Synthesis, Spectroscopic Studies and X-ray Crystal Structures of New Pyrazoline and Pyrazole Derivatives

The synthesis and characterization of some pyrazoline compounds of 1,3-diketones with hydrazine derivatives, namely, 1-(S-benzyldithiocarbazate)-3-methyl-5-phenyl-5-hydroxypyrazoline (1); 1-(2-thiophenecarboxylic)-3-methyl-5-phenyl-5-hydroxypyrazoline (2); 1-(2-thiophenecarboxylic)-3,5-dimethyl-5-hydroxypyrazoline (3); 1-(S-benzyldithiocarbazato)-3-methyl-5-phenylpyrazole (4); 1-(2-thiophenecarboxylic)-3-methyl-5-phenylpyrazole (5) and 1-(S-benzyldithiocarbazate)-3,5-dimethylpyrazole (6) are reported. Studies by IR, ((1)H, (13)C)-NMR spectroscopies and single crystal X-ray diffraction revealed that compounds (1)(,) (2) and (3) are formed as pyrazoline, whereas (4) and (5) are formed as pyrazole derivatives only under acidic conditions. Compound (1) crystallizes in orthorhombic P2(1)2(1)2(1), a = 6.38960(10) angstrom, b = 12.9176(3) angstrom, c = 21.2552(5) angstrom, (2) crystallizes in monoclinic, P2(1)/n, a = 11.3617(2) angstrom, b = 8.4988(2) angstrom, c = 92.8900(10)angstrom and beta = 92.8900(5)degrees, (3) crystallizes in monoclinic, C2/c, a = 15.9500(5) angstrom, b = 9.3766(3) angstrom, c = 16.6910(5)angstrom and beta = 113.825(2)degrees, (4) crystallizes in monoclinic, P2(1)/c, a = 15.228(4) angstrom, b = 5.5714(13) angstrom, c = 19.956(5)angstrom and beta = 91.575(7)degrees and (6) crystallizes in orthorhombic, P2(1)2(1)2(1), a = 5.3920(2) angstrom, b = 11.2074(5) angstrom, c = 21.885(1)angstrom . The (3) derivative represents the first pyrazoline compound prepared from 2,4-pentanedione and characterized crystallographically.

Structural and Electronic Properties of Dipyridamole and Derivatives

Quantum mechanical calculations at the B3LYP theory level, together with the 6-31G* basis set, were employed to obtain the energy, ionization potential, and polarizabilites for dipyridamole and derivatives, which are compared with their biological activity. Density functional calculations of the spin densities were performed for radical formed by electron abstraction of dipyridamole and derivatives. The unpaired electron remains in dipyridamole is localized on the nitrogen atoms in the substituent positions 1, 3, 5, 7, 11, 12, 13, 14, with participation of the 9 and 10 carbons in the pyrimido-pyrimidine ring. The antioxidant activity is related with ionization potential, polarizability and Log P.

Synthesis, spectroscopic characterization and X-ray structures of five-coordinate diorganotin(IV) complexes containing 5-hydroxypyrazoline derivatives as ligands

Four new diorganotin(IV) complexes have been prepared from R(2)SnCl(2) (R = Me, Ph) with the ligands 5-hydroxy-3-metyl-5-phenyl-1-(S-benzildithiocarbazate)-pyrazoline (H(2)L(1)) and 5-hydroxy-3-methyl-5-phenyl-1-(2-thiophenecarboxylic)-pyrazoline (H(2)L(2)). The complexes were characterized by elemental analysis, IR. (1)H (13)C, (119)Sn NMR and Mossbauer spectroscopes The complexes [Me(2)SnL(1)], [Ph(2)SnL(1)] and [Me(2)SnL(2)] were also studied by single crystal X-ray diffraction and the results showed that the Sn(IV) central atom of the complexes adopts a distorted trigonal bipyramidal (TBP) geometry with the N atom of the ONX-tridentate (X = O and S) ligand and two organic groups occupying equatorial sites. The C-Sn-C angles for [Me(2)Sn(L(1))] and [Ph(2)Sn(L(1))] were calculated using a correlation between (119)Sn Mossbauer and X-ray crystallographic data based on the point-charge model Theoretical calculations were performed with the B3LYP density functional employing 3-21G(*) and DZVP all electron basis sets showing good agreement with experimental findings General and Sn(IV) specific IR harmonic frequency scale factors for both basis sets were obtained from comparison with selected experimental frequencies (C) 2010 Elsevier B V All rights reserved

Antifungal activity of tri- and tetra-thioureido amino derivatives against different Candida species

The in vitro antifungal activity of six thioureido substituted amines (P1-P6) was evaluated against Candida species, including Candida albicans, C. glabrata, C. krusei and C. parapsilosis. These tri- and tetra-thioureido amino derivatives with different methylation levels were synthesised through easy synthetic routes to evaluate their antifungal properties against Candida species. Among all studied derivatives, the tri-(2-thioureido-ethyl)-amine (P1) was the most active compound inhibiting C. albicans and C. glabrata at a concentration of 0.49 mu g ml(-1); P3, the N,N `,N ``,N ```-hexamethyl-derivative, also showed inhibitory activity against C. albicans and C. glabrata, but in higher concentrations (250 mu g ml(-1)). The N,N `,N ``,N ```-tetramethylated amine (P5) only inhibited the growth of C. glabrata, but its corresponding N,N `,N ``,N ```-octamethyl derivative (P6) was also active against C. glabrata (125 mu g ml(-1)) and it was the only compound active against C. parapsilosis. P2 and P4 showed no significant antifungal activity. The structure-activity relationship of the thioureido-substituted derivatives indicates that the molecular branching and the alkylation levels can influence the antifungal activity. This study demonstrated that thioureido derivatives exhibited significant antifungal activity against Candida species and that they can be considered as a very promising bioactive lead compound to develop novel antifungal agents.

Dodd Frank act and the Brazilian capital market: extraterritorial effects of regulation to the over-the-counter derivatives market

This paper aims to describe the chief alterations proposed by the Dodd Frank Act to the American over-the-counter derivatives market and, at the same time, understand the extraterritorial reach of this law compared to the regulatory framework of the Brazilian derivative market. In order to do so, I will study the extraterritorial effects of the law, particularly in reference to the international nature of Title II of the Dodd Frank, which deals with the over-the-counter derivatives, in order to evaluate its reach to foreign markets, especially the Brazilian market.

Evaluation of anti-inflammatory activity of derivatives from aerial parts of Baccharis uncinella

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

Investigation of the two-photon absorption cross-section in perylene tetracarboxylic derivatives: Nonlinear spectra and molecular structure

We investigated the 2PA absorption spectrum of a family of perylene tetracarboxylic derivatives ( PTCDs): bis( benzimidazo) perylene ( AzoPTCD), bis( benzimidazo) thioperylene ( Monothio BZP), n-pentylimidobenzimidazoperylene ( PazoPTCD), and bis( n-butylimido) perylene ( BuPTCD). These compounds present extremely high two-photon absorption, which makes them attractive for applications in photonics devices. The two-photon absorption cross-section spectra of perylene derivatives obtained via Z-scan technique were fitted by means of a sum-over-states ( SOS) model, which described with accuracy the different regions of the 2PA cross-section spectra. Frontier molecular orbital calculations show that all molecules present similar features, indicating that nonlinear optical properties in PTCDs are mainly determined by the central portion of the molecule, with minimal effect from the lateral side groups. In general, our results pointed out that the differences in the 2PA cross-sections among the compounds are mainly due to the nonlinearity resonance enhancement.

Two-photon absorption in perylene derivatives

This work reports on the two-photon absorption (2PA) cross-section for bis (n-butylimido) perylene (BuPTCD), bis (benzimidazo) perylene (AzoPTCD), bis (benzimidazo) thioperylene (Monothio BZP), bis (phenethylimido) perylene (PhPTCD), bis (benzylimido) perylene (BePTCD) and n-pentylimido-benzimidazo perylene (PAzoPTCD) solutions measured using the Z-scan technique with femtosecond laser pulses at 775 nm. All perylene derivatives studied present large 2PA cross-sections, only comparable to the best ones reported in the literature. The experimental 2PA cross-sections obtained for each PTCD compound are in good agreement with a simplified sum-over-state calculation. The results of the present work indicates perylene derivatives as promising materials for two-photon applications. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Perylene derivatives with large two-photon-absorption cross-sections for application in optical limiting and upconversion lasing

Perylene tetracarboxylic derivatives (PTCDs) display exceptionally high two-photon absorption (2PA) cross-sections (6, see Figure). In addition, the 2PA saturation behavior and strong two-photon-pumped fluorescence suggest that PTCD compounds may be attractive candidates for applications in optical limiting and two-photon-pumped upconversion lasing.

Topliss method in the optimization of salicylic acid derivatives as potential antimycobacterial agents

The Topliss method was used to guide a synthetic path in support of drug discovery efforts toward the identification of potent antimycobacterial agents. Salicylic acid and its derivatives, p-chloro, p-methoxy, and m-chlorosalicylic acid, exemplify a series of synthetic compounds whose minimum inhibitory concentrations for a strain of Mycobacterium were determined and compared to those of the reference drug, p-aminosalicylic acid. Several physicochemical descriptors (including Hammett's sigma constant, ionization constant, dipole moment, Hansch constant, calculated partition coefficient, Sterimol-L and -B-4 and molecular volume) were considered to elucidate structure-activity relationships. Molecular electrostatic potential and molecular dipole moment maps were also calculated using the AM1 semi-empirical method. Among the new derivatives, m-chlorosalicylic acid showed the lowest minimum inhibitory concentration. The overall results suggest that both physicochemical properties and electronic features may influence the biological activity of this series of antimycobacterial agents and thus should be considered in designing new p-aminosalicylic acid analogs.

Synthesis and in vitro anti Mycobacterium tuberculosis activity of a series of phthalimide derivatives

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

Searching for gallium bioactive compounds: Gallium(III) complexes of tridentate salicylaldehyde semicarbazone derivatives

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

Synthesis and Anti-Mycobacterium tuberculosis Evaluation of Aza-Stilbene Derivatives

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)