Cycloaddition Reactions: Reaction of 3-Methyl-2-phenylpyrrocoline with Dimethyl Acteylenedicarboxylate

Reaction of 3-methyl-2-phenylpyrrocoline(I) and dimethyl acetylenedicarboxylate(II) in refluxing toluene furnishes cis-7',8-dihydro.4,5,8,9-tetramethoxycarbonyl-7'-phenyl-7' -methylazocino(2,1,8-cd]pyrrolizine (III) and trans-7',8-dihydro-4,5,8,9-tetramethoxycarbonyl-7-phenyl-7'-methylazocino[2,1,8-cd]pyrrolizine (IV), while the same reaction at ambient temperature yields 1-[(1,2-trans-dimethoxycarbonyl)vinyl]-3-methyl-2-phenylpyrrocoline (V) and 1-[(1,2-cis-di(methoxycarbonyl)vinyl)--methyl-2- phenylpyirocoUne (V) and 1-[(I,2-cis-di(methoxycarbonyl)Yinyl]-3-metbyl-2-phenylpyrrocoline(VI) as the major products. The structure of IV has been determined by X-ray crystallography.A possible mechanism of formation of these products is also discussed.

Determinação espectrofotométrica do bromidrato de fenoterol em preparações farmacêuticas

Um método espectrofotométrico simples foi desenvolvido para a determinação do bromidrato de fenoterol (BF) em comprimidos, gotas e xarope, como princípio ativo único e associado ao ibuprofeno. O método se baseia na reação de acoplamento oxidativo do BF com o 3-metil-2-benzotiazolinona hidrazona (MBTH), na presença de sulfato cérico, como agente oxidante. A mistura de BF, MBTH e sulfato cérico, em meio ácido, produz um composto colorido (vermelho castanho) com máximo de absorção a 475 nm. A curva de calibração foi linear num intervalo de concentração de 3,0 a 12,0 µg/mL, com coeficiente de correlação linear de 0,9998. Os parâmetros experimentais que afetam o desenvolvimento e a estabilidade do produto colorido foram cuidadosamente estudados e otimizados. O método foi aplicado em amostras comerciais e simuladas, obtendo-se coeficientes de variação entre 0,25 % a 0,82 % e médias de recuperação do padrão que variaram de 98 % a 102 %. O método proposto mostrou-se exato, preciso, linear e não é passível de interferência de excipientes, para as formas farmacêuticas comprimidos e gotas. Não houve interferência do ibuprofeno que consta de uma das formulações analisadas, associado ao BF. Quanto ao xarope, houve interferência do veículo sugerindo reações de seus componentes com o MBTH.

Spectrophotometric determination of fenoterol hydrobromide in pharmaceutical preparations

A simple spectrophotometric method has been developed,for the determination of fenoterol hydrobromide (FH) in tablets, drops and syrup, as the only active principle and associated with ibuprofen. The method is based on the oxidative coupling reaction of the FH with 3-methyl-2-benzothiazolinone hydrazone (MBTH) and ceric sulphate as oxidant reagent. The mixture of the drug, MBTH and ceric sulfate, in acid medium, produces a red brown color compound, with absorption maximum at 475 nm. The calibration curve was linear over a concentration range from 3.0 to 12.0 mu g/mL, with correlation coefficient of 0.9998. The different experimental parameters affecting the development and stability of the color compound were carefully studied and optimized. The method was applied successfully to assay FH in dosage forms and simulated samples. The coefficient of variation was from 0.25 % to 0.82 % and average recoveries of the standard from 98 % to 102 %. The excipients (tablets and drops) did not interfere in the analysis and the results showed that method can be used for determination of the FH isolated or associated with ibuprofen with precision, accuracy and specificity. In case of syrup, the interference in the analysis suggests a possible reaction between vehicle components with MBTH.

Incidence of patulin in fruits and fruit juices marketed in Campinas, Brazil

One hundred and eleven samples of processed fruit juices (apple, grape, pineapple, papaya, guava, banana and mango) and 38 samples of sound fruits (apple, papaya, mango, pear and peach) produced and marketed in Brazil, were analysed for patulin by HPLC. Only one out of 30 samples of apple juice was found positive at 17 μg/l. Patulin was not detected in the other foodstuffs. It was found in 14 samples of spoiled fruit samples of apple (150-267 μg/kg), pear (134-245 μg/kg) and peach (92-174 μg/kg). Confirmation of the identity of patulin was based on the UV spectrum obtained by the HPLC diode array detector, compared with that of standard patulin, TLC developed by several solvent systems and sprayed with 3-methyl-2-benzothiazolinone hydrazone, and by acetylation with acetic anhydride.

An Efficient Multi-component Synthesis of 6-Amino-3-methyl-4-Aryl-2,4- dihydropyrano[2,3-c]Pyrazole-5-carbonitriles

Multi-component reactions are effective in building complex molecules in a single step in a minimum amount of time and with facile isolation procedures; they have high economy1–7 and thus have become a powerful synthetic strategy in recent years.8–10 The multicomponent protocols are even more attractive when carried out in aqueous medium. Water offers several benefits, including control over exothermicity, and the isolation of products can be carried out by single phase separation technique. Pyranopyrazoles are a biologically important class of heterocyclic compounds and in particular dihydropyrano[2,3-c]pyrazoles play an essential role in promoting biological activity and represent an interesting template in medicinal chemistry. Heterocyclic compounds bearing the 4-H pyran unit have received much attention in recent years as they constitute important precursors for promising drugs.11–13 Pyrano[2,3-c]pyrazoles exhibit analgesic,14 anti-cancer,15 anti-microbial and anti-inflammatory16 activity. Furthermore dihydropyrano[2,3-c]pyrazoles show molluscidal activity17,18 and are used in a screening kit for Chk 1 kinase inhibitor activity.19,20 They also find applications as pharmaceutical ingredients and bio-degradable agrochemicals.21–29 Junek and Aigner30 first reported the synthesis of pyrano[2,3-c]pyrazole derivatives from 3-methyl-1-phenylpyrazolin-5-one and tetracyanoethylene in the presence of triethylamine. Subsequently, a number of synthetic approaches such as the use of triethylamine,31 piperazine,32 piperidine,33 N-methylmorpholine in ethanol,34 microwave irradiation,35,36 solvent-free conditions,37–39 cyclodextrins (CDs),40 different bases in water,41 γ -alumina,42 and l-proline43 have been reported for the synthesis of 6-amino-4-alkyl/aryl-3-methyl- 2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles. Recently, tetraethylammonium bromide (TEABr) has emerged as mild, water-tolerant, eco-friendly and inexpensive catalyst. To the best of our knowledge, quaternary ammonium salts, more specifically TEABr, have notbeen used as catalysts for the synthesis of pyrano[2,3-c]pyrazoles, and we decided to investigate the application of TEABr as a catalyst for the synthesis of a series of pyrazole-fused pyran derivatives via multi-component reactions

Gota suspensa para avaliação de aldeído total no ar interno e externo do ambiente

A sensitive and simple system was proposed for the in situ measurement of total aldehyde in outdoor or indoor ambient. The method is based on the use of a reagent drop as an useful interface to preconcentrate the sample prior to determination of total aldehyde as formaldehyde. The drop is formed at the tip of a cylindrical tube that contains two optical fibers placed on opposite sides and in contact with the reagent solution. One optical fiber carries the red light to the drop form a light emitting diode (LED). The transmitted light is measured by a second optical fiber/photodiode system. The analytical signal is read and converted into absorbance. The reagent solution of 3-methyl-2-benzothiazoline hydrazone (MBTH) forms a blue cation during reaction with formaldehyde that can be measured at 660 nm. Some aspects of kinetics reaction formation of dye were reevaluated. The formaldehyde reacts with MBTH and forms the azine in about 12 min. The oxidation of MBTH by Fe (III) and the formation of dye requires 3 min. The absorbance of the reagent drop is proportional to the sampling time and to the analyte concentration. The absorbance signal increases with increased sample gas flow until a maximum is reached then decreases until it forms a plateau. The proposed method was evaluated using both outdoor and indoor samples, and it was shown to viable provide an accurate measure of total aldehyde.

Avaliação de contaminantes inorgânicos e orgânicos em álcool combustível utilizando eletroforese capilar

This work reports the analysis of inorganic and organic contaminants in alcohol fuel samples using capillary electrophoresis. Chloride and sulfate were analyzed in nitrate/ monochloroacetic acid at 10 mmol L-1 concentration each under indirect UV detection (210 nm). The analysis of aldehydes is based on the 216 nm detection of 3-methyl-2-benzothiazoline hydrazone adducts. The running buffer consisted of 20 mmol L-1 tetraborate , 40 mmol L-1 sodium dodecyl sufate and 12 mmol L-1 beta-ciclodextrin. Both methodologies were applied to real samples indicating inorganic ion concentrations from 0.15 to 6.64 mg kg-1 and aldehydes from 32.0 to 91.3 mg L-1.

Gota suspensa para avaliação de aldeído total no ar interno e externo do ambiente

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação de contaminantes inorgânicos e orgânicos em álcool combustível utilizando eletroforese capilar

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Determination of low-aliphatic aldehydes indoors by micellar electrokinetic chromatography using sample dissolution manipulation for signal enhancement

This work describes a novel approach for the analysis of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and acrolein) and acetone in environmental samples using micellar electrokinetic chromatography (MEKC). The method is based on the reaction of carbonyl compounds with 3-methyl-2-benzothiazoline hydrazone (MBTH) that gives an azine intermediate with maximum absorbance at 216 nm. A systematic evaluation of sample dissolution medium was conducted as a means to enhancing sensitivity. In the best condition, samples were dissolved in 0.030 mol.L-1 tetraborate solution. This condition presented enhancement factors in the range of 35-54 for the aldehydes under investigation, computed as the improvement of the concentration limits of detection (LODs) with reference to the sample dissolved in pure water. The running buffer was 0.020 mol.L-1 tetraborate, pH 9.3, containing 0.050 mol-L-1 sodium dodecyly sulfate (SIDS). The overall methodology presented several advantages over established methods for aldehydes. Worthy mentioning that MBTH is available in high purity degree, dispensing laborious reagent purification procedures. A few method validation parameters were determined revealing good migration time repeatability (< 2.5% coefficient of variation, CV) and area repeatability (< 4% CV), excellent linearity (20-120 mug/L, r > 0.995) and adequate sensitivity for environmental applications. The LODs with respect to each single aldehyde were in the range of 0.54-4.0 mug.L-1 and 11 mug.L-1 for acetone. The methodology was applied to the determination of aldehydes indoors. Samples were collected in an impinger flask containing 0.05% MBTH solution, at a flow rate of 0.80 L.min(-1), during 2.5 h, at different times during the day. The most abundant carbonyls in the samples were acetone, followed by formaldehyde and acetaldehyde, with estimate peak concentrations of 452, 5.2 and 2.2 ppbv, respectively.

Measurement of atmospheric formaldehyde using a drop collector and in-situ colorimetry

A sensitive and affordable approach is described for the in-situ measurement of ambient formaldehyde. Air is sampled around a 100 microliter aqueous drop containing 3-methyl-2-benzothiazoline hydrazone. After a desired period of sampling (typ. 5 min) and a waiting period of 10 min for the reaction to be completed, a second reagent (FeCl3) is added to the drop by means of a conjoined conduit. A blue product is formed and is read after an additional 10 min of reaction by a fiber-optic/light emitting diode based photodetector. A fresh drop is then formed and the process begins anew. As demonstrated here, the limit of detection is similar to 6.25 mu g m(-3) HCHO but can be significantly improved by using longer sampling times and a sampling rate higher than 100 mi min(-1) used in most of this work. This is the first example of a chromogenic drop sensor that utilizes sequential reagent addition.

5-Methyl-2,4-bis(methylsulfanyl)tricyclo[6.2.1.0(2,7)]undeca-4,9-diene-3,6-dione

The structure analysis of the title compound, C(14)H(16)O(2)S(2), shows the SMe and H atoms of the bond linking the six-membered rings to be syn and also to be syn to the bridgehead -CH(2)- group. Each of the five-membered rings adopts an envelope conformation at the bridgehead -CH(2)- group. The dione-substituted ring adopts a folded conformation about the 1,4-C center dot center dot center dot C vector, with the ketone groups lying to one side. The cyclohexene ring adopts a boat conformation.

1-Methyl-3-phenylsulfonyl-2-piperidone

The piperidone ring in the title compound, C12H15NO3S, has a slightly distorted half-chair conformation with the methyl, carbonyl and phenylsulfonyl ring substituents occupying equatorial, equatorial and axial positions, respectively. Molecules are connected into centrosymmetric dimers via C-H center dot center dot center dot O interactions and these associate into layers via C-H center dot center dot center dot O-S contacts. Further C-H center dot center dot center dot O interactions involving both the carbonyl and sulfonyl O atoms consolidate the crystal packing by providing connections between the layers.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.