Abstract: Composite of magnetic and conductive Hollow polyaniline/CnFe₂O₄ nanosphere with novel core-shell structure were successfully prepared by in-situ polymerization in the presence of ammonium persulfate (APS) as the oxidant and dodecyl benzene sulfonic acid (DBSA) as the surfactant and dopant. The synthesized hollow microsphere composites were characterized by FT-IR and UV/Vis spectrophotometry. X-ray photoelectron spectroscopy was used to determine the degree of coating with a conducting polymer. Its morphology was characterized by scanning electron Microscopy (SEM). The changes of the magnetic properties before and after polyaniline coating were investigated by using vibrating sample magnetometer (VSM).

Abstract: We report herein that acylals can be prepared very fast and in excellent yields by the direct condensation of aldehydes with acetic anhydride under solvent-free condition by employing of a mesoporous derivatized Mobile Crystalline Material, MCM-41-SO₃H as heterogeneous catalyst at room temperature.

Abstract: N-Tosyl-2-nitropirrole and N-Tosyl-3-nitropirrole reacts with poorly and activated dienes using protic ionic liquids as reaction media. They exhibit a dienophile character producing the corresponding indoles through a Diels-Alder process. In all cases the presence of protic ionic liquids as reaction media improve the yields respect to use of molecular solvent, while the temperature and the reaction time decrease.

Abstract: In this research, a new series of substituted 4H- pyrans and 4H-chromenes derivatives has been synthesized at ambient temperature in the presence of catalytic amount of sodium carbonate (20 mol %) via one-pot three-component cyclocondensation reactions of malononitrile, dialkylacetylenedicarboxylates and 1,3-diketones in ethanol under ultrasound irradiation. The synergistic effect of MCRs and ultrasound has been successfully demonstrated to offer an easy way for the synthesis of these compounds in excellent yields.

Abstract: The fluoroscent dyes are used as probes for the detection of heavy metal ions, aminoacids and other biomolecules in recent years. Some of these dyes, including Nile Blue deivatives, which belong to the benzophenoxazine family, fluoresce at near the far visible-near infrared region with minimum interference from absrption scattering and reduced risk of photodecomposition.¹ As previously reported by our group,^2,3 benzo[a]phenoxazinium dyes are involved in an acid-base equilibra where the 5-amino position is the main site of deprotection.⁴ The quantum yield of the basic form is almost ten times lower than the cationic acid form. This has an impact in the overall fluorosence quantum yield. In continuation of our research intrests,2-4 the present work describes the study of fluoresence quantum yileds of pure cationic forms by shifting the acid-base equilibria with the addition of a strong acid. The photophysical behaviour of these novel compounds in AOT/cyclohenxane/water w/o microemulsions as a function of water content will also be discussed. Acknowledgements: Thanks are due to Fundacao para a Ciencia e Tecnologia (Portugal) for its financial support of a BPD to B. R. Raju (SFRH/BPD/62881/2009), Centro de Quimica and Centro de Fisica (Universidade do Minho). The NMR Spectro meter Bruker Avance III 400 is part of the National NMR Network, and was purchased in the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT. Refrences: 1. Goncalves, M. S. T. Chem. Rev. 2009, 109, 190. 2. Alves, C. M. A.; Naik, S.; Coutinho, P. J. G. Goncalves, M. S. T. Tetrahedron 2009, 65, 10441. 3. Alves, C. M. A.; Naik, S.; Coutinho, P. J. G. Goncalves, M. S. T. Tetrahedron Lett. 2011, 52, 112. 4. Naik, S.; Alves, C. M. A.; Coutinho, P. J. G. Goncalves, M. S. T. Euro. J. Org. Chem. 2011, 13, 2491.

Abstract: Polyfluoroarylmetallic compounds are the important group of polyfluoroarenes. Among the chemical transformations of polyfluoroarylmetallic compounds, it is of interest to study the properties of polyfluoroaromatic zinc compounds and their role as reactive intermediates. Polyfluoroaromatic zinc compounds were prepared from chloropentafluorobenzene and perfluoroarenes [1,2]. Recently, these organozinc compounds were converted to hydro-, bromoperfluoroarenes, perfluorobiaryls, allylpolyfluoroarenes, N,N-dimethyl-bis(polyfluoroaryl)methanamines, polyfluoroaromatic ketones [1-4]. Search for the ways of synthesis of polyfluoroaromatic aldehydes is another important aspect of chemistry of polyfluoroarylzinc compounds. We have found that interaction of these organozinc compounds with Vilsmeier-Haack reagent formed from oxalyl chloride and DMF, and subsequent treatment of the reaction mixtures with water led to the corresponding polyfluoroaromatic aldehydes. When methanol was used instead of water, polyfluorinated acetales were obtained. From 1,4-dibromo-2,3,5,6-tetrafluorobenzene and zinc in the presence of tin (II) chloride in DMF, dizinc compound was obtained that was then converted to 2,3,5,6-tetrafluoroterephthalaldehyde by reaction with Vilsmeier-Haack reagent. The mechanisms of transformations are discussed. References [1] A.O. Miller, V.I. Krasnov, D. Peters, V.E. Platonov and R. Miethchen, Tetrahedron Lett., 2000, 41, 3817-3819. [2] A.S. Vinogradov, V.I. Krasnov and V.E. Platonov, Russ. J. Org. Chem., 2008, 44, 95-102. [3] A.S. Vinogradov, V.I. Krasnov and V.E. Platonov, Coll. Czech. Chem. Commun. 2008, 73, 1623–1630. [4] A.S. Vinogradov, V.I. Krasnov and V.E. Platonov, Russ. J. Org. Chem., 2010, 46, 344-351.

Abstract: 2,2'-Dicarbazole-1,1'-diphenyl (2,2'-CBP) is a prospective host material for phosphorescent light emmiting diodes (PHOLED)s. The synthesis of 2,2'-CBP is limited by the availability of starting materials. We wish to report an efficient protocol for the synthesis of 2,2'-CBP with overal yield about 90% starting from o-nitrobenzoic acid. Thus, Pd catalized homocoupling of o-nitrobenzoic acid affords 2,2'-dinitro-1,1'-diphenyl (2,2'-DNDP) in 95% yield. Pd catalized reduction of 2,2'-DNDP and the following double arylation of 2,2'-diaminodiphenyl with 2,2'-dibromo-1,1'-diphenyl (which can be obtained from 2,2'-diamino-1,1'-diphenyl in 70-76% yield) affords the final product in 95% yield with overal yield after 3 steps of 90 %.

Abstract: New thermotropic liquid crystals containing benzoxazole core and alkanoyloxy chain at the end group of the molecules (C_n-1H_2n-1COO-, n = 14, 16, 18) was synthesized. The present compounds are enantiotropic smectic A liquid crystals.It was also found that the end groups of the molecules and polar chloro substituent at the benzoxazole fragment had effect on the mesomorphic properties.

Abstract: We have explored the reaction of substituted alkenylaluminums that were prepared by various methods with sulfonyl halides, which we believed to be effective sources of electrophilic halogen. Alkenylaluminums obtained in Zr-catalyzed methylalumination of terminal alkynes react with sulfonyl chlorides and bromides to give corresponding alkenyl halides in high yield. Cycloalumination of 1-decyne and phenylacetylene affords aluminacyclopent-2-enes, which react with 1 equivalent of sulfonyl chlorides and bromides to give after deuterolysis alkenyl halides in high yield. The halogenation proceeds regioselectively only at the sp²-hybridized carbon atom and with the retention of the configuration of the double bond. To our surprise, b-substituted vinylaluminums that were obtained by hydroalumination of terminal alkynes (1-octyne, phenylacetylene) by DIBAL-H do not react with sulfonyl halides (MsCl, TsCl, MsBr). Thus, the sulfonyl chlorides and bromides are more convenient halogenation agents for b,b- and a,b,b-substituted vinylaluminums that were prepared by Zr-catalyzed methylalumination and cycloalumination compared to NCS and NBS, which is manifested in the facts that: a) the reaction proceeds at room temperature; b) the reaction does not require the use of ether solvent (moreover, the latter inhibits the halogenation), c) higher regioselectivity for the bromination of aluminacyclopent-2-enes is observed.

Abstract: Dyes ions have a tendency to self-associate in aqueous solutions. Since almost all textile dyes are applied from aqueous systems, it is important to understand the association of dyes in water, and to determine the number of chemical species presented in the system. The main factors influencing aggregation are dye concentration, electrolyte concentration, and temperature. In the present work, the influence of the coupling component structure on the dye aggregation is presented. The molecular aggregation has been studied spectrophotometrically in aqueous solutions as a function of dye concentration (10^-6 ¸ 10^-3 mol/L). As the concentration increases, different changes were observed in the dyes UV-vis spectra indicating that the molecules are beginning to aggregate. The shapes of the obtained spectra were totally different as the coupling component structure was changed in the dye molecule.From the matriceal analysis, the number of chemical species presented in the system (in domain of concentrations studied) was determined. The mathematical calculations confirm the experimental data regarding the aggregation of the investigated dyes.

Abstract: Two new symmetrical disazo direct dyes containing 4,4'-diaminostilbene-2,2'disulphonic acid as middle component and 3-bromosalicylanilide and 4-bromosalicylanilide as coupling components were synthesized. The dyes were characterised by TLC, VIS, FT/IR, ¹³C-NMR spectroscopy, and HPLC technique. The colour, spectrophotometric study of the two disazo stilbene dyes with symmetrical structure was performed using the CIE 1976 (CIELAB) uniform colur space parameters, under the CIE (Commission Internationale d'Eclairage) recommended illuminants: D65 (natural day light), A (tungsten light), F2 (fluorescent light) and the standard 10° observer respectively. The colour differences (ΔEab*) and (ΔE_CMC) were calculated against one standard, revealing a high colouring power for the two new studied dyes.

Abstract: Several research studies involving fused heteroaromatic dyes based on the oxazine moiety have been focused on their absorption and fluorescence spectroscopic properties.¹ These long-wavelength fluorophores find applications as biological probes, namely in covalent labeling of amino acids, proteins, peptides and DNA.² Also, more frequently they have been used in non-covalent labeling, such as staining nucleic acids in a variety of context, monitoring protein conformation alterations or for therapeutic purposes.³ Although the interest of photophysical properties, several compounds possessing the phenoxazine nucleus have been stressed due to their antiproliferative properties with potential applications both as antitumour and as antimicrobial agents. Considering our promising previous results in this field,⁴ and having in mind future evaluation of biological activity, we decided to synthesise new benzo[a]phenoxazinium salts having chlorinated terminals at their substituents in 2- and 9- positions. Furthermore, these compounds can also be used as covalent and non-covalent probes, and consequently the photophysical properties were also studied in ethanol and water in simulated physiological conditions. Acknowledgements: Thanks are due to the Foundation for Science and Technology (Portugal) for its financial support of Centre of Chemistry. The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network (RNRMN) and was purchased in the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT. References 1. Jose, J.; Burgess, K. Tetrahedron 2006, 62, 11021-11037. 2. Salomi, B. S. B.; Mitra, C. K.; Gorton, L. Synth. Met. 2005, 155, 426-429. 3. Nakanishi, J.; Nakajima, T.; Sato, M.; Ozawa, T.; Tohda, K.; Umezawa, Y. Anal. Chem. 2001, 73, 2920-2928. 4. Frade, V. H. J.; Sousa, M. J.; Moura, J. C. V. P.; Gonçalves, M. S. T. Bioorg. Med. Chem. 2008, 16, 3274-3282.

Abstract: Carbohydrates play a fundamental role in a wide number of molecular recognition phenomena. In fact they are the most important mediators in the intercellular interactions and with extracellular matrix components, such as enzyme, hormones, toxins, bacteria, virus, etc. For this reason, during last years there has been a growing interest in bioactive oligosaccharides, since tailor-made sugar based compounds able to interfere in key biological mechanisms would represent a powerful weapons in biomedicine. However the development of saccharide-based drugs has beeen largely hampered by the typical challenges associated with classical carbohydrate synthesis. Sugar mimics endowed with very similar biological properties, but structurally and synthetically simpler than their natural counterparts, may offer a valuable alternative.A simple and efficient approach to the synthesis of pseudo-oligosaccharides based on intramolecular cyclization promoted by various selenium electrophile of heterodymer sugar olefin is described. Various selenocyclic ether are obtained as two diastereoisomers trans and cis and after column chromatography are isolated in enantiomerically pure form These compounds can be seen as potential precursors of carbohydrate mimics, in fact via syn elimination of selenoxides followed by further functionalization of the C-C double bond is possible to obtain analogous tryciclic sugar. This procedure represent an innovative use of selenium chemistry applied at the carbohydrates.

Abstract: The interest of fluorescent carbohydrates is due to wide applications in biology and environmental technology. For example, water soluble glucose based imino-anthracenyl derivatives have been shown to recognize specifically Hg²⁺ (which is highly toxic and causes DNA damage and impair mitosis) by switch-on fluorescence.[1] Fluorescence is a powerful technique as a consequence of its highly sensible and specific detection methods. [2]^,[3] With the aim to generate new derivatives with biological, pharmacological and technological properties, we design the here presented compounds using as diversity point (see Scheme), the amino group. We have selected coumarins as chromophore units (CU), due to their demonstrated anticoagulant activity and easy availability. On the other hand, fluorescent aldehydes have been chosen as fluorescence sources for their chemosensor potential activity in a wide variety of fields. We report here on new fluorescent derivatives of D-glucosamine (1) previous protection of its hydroxyl groups. These derivatives having general structures 2 and 3, have been prepared in good yields by: a) nucleophilic attack of the amino group to activated carboxycoumarins, and b) by reductive amination, respectively. We thank the AECID (Projects A/023577/09 and A/040322/10) and the 'Junta de Andalucía' (FQM 142 and Project P09-AGR-4597) for financial support. [1] Mitra, A.; Mittal, K. A. and Rao, P. C. Chem. Comm., 2011, 47, 2565 and references therein. [2] Lee, D.Y.; Singh, N. and Jang, D. O. Tetrahedron Lett. 2010, 51, 1103 [3] a) Rettig, W. Applied Fluorescence in Chemistry, Biology and Medicine; Springer: New York, 1999. b) Christensen, L.; Norgaard, R.; Bro, S. and Engelsen, B. Chem. Rev. 2006, 106, 1979.

Abstract: Today the aminoglycosides are still the most commonly used antibiotics worldwide thanks to the combination of their high efficacy with low cost. The interest of aminoglycoside antibiotics is due to their use in treatment of wide variety infections. These compounds act on gram-positive and gram-negative bacteria as protein synthesis inhibitors.[1] However, they are nephrotoxic and ototoxic in some cases, thus limiting its use. Kanamycin is an aminoglycoside antibiotic with multiple therapeutic applications. A previous step of their synthesis is the formation of 3-amino-3-deoxy-D-glucose from commercial available products. Integration of phenylhydrazine with a sugar derived dialdehyde (2) in water, as a key step, has been used[2] as an elegant and easy strategy synthesis. However, a low reproducibility of this method makes synthetic chemists reluctant to its use, in such a way that other routes of synthesis of 3-amino-3-deoxy-D-glucose are preferred.[3] All this, despite the fact that the above mentioned integration reaction can be considered as a representative example of green chemistry.[4] We have revisited this process and we report herein new NMR and IR data of compounds 2 and 3 that they confirm the structures proposed in literature. In addition, we describe novel different conditions for their synthesis that reduce the time of reactions, especially in case of dialdehyde 2. We thank the AECID (Projects A/023577/09 and A/040322/10) and the 'Junta de Andalucía' (FQM 142 and Project P09-AGR-4597) for financial support. [1] a) Li, J.; Chang. T., Anti-Infec. Agents in Med. Chem. 2006, 5, 255.; b) Corey, E. J.; Czakó, B.; Kürti, L., Molecules and Medicine. John Wiley & Sons, New Jersey, 2007 [2] Patroni, J.; Stick, R. Aust. J. Chem, 1985, 38, 947 and reference therein. [3] Faghih, R.; Cabrera-Escribano, F. et al, J. Org. Chem. 1986, 51, 4558 [4] Anastas, Y.; Warner, J.C. Green Chemistry: theory and practice.Oxford University Press, New York, 1998

Abstract: Polyfluoroarenesulfonyl halides can be successfully used for the introduction of polyfluoroarenesulfonyl moiety in organic compounds. Recently we realized a simple and efficient method for preparation of polyfluoroarenesulfonyl bromides by the action of electrophilic brominating agents on polyfluoroarenethiols. We have shown that the nature of halogen atom in SO₂Hal group influence the chemical properties of polyfluoroarenesulfonyl halides. Thus, the reactions of polyfluoroarenesulfonyl bromides with alkenes such as hexene-1 or allyl chloride provided the corresponding adducts in high yields, while the conversion of polyfluoroarenesulfonyl chlorides at the same conditions was poor and C₆F₅SO₂F was unreactive. The formation of adducts apparently occurs with participation of polyfluoroarenesulfonyl radicals. At the same time the reaction of polyfluoroarenesulfonyl bromides with allyl bromide resulted in allyl polyfluoroaryl sulfones. This fact is explained by the addition of polyfluoroarenesulfonyl radical to alkene double bond and subsequent elimination of bromine. In reactions of allyl polyfluoroaryl sulfones with polyfluoroarenesulfonyl bromides the replacement of Ar_FSO₂ group in sulfone by another one takes place. According to these data the reversibility of allyl polyfluoroaryl sulfone formation can be suggested. Surprisingly the reactions of polyfluoroarenesulfonyl chlorides or bromides with polyfluoroarenethiols gave mixtures of polyfluorinated diaryl disulfides, whereas replacement of fluorine atom at the 4-position of aromatic ring of C₆F₅SO₂F occured. It turned out that reactions of polyfluoroarenesulfonyl chlorides or bromides with some n‑nucleophiles probably proceeded with electron transfer. For example, such process could take place in reactions of polyfluoroarenesulfonyl chlorides or bromides with alkali metal halides.

Abstract: Abstract:Surfactants are a class of chemical compounds with unique properties, structure of which is consisted of hydrophobic and hydrophilic parts. This double structure gives rise to their unique behaviors in various conditions. Bolaforms are organic molecules compounds of two charged groups which are connected via a linear poly methylen chain.Bolaforms' surfactants don't work as well as Conventional surfactant (having a head group and one alkyl chain) in reducing surface tension. Bolaforms are absorbed in water – air interface, however, their effectiveness in terms of reducing water surface tension is not considerable compared to common surfactants. In this study, synthesis of two kinds of bolaforms which the same spacer length and different heads is investigated. The structural formula for synthesized kinds is as follows: bolaform A with structural formula Br^-(CH₃)₃N⁺(CH₂)₃ N⁺(CH₃)_­3 Br ^{– ­}with methyl side branches in head group and bolaform B with structural formula of Br^-(CH₃ CH₂)₃N⁺(CH₂)₃ N⁺(CH₃ CH₂)₃Br ^{–. IR and NMR identification techniques approves obtained product. Using surface tension measurement device it can be observed that synthesized bolaforms have high CMC; in other words, bolaform's surfactants with short spacer play electrolytic role.}

Abstract: A library of 2-amino-9-aryl-3-cyano-4-methyl-7-oxo-6,7,8,9-tetrahydropyrido[2',3':4,5]thieno[2,3-b]pyridines which recently have been reported as selective progesterone receptor agonists was synthesized by ternary condensation of N-methylmorpholinium 4-aryl-3-cyano-6-oxo-1,4,5,6-tetrahydropyridine-2-thiolates with malononitrile and acetone, and alternatively by reaction of bis(4-aryl-3-cyano-6-oxo-1,4,5,6-tetrahydropyridine-2-yl)disulfides with acetone and malononitrile in basic media. The mechanism, scope and limitations of the reactions are discussed.

Abstract: A facile protocol for the one-pot synthesis of pyrimidinone derivatives through Biginelli reaction in the presence of catalytic amount of the nano-ordered MCM-41-SO3H anchored sulfonic acid (MCM-41-SO3H) has been described. The reaction proceeds smoothly under solvent-free conditions on grinding of a mixture of different aldehydes, ethyl acetoacetate and urea in a mortar.

Abstract: Oxalyl chloride (1) has been known to be involved as C1 synthon for ketone synthesis,¹ as an alternative route for carbonylation with CO gas. Given the importance of ketones in pharmaceutical and industrial applications,there is a permanent interest in finding new ways for their synthesis. Based on the exceptional leaving group ability of the trialkylstannyl group in EAS, we have recently proposed efficient catalyst-free and regioselective synthesis of unsymmetrical ketones using different acyl chlorides.² Driven by these results we initiated studies on the reaction of arylstannanes with 1. Now, we describe a novel regioselective synthesis of symmetrical diaryl ketones using 1 as C1 carbonyl synthon, under catalyst-free conditions. These results are significant from the point of view of its simplicity, the wide range of synthetically³ or commercially available arylstannanes and the associated convenience in the utilization of 1 as carbonyl synthon, instead of specific acyl chlorides. All the reactions studied went, exclusively, through an ipso-substitution independently whether the directing influences of the aryl substituents and the trialkylstannyl group are either matched or mismatched. We suggest a mechanism by which 1 acts as C1 synthon on these reactions. In addition, a special work up is proposed in order to recover the trialkyltin chlorides generated. ¹ Rao, M. L. N.; Venkatesh, V.; Dasgupta, P. Tetrahedron Lett. 2010, 51, 4975-4980. ²Lo Fiego, M. J.; Silbestri, G. F.; Lockhart, M. T.; Chopa, A. B. J. Org. Chem. 2011, 76, 1707-1714. ³ Silbestri, G. F.; Lo Fiego, M. J.; Lockhart, M. T.; Chopa, A. B. J. Organometal. Chem. 2010, 695, 2578-2585.

Abstract: A simple, convenient, and practical method for the synthesis of α-amino nitriles through a one-pot, three-component Strecker reaction of diverse carbonyl compounds and amines with trimethylsilyl cyanide (TMSCN) under mild conditions in EtOH 96 % has been developed. Reactions proceed efficiently in the presence of a catalytic amounts of new and recoverable ionic liquid of N-butyl-N-methyl imidazolium Phthalimide-N-Oxyl {[Bmim] PINO} at room temperature.

Abstract: A simple, inexpensive, environmentally friendly and efficient route for the synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives via the one-pot three-component Biginelli reaction using pentafluorophenylammonium triflate (PFPAT) as a catalyst is described. PFPAT organocatalyst is air-stable, cost-effective, easy to handle, and easily removed from the reaction mixtures.

Abstract: Nano-ordered MCM-41 anchored sulfonic acid (MCM-41-SO3H) was found to be an efficient catalyst for condensation of indoles with various carbonyl compounds to afford the corresponding bis(indolyl)methanes in high yields under solvent-free conditions using ball milling at room temperature.

Abstract: Peculiarities of 2,1-benzisoxazol-3(1H)-one synthesis by means of the photochemical cycle forming reaction of 2-azidobezoic acid in ethanol. Based upon HPLC kinetical data we have observed the 2,1-benzisoxazol-3(1H)-one yield decrease in the course of decreasing of the starting azide concentration. It was stated that the 2,1-benzisoxazol-3(1H)-one formation effectiveness depended on the actinic light wavelength. Changing the light wavelength from 365 to 253.7 nm we observed an increase of the cycle formation yield. The decrease of the 2,1-benzisoxazol-3(1H)-one yield in the course of irradiating at 365 nm was explained by the secondary photolysis.

Abstract: Surfactants are organic compounds which contain hydrophobic groups acting as tail and hydrophilic groups acting as head, thus they are solved hardly in water and organic solvents.Surfactants are able to change surface energy within levels considerably. Property of surfactant comes from its double molecular structure. It means that it contains two hydrophilic and hydrophobic groups at the same time. A novel type of surfactants known as bolaform is studied and synthesized in this study. Bolaforms have two polar head groups connected via a poly methylen chain. They are categorized into anionic, cationic and non ionic depending on the head group's charge. Micelle extraction of metallic ions, using as molecules sensitive to light and usage in synthesis of mesoporous silica structure for different applications such as in catalysts are among bolaforms' applications. Structural formula of synthesized kinds with the same spacer and different heads is as follows. Bolaform A with structural formula of Br^-(CH₃)₃N⁺(CH₂)₁₂ N⁺(CH₃)Br ^– with side branches of methyl in head group and bolaform B with structural formula of Br^-(CH₃ CH₂)₃N⁺(CH₂)₁₂ N⁺(CH₃ CH₂)₃Br ^– . IR and NMR identification techniques approves obtained product. Using surface tension measurement device it can be observed that synthesized bolaforms have suitable CMC (relatively low); in other words, bolaform's surfactants with long spacer have surface activity property.

Abstract: Bitopic pyrazole-containing ligands attract interest because of their potential use as building blocks for crystal engineering and for synthesis of heterobimetallic complexes for catalysis. Several new bitopic pyrazole-containing ligands were prepared from the corresponding pyrazoles and tetrahalogen- or tetratosyloxy derivatives of o-xylene and neopentane in a superbasic medium (KOH-DMSO). The reaction of unsubstituted pyrazole with 1,3-dibromo-2,2-dibromomethylpropane yields a new tetrapyrazole ligand with a neopentane backbone, while no reaction occurs in case of 3,5-dimethylpyrazole. The product represents a bitopic ligand comprising two 1,3-bis(pyrazol-1-yl)propane units directly linked together. The use of tetratosyloxy- instead of tetrabromo-derivative gives previously unknown 1,1-bis(3,5-dimethylpyrazol-1-ylmethyl)oxetane, while the unsubstituted pyrazole in the same conditions yields a mixture tetrapyrazolyl-neopentane and dipyrazolyloxetane derivatives. A new bitopic ligand with aromatic o-xylene linker inaccessible by other routes was prepared from o-bis(dibromomethyl)benzene and pyrazole in a superbasic KOH-DMSO medium. In case of 3(5)-methylpyrazole and 3,5-dimethylpyrazole no products could be isolated, apparently due to steric hindrance.

Abstract: A new class of β-amino alcohol and diamine ligands has been prepared from isosorbide as a chiral renewable source. The efficiency of these ligands has been evaluated for the metal-catalyzed enantioselective reduction of aromatic ketones by transfer hydrogenation, giving excellent conversion and good enantioselectivity.

Abstract: Reaction of a-D-glucosamine hydrochloride with different substituted benzaldehyde have been investigated in the presence of various inorganic and organic bases. Based on obtained results, the general synthetic method for azomethines of a-D-glucosamine hydrochloride and substituted benzaldehyde proposed.

Abstract: Some novel substituted acetophenone and benzaldehyde (2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyl)-thiosemicarbazones were synthesized by reaction of 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl thiosemicarbazide and substituted acetophenones and benzaldehydes. The reaction was performed using microwave-assisted method. The compounds have converted into 2-iminothiazolidin-4-ones by reaction with ethyl bromoacetate in dichloromethane in the presence of anhydrous sodium acetate. Structures of obtained compounds were confirmed by spectroscopic methods.

Abstract: The ring-opening of epoxides with different nucleophiles is an important strategy for the formation of 1,2-bifunctionalized building blocks. A wide variety of nucleophiles such as alcohols, phenols and carboxylic acids have been utilized in this reaction. Oxygen nucleophiles are among the most important ones as they lead to pharmaceutically important Þ-alkoxy and Þ-aryloxy alcohols.¹ Recently, we reported the first ring-opening of epichlorohydrin with salicylaldehyde derivatives in the presence of Jacobsen' s Co(III)salen catalyst.² The final ring-opened product is a multifunctional aldehyde containing a stereocenter in addition to the alkyl halide and alcohol functional groups. In this study, we report the preparation of multifunctional chiral Schiff base ligands by the condesation of 4-(3-chloro-2-hydroxypropoxy)-2-hydroxybenzaldehyde with primary amines (2-aminophenol and 2-amino-2-methyl-1-propanol). The ligands have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopies. References 1. J. M. Ready, E. N. Jacobsen, J. Am. Chem. Soc., 1999, 121, 6086. 2. L. Karadeniz, G. Koz, K. Aydin, S. T. Astley, Turkish Journal of Chemistry, 2010, 34, 711.

Abstract: N'-[(4-oxochromen-3-yl)methylidene]-4-R-furo[3,2-b]pyrrole-5-carboxhydrazides 3 were prepared by treatment of substituted carboxhydrazides 1 with 4-oxo-4H-chromen-3-carboxaldehyde 2 in ethanol in the presence of p-TsOH. Compounds 3 were subsequently used as ligands in complexation reactions with solutions of metal (M²⁺) chlorides or nitrates: [Ni(NO₃)₂.6H₂O, Co(NO₃)₂.6H₂O, CoCl₂.6H₂O, CuCl₂.2H₂O] to give complexes 4.

Abstract: The development of new antimicrobial and anti cancer therapeutic agents is one of the fundamental goals in medicinal chemistry. Chiral thioureas and their derivatives display a wide range of biological activities such as antibacterial, antiviral and antifungal (1). In addition, some of these compounds could be used as catalysts in the asymmetric reactions such as the Michael addition to nitroalkenes and the Biginelli reaction. Therefore, recent efforts have been devoted to the synthesis of these compounds (2). In the light of this information, novel chiral thioureas bearing amino acids and 2-aminophenol moieties were synthesized in good yields and the structures of the compounds were characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR. References (1) Saeed, S., Rashid, N., Jones, P., Ali, M., Hussain, R., Eur. J. Med. Chem. 45, 2010, 1323-1331 (2) Sheng-Li, Z., Chang-Wu, Z., Gang, Z., Tetrahedron: Asymmetry, 20, 2009, 1046-1051

Abstract: Because of their ready availability, great structural and electronic diversity, easy handling and peculiar chemical behaviour organoselenium compounds are nowadays considered versatile reagents for many synthetic transformations. a,b-Unsaturated selenones represent an interesting example: the electron-withdrawing effect combined with the excellent nucleofugal ability of the phenylselenonyl group makes these compounds useful 1,2-bis(electrophilic) synthons. Recently we have conveniently employed readily available a,b-unsaturated selenones and 1,3-dicarbonyl compounds or cyanoacetates for the organocatalytic asymmetric assembly of structurally complex spirolactones or cyclopropanes. We now report some preliminary results concerning the use of phenyl vinyl selenone and cyclic b-ketoesters for the stereoselective formation of sterically constrained b-aminoesters containing two adjacent stereocenters. The sequential synthesis involves the following steps: a) a highly enantioselective Michael addition catalyzed by a cinchona alkaloid derived catalyst, b) the conversion of the resulting Michael adduct to the corresponding azide by nucleophilic substitution of the phenylselenonyl group, c) a cyclization reaction via a Staudinger/aza-Wittig sequence, d) a diastereoselective reduction of the resulting cyclic imine. b-Aminoesters are obtained with good yields and excellent stereocontrol.

Abstract: The research on fluorescent carbostyrils of the general type I has been going on in our work group for several years. In the course of these investigations we found that carbostyrils of type II having a 4-p-toluenesulfonyl group in position 4 - formed as not isolated intermediates in many cases during our investigations of strongly fluorescent 4-cyano-carbostyrils - showed surprisingly strong fluorescence: they exhibit long-wave absorption and fluorescence properties, and high quantum yields. These findings prompted us to investigate the synthesis and luminescence properties of 4-p-toluenesulfonyl-carbostyrils of type II dependent on the nature of substituents in position 3. In this contribution new types of the acceptor group in position 4 such as toluenesulfonyl and toluenesulfonyloxy groups are investigated, which were in earlier investigations applied as intermediates for e.g. strong fluorescent cyano-carbostyrils. Observations during the reaction sequences revealed that they have already similar strong fluorescence properties as the desired target molecules.

Abstract: Mitotic spindle dynamics represents an important target of anticancer drugs. Many small natural and semi-synthetic drugs influence tubulin assembly and cause apoptosis of excessively dividing cells. Molecules attacking the colchicine domain of tubulin block its polymerization. Despite this there are colchicine site inhibitors (CSIs) not used in cancer treatment due to their high toxicity, low activity or poor solubility. On the basis of the structure-activity relationships, aryltetralin and dibenzylbutyrolactone lignan-like molecules were designed in an attempt to obtain active drugs. Structure modifications embraced the elimination of typically toxic groups. Two new dibenzylbutyrolactone-type compounds were prepared by total synthesis from substituted benzaldehyde, benzyl bromide and dimethyl succinate. The Stobbe condensation of the substituted benzaldehyde with dimethyl succinate followed with the selective hydrogenation of the double bond and the selective reduction of the ester in the presence of carboxyl led to the β-benzylbutyrolactone. Alkylation of butyrolactone enolate with a substituted benzyl bromide provided the final 2-hydroxy-5'-methoxy-4'-O-methyl arctigenin (1) after phenolic group deprotection. The target 2,5'-dimethoxy-4'-O-methyl arctigenin (2) was obtained by means of one-step methylation of dibenzylbutyrolactone derivative 1.

Abstract: Amines are present in many naturally occurring bioactive molecules showing interesting herbicidal and fungicidal activities, and they are also utilised as versatile intermediates for the synthesis of pharmaceuticals, agrochemicals, dyes, and as valuable building blocks in synthetic organic chemistry. Amines can be synthesized by the reaction of aldehydes or ketones with ammonia, primary or secondary amines in presence of different reducing agents. This is the so-called reductive amination reaction which is described as direct when the carbonyl compound and the amine are mixed together with a suitable reducing agent in a single operation, without preformation of an imine or an iminium salt. On the other hand, the reducing systems based on the use of alkali-metals in combination with arenes in aprotic media, with the arene acting as electron carrier have received much attention. In the last years, we have been working on the preparation of transition metal nanoparticles by fast reduction of the corresponding metal chlorides with lithium and a catalytic amount of an arene [naphthalene, 4,4´-di-tert-butylbiphenyl (DTBB)] as electron carrier. In this work we want to introduce a simple and efficient procedure for the direct reductive amination of aldehydes for the one-pot synthesis of secondary amines, using primary amines as starting materials in the presence of lithium powder and a catalytic amount of DTBB or a polymer supported naphthalene as electron carrier. The direct reductive amination of a variety of aldehydes was achieved simply by adding a mixture of the corresponding carbonyl compound and the amine, over a solution of the lithium arenide in THF at room temperature. For most of the substrates tested the main reaction products were the secondary amines along with variable amounts of the corresponding alcohol and imine products. DFT methods have been applied in order to explain the differences in reactivity observed.

Abstract: In the past few decades, the synthesis of new heterocyclic compounds has been a subject of great interest due to their wide applicability. Among a large variety of heterocyclic compounds, heterocycles containing phthalazine moiety were reported to possess anticonvulsant, cardiotonic, and vasorelaxant activities. Therefore, a number of methods have been reported for the synthesis of phthalazine derivatives. Despite the available methods, the development of new synthetic methods for the efficient preparation of heterocycles containing phthalazine ring fragment is therefore an interesting challenge. With these precedents and with the aim of preparing new derivatives with potential pharmacological activity, we have synthesized new phthalazinedione derivatives by introducing halogenoalkyl substituents in one of the NH-nucleophilic groups. So, we started with 4-chloro-phthalic anhydride, which reacted with methyl- hydrazine, in MW mild conditions. After purification, we obtained two different isomers of phthalizediones, 8-chloro-2-methyl-2, 3-dihydro-phthalazine-1, 4-dione and 8-chloro-3-methyl-2, 3-dihydro-phthalazine-1,4-dione. Then halogenoalkyl substituents with different chain length were introduced in the nitrogen group in a very efficient way. Finally halogen atom of alkyl chains was replaced by an azide group. The described synthetic route will allow us to condense a nitrogen heterocyclic ring on the phatalazinone moiety and obtain a new tricyclic scaffold with promising pharmacological properties.

Abstract: Bacterial diseases of freshwater fish epithelia have been extensively studied; however in marine fishes relatively few bacterial skin and gill diseases have been characterized. Tenacibaculum maritimum, a Gram-negative and filamentous bacterium, has been described as the etiological agent of tenacibaculosis in marine fish. Since 1990, as the farming of fish became a steadily growing industry, this disease has been widely distributed in several countries and is considered a limiting factor for the culture of many species of commercial value in the world. Among the drugs used in the past few years enrofloxacin proved to be the most useful compound in the control of tenacibaculosis outbreaks, although the rapid appearance of resistant strains has already been described. Therefore, it is important to discover new classes of selective antimicrobial drugs. Coumarin derivatives are a class of compounds that present a wide range of pharmacological activities. Among others, recent studies pay special attention to the antibiotic properties of the coumarin moiety. In order to contribute to the development of new agents, in the present communication we have synthesized new 3-arylcoumarin derivatives, structurally related with well know antibiotic novobiocin. On this scaffold we introduced substituents with different electronic, steric and/or lipophilic properties in different positions of the aromatic rings. The compounds have been prepared via a palladium-catalyzed coupling type Suzuki reaction of phenyliodonium zwitterion species previously synthesized by us. Further, were evaluated for antibacterial activity against bacterial and fungal strains. The preliminary results of biological activity and/or selectivity against Tenacibaculum Maritimum will be presented.

Abstract: The hypothesis of vector alignment should allow for the rational design of intensely colored conjugated organic dyes by providing a means of predicting the structures that provide a straight path for the π electrons to move across the entire molecule in response to perturbation by a passing photon.

Abstract: Triethylammonium 4-aryl-3,5-dicyano-6-oxo-1,4,5,6-tetrahydropyridine-2-olates were obtained by reaction of (E)-3-aryl-2-cyanoacrylamides with 1-cyanoacetyl-3,5-dimethylpyrazole in the presence of 1.5 eq. of Et₃N (20 °C, acetone) in 55-98% yields.

Abstract: The use of fluorescent probes for detection of biological and organic molecules has increased in the last years due to their high sensitivity and ease of use compared to radiochemical methods. Interference with the measurement of the label fluorescence could occur in many biological samples, which display some fluorescence of their own, usually in the blue or green region of the spectrum. Consequently, in studies with biomolecules it is desirable to improve the sensitivity of detection using dyes with absorption and fluorescence in the red or near infrared spectral region. Therefore, in these spectral regions it is possible the use of inexpensive and effective excitation sources, e.g. laser diodes.^1,2 Having these facts in mind and as a continuation of our previous research,³ fluorescent benzo[a]phenoxazinium chlorides possessing different substituents at position 2, namely propoxyl, 4-ethoxy-4-oxobutoxyl or 3-carboxypropoxyl groups, and at positions 5, 9 and 10 of the tetracyclic system, the amino, ethylamino and methyl groups, respectively, were synthesised. Absorption and emission studies of all compounds were also carried out in ethanol, water and at simulated physiological conditions (pH 7.4). Acknowledgements: Thanks are due to the Foundation for Science and Technology (Portugal) for its financial support of Centre of Chemistry. The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network (RNRMN), and was purchased in the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT. References 1. Gonçalves, M.S.T. Chem. Rev. 2009, 109, 190. 2. Gonçalves, M.S.T. Optimized UV/Visible Fluorescent Markers in Advanced Fluorescence Reporters in Chemistry and Biology I. Fundamentals and Molecular Design, Demchenko A.P. (Volume Ed.), O.S. Wolfbeis (Series Ed.), Springer Series on Fluorescence, Vol. 8, Ch. 2, 27-64, Springer, Heidelberg, Germany, 2010. 3. a) Alves, C.M.A. et al Tetrahedron Lett. 2011, 52, 112. b) Naik, S. et al Eur. J. Org. Chem. 2011, 2491.

Abstract: Recently we have observed accelerating influence of trimethyl silyl chloride addition on the rate of the reactions of 5-(α-amino- α'-hydroxy)methylene Meldrum's Acids with amines particularly in the case of highly basic amines. However the nature of the aforementioned process remain unexplained. In proposed communication we wish to report insightful elucidation of this mechanism. The reaction under investigation involves simply addition of the trimethyl silyl chloride to the mixture of amine and carbamoyl Meldrum's acid derivative. We considered three potentially possible ways for the TMSCl action. The first possibility is formation of the O-silylated Meldrum acid, which would exclude formation of salt Meldrum's acid with amine, what undoubtedly hindered this reaction. The next way for the acceleration of the process is silylation of amine and subsequent reaction of silylated amine with carbamoyl Meldrum's acid. The last possibility is connected with the formation of equimolar amount of HCl during the reaction of TMSCl with carbamoyl Meldrum's acid or amine which should speed up the rate of decomposition of the Meldrum's acid derivative. The NMR monitored experiments as well classical experiments in which predicted intermediated were added to the reaction mixtures excluded formation of O-silylated Meldrum's acid as well as influence of formed HCl as a reason of the acceleration investigated reaction. Our experiments revealed that silylated amine is responsible for rate acceleration of the reaction amines and 5-(α-amino- α'-hydroxy)methylene Meldrum's Acids in the presence of TMSCl.

Abstract: The copper catalyzed Huisgen reaction was used for the synthesis of two derivatives of 1H-1,2,3-triazol-1,3,5-triazinane-2,4,6-trione. One from tris(2-azidoethyl)-1,3,5-triazinane-2,4,6-trione and phenylacetylene, and the other by coupling of 1,3,5-tri(prop-2-yn-1-yl)-1,3,5-triazinane-2,4,6-trione with benzyl azide.

Abstract: In this communication we present our initial synthetic studies to the natural product tulearin A. The total synthesis relies on the assembly of two chiral building blocks through regioselective nucleophilic epoxide opening and macrolactonization for the construction of 18-membered lactone skeleton. In this initial contribution we report the partial synthesis of the fragment C₁-C₇ containing three stereogenic centers where the key step is an asymmetric aldol condensation.

Abstract: The title compound was prepared from 2,6-difluorophenol in four steps. Acetylation, followed by nitration, reduction to the amine and diazotization/azide formation proceeded in the expected fashion. A copper-catalyzed Huisgen cyclization between the compound and phenylacetylene was carried out as a model and the triazole isolated. The propargyl ester of naproxen was prepared (naproxen/propargyl alcohol/carbodiimide) and the subsequent click reaction carried out. It is expected that this strategy will afford access to materials with dual biological activity.

Abstract: α-Alkylidene-γ-lactams and lactones are the active constituents of many natural and synthetic compounds exhibiting pronounced biological properties. They are able to act as Michael acceptors in the reaction with thiol groups of bionucleophiles or can readily form [2 + 2] cycloadducts with DNA bases. We have developed concise synthetic approaches towards exemplary representatives of α-methylene models that hinges upon the preliminary assembly of the lactam and lactone template. Subsequent installation of the methylidene by a metallation/alkylation/elimination sequence completed the elaboration of the racemic title compounds. The presence of a quaternary carbon center bearing the carboxylate function precluded the undesirable isomerization leading to the corresponding endocyclic unsaturated analogues.

Abstract: We have recently reported an experimental and computational study on [1,5]-H shifts in acetal-ketenimines and acetal-carbodiimides in which the acetalic H atom migrates to the central electrophilic carbon atom of the heterocumulenic fragment. These rearrangements occur under unusual mild thermal conditions, and were chemically interpreted as hydride shifts. The resulting intermediates undergo 6π electrocyclic ring closure to give, respectively, quinoline and quinazoline rings. As a continuation we considered the replacement of the ketenimine and carbodiimide functions by cumulene fragments. As expected, the thermal treatment of several acetal-allenes led to 1,2-dihydronaphthalenes by a similar [1,5]-H/6π electrocyclic ring closure tandem process. Next, as we will describe in this communication, we essayed the cyclization of acetal and dithioacetal-allenes, by activating the electron-rich cumulene function with a protic acids Surprisingly, these reactions provided new heterocyclic fused indenes as reaction products. A mechanistic rationale for explaining these results will be also disclosed.

Abstract: The Diels-Alder reaction of various reactive dienophiles with cyclopentadiene is reported. Rather than cracking dicyclopentadiene in a separate step, the reagents were mixed in a sealed tube and the reactions carried out at 185C. Conversion to the adducts is dependent on the nature of the dienophile and the reaction time. In those cases where stereochemistry is relevant, the endo/exo ratios are reported and compared to those reported at lower temperatures.

Abstract: Selenium-based reagents bear a high potential for the improvement of known reactions not only from an environmental and pharmaceutical point of view, but also as interesting reagents for the development of, completely new synthetic transformations and as potential ligands in catalytic reactions. A variety of organoselenium compounds have been proven to be useful for organic synthesis over several decades. Organoselenium species can be introduced as either nucleophiles or electrophiles to other organic molecules, producing useful intermediates for organic synthesis. Optically active organoselenium derivatives and their application to highly selective asymmetric synthesis are also of current interest. Probably the most interesting aspect, which emerged in recent years, concerns the possibility of effecting some functional group conversions using catalytic amounts of the selenium reagent or using selenium containing compounds as chiral ligands in metal catalyzed reactions. The developments of all these catalytic processes represent the most important results which have been reported recently in this field and their conceptual and synthetic relevance considerably increases the use of some organoselenium derivatives as Green Catalysts. [1] In consideration that in Nature, the main biological function of selenium is associated with its incorporation in the form of selenocysteine (Sec) into certain proteins having redox motifs different selenium containing compounds can be investigated as bio-inspired catalysts in the carbon-carbon multiple bond oxidation mediated by H₂O₂ in water. These catalysts resulted to be also interesting good GPx-mimetics. Acknowledgement: Financial support from M.I.U.R.-PRIN2007, Consorzio CINMPIS, Bari, University of Perugia, the grant "British-Italian Partnership" from the British Council/CRUI. References [1] a) D. M. Freudendahl, S. Santoro, S. A. Shahzad, C. Santi, T. Wirth Angew. Chem. Int. Ed.2009, 8, 8409.b) C. Santi, M. Tiecco, L. Testaferri, C. Tomassini, S. Santoro, G. Bizzoca Phosphorus Sulfur Silicon Relat. Elem. 2008,183, 956. c) S. Santoro, C. Santi, M. Sabatini, L. Testaferri, M. Tiecco Adv.Synth. Catal. 2008, 350, 2881. d) S. Santoro, B. Battistelli, B. Gjoka, C-w.S.Si, L.Testaferri, M. Tiecco, C. Santi Synlett, 2010, 1402.

Abstract: The authors report on the use of the reaction system BrCCl₃/PPh₃ in the amidation of carboxylic acids, in the preparation of anhydrides from carboxylic acids and in the esterification of carboxylic acids with cholesterol, where cinnamic acids were used as acid component in all three transformations. Furthermore, the use of BrCCl₃/PPh₃ in the dehydration of benzcarboxamides to benzonitriles was studied as well as the preparation of N-(phenylsulfonyl)-triphenylphosphoranylideneamide from benzenesulfonamide.