nifedipine in serum was developed and validated. It includes a liquid-liquid extraction, and carbamazepine as internal standard. Chloroform: ethyl acetate: cyclohexane (19:2:2, v/v/v) was the mobile phase. The method showed good relationship (r = 0.996) (2.00 to 25.00 ng/band, corresponding to 0.02 and 0.25 ng/µL in serum). The % RSD of intra-assay and inter-assay, were between 0.57 and 3.56 and 1.16 to 3.60, respectively. LOD and LOQ were 0.72 and 0.86 ng/band, respectively. The recovery values were between 93 and 102%. Rf for nifedipine and carbamazepine were 0.31 and 0.10, respectively.

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.

Phenolic derivatives and other chemical compounds from Cochlospermum regium

This study describes the chemical investigation of the ethyl acetate fraction obtained from the hydroethanolic extract of the xylopodium of Cochlospermum regium (Mart. & Schr.) Pilger, which has been associated with antimicrobial activity. Phytochemical investigation produced seven phenol derivatives: ellagic acid, gallic acid, dihydrokaempferol, dihydrokaempferol-3-O-β-glucopyranoside, dihydrokaempferol-3-O-β-(6"-galloyl)-glucopyranoside, pinoresinol, and excelsin. It also contained two triacylbenzenes, known as cochlospermines A and B. The hydroethanolic extract and its fractions exhibited antimicrobial activity (0.1 mg/mL) against Staphylococcus aureus and Pseudomonas aeruginosa. Gallic acid showed activity against S. aureus. Dihydrokaempferol-3-O-β-(6"-galloyl)-glucopyranoside is reported here for the first time in the literature.

Evaluation of antimicrobial activity and toxic potential of extracts and triterpenes isolated from Maytenus imbricata

The phytochemical study of hexane/ethyl ether (1:1) extract of the roots of M. imbricata, Celastraceae, resulted in the isolation and characterization of six known triterpenes: 11α-hydroxylup-20(29)-en-3-one, previously isolated from this species besides, 3β,11α-di-hydroxylup-20(29)-ene, 3,7-dioxofriedelane, 3-oxo-29-hydroxyfriedelane, tingenone and 6-oxo-tingenol. The chemical structures of these triterpenes were established by spectrometric data (IR, ¹H and 13C NMR) and through comparison with literature data. The hexane/ethyl ether (1:1), ethyl acetate and methanol extracts, and 11α-hydroxylup-20(29)-en-3-one, tingenone and 6-oxo-tingenol, showed antimicrobial properties on in vitro assays. All extracts and triterpenes, except 3β,11α-di-hydroxylup-20(29)-ene, presented toxicity demonstrated by the larvicidal effect test using Artemia salina.

Montmorilonita modificada como catalisador heterogêneo em reações de esterificação (m)etílica de ácido láurico

ABSTRACT Montmorillonite was modified with zirconium polyoxycations in the presence of ammonium sulphate. The material was characterized and used as a catalyst in the esterification of lauric acid, the reactions being accompanied by 2³ factorial design. Conversions of up to 95.33 and 83.35% were observed for the methyl and ethyl esterification reactions respectively, proving superior to results obtained by thermal conversion. The material was submitted to three reaction cycles and similar conversions were observed, indicating the catalyst is not significantly deactivated after reuse. The catalyst was also tested under reflux conditions, yielding a maximum conversion of 36.86%.

A fração volátil das aguardentes de cana produzidas no Brasil

The volatile fraction of sugar cane spirits plays a key role in the quality and acceptance of these beverages. The composition of this fraction is dependent on the way sugar cane collection, fermentation, distillation and aging are carried out. The materials used in these processes strongly influence chemical composition. Acetic acid, acetaldehyde, ethyl acetate, ethanol, 2.3-butanedione, n-propanol, 3-methyl-buthanol and isobuthanol were the major volatiles in spirits. Dimethyl sulfide and n-propanol impaired beverage flavor. Ethyl octanoate, 1.1-diethoxy-ethane, 2-phenylethanol and 3-methyl-butanol were important aroma contributors. Ageing allows the extraction of flavor-active components (e.g., phenolic compounds) from wood.

Montagem de uma prensa para fios de sódio metálico

Several organic chemistry labs in Brazil suffers from the absence of a safe method to extrude sodium wire, used to obtain anhydrous solvents such as THF or ethyl ether. This technical note presents the assembly instructions for a sodium wire press, similar to the one that has been used for the past four years in our laboratory without any maintenance.

Novas N-benzoiltiraminas de Swinglea glutinosa (Rutaceae)

Phytochemical studies of the leaves and fruits have led to the identification of the known amides (E)-N-methyl-cinnamamide, N-benzoyltyramine, N-benzoyl-O-geranyltyramine, N-benzoyl-O-(4-acetoxyl)-geranyltyramine, in addition to the new N-{2-[4-(butoxyl-3-one)phenyl]ethyl}benzamide, N-{2-[4-(2,3-dihydroxy-2-methyl-butoxylanal)phenyl]ethyl}benzamide, N-{2-[4-(2,3-dihydroxy-2-methyl-butoxyloic)phenyl]ethyl}benzamide, N-benzoyl-O-(4-acetoxyl-6,7-epoxy)-geranyltyramine, N-benzoyl-O-(4-acetoxyl-6,7-dihydroxy)-geranyltyramine and N-benzoyl-O-(6-acetoxyl-4,7-dihydroxy)-geranyltyramine. The isolated compounds clearly point to Swinglea phytochemical affinities with other Aurantioideae species.

Sesquiterpenos produzidos pelo fungo endofítico Phomopsis cassiae com atividade antifúngica e inibidora de acetilcolinesterase

SESQUITERPENES PRODUCED BY ENDOPHYTIC FUNGUS Phomopsis cassiae WITH ANTIFUNGAL AND ACETYLCHOLINESTERASE INHIBITION ACTIVITIES. Two new diastereoisomeric cadinanes sesquiterpenes 3,9-dihydroxycalamenene (1-2), along with the known 3-hydroxycalamen-8-one (3) and aristelegone-A (4), were isolated from ethyl acetate extract of Phomopsis cassiae, an endophytic fungus in Cassia spectabilis. Their structures, including relative stereochemistry, were determined on the basis of detailed interpretation of 2D NMR spectra and comparison with related known compounds. Compounds 1-4 displayed antifungal activity against the phytopathogenic fungi Cladosporium cladosporioides and C. sphaerospermum, as well as inhibition of acetylcholinesterase.