Chemoselective thioacetalization and transthioacetalization of carbonyl compounds catalyzed by immobilized scandium(III) triflate in ionic liquids

Immobilized scandium triflate [Sc(OTf)₃] in ionic liquids has been found to be an extremely efficient and recyclable catalyst for the thioacetalization and transthioacetalization of both aromatic and aliphatic aldehydes. Significant rate acceleration and chemoselectivity was achieved by employing this catalytic system.     

The use of Nafion-H® as an efficient catalyst for the direct conversion of primary and secondary trimethylsilyl ethers to their corresponding ethers under mild and heterogeneous conditions

Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence Nafion-H® with good to excellent yields under mild and heterogeneous conditions.     

Ammonium tetraphenylborate-naphthalene adsorbent for the preconcentration and trace determination of iron in alloys and biological samples using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by third derivative spectrophotometry

A solid ion-pair material produced from ammonium tetraphenylborate on naphthalene (ATPB-naphthalene) provides a simple, rapid, economical and selective technique for preconcentrating iron from approximately 500 ml of aqueous solution of standard alloys and biological samples. Iron reacts with 2-(5-bromo-2-pryidlazo)-5-diethylaminophenol (5-Br-PADAP) to form a water-soluble cationic complex. When the aqueous solution of this cationic species in the pH range 3.2-8.5 is passed over the adsorbent ATPB-naphthalene at a flow rate of 1 ml min(-1), it is quantitatively retained on naphthalene as an uncharged ion-associated complex. The solid mass from the column was dissolved out with 5 ml of dimethylformamide (DMF) and iron is determined by third derivative spectrophotometry by measuring the signal d(3)A/ dlambda(3) between lambda(2)(773 nm) and lambda(3)(737 nm). The calibration curve is linear over the concentration range 0.10-25.0 mug of iron in 5 ml of DMF solution. Eight replicate determinations of 5 mug of iron gave a mean intensity (peak-to-peak signal between lambda(2) and lambda(3)) of 1.534 with a relative standard deviation of 0.90%. The sensitivity of the method is 0.307 (d(3)A/dnm(3) )/mug found from the slope of the calibration curve. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of iron in various standard alloys and biological samples.     

A study of the formation of silica-supported mixed magnesium-manganese spinel oxides from multicomponent gels

The effects of thermal treatment on composite materials prepared by the gelation of sols comprising large concentrations of metal oxide precursor salts have been investigated, in order to determine the compositional and thermal requirements for forming spinel magnesium manganates in such systems. The preparative technique has been found to give rise to derived gel materials in which the metal oxide phase, in the form of regular spherical particles, is dispersed throughout a continuous silica matrix. Silica-supported mixed magnesium and manganese spinel oxide phases were obtained for systems comprising at least 30 wt% metal nitrate after heating to temperatures between 700 and 850°C, but not without concomitant formation of Mn₂O₃ and modification of the silica network by magnesium.     

Synthesis, characterization, and electrochemical and electrochromic properties of sandwich dilutetium tetraphthalocyanine

A new sandwich-tpype dilutetium tetraphthalocyanine 4 has been synthesized by the reaction of dimeric lutetium(III) phthalocyanine 3 with two equiv. of dilithium octakishexylthiophthalocyanine in amyl alcohol. Compound 3 was prepared from 4',5',4",5"-tetraiminoisoindoline(1,4,7,10-tetrathia-12-crown-4) 1, 4,5-bis(hexylthio)-1,2-diiminoisoindoline and lutetium acetate in amyl alcohol. Compounds 3 and 4 were characterized by elemental analysis, UV/visible, IR, (1)H NMR and ESR spectroscopy. The electrochemical and electrochromic properties of 3 and 4 have been examined by cyclic voltammetry. Both 3 and 4 displayed well-defined electrochromic behavior.     

A novel and expeditious approach to unusual spirolactam building blocks

A rapid access to 7-azaspiro[4.5]decan-6-ones 1 involving three regio- and chemoselective reactions starting from tetrabromonorbornyl derivatives is described. The alkaline H(2)O(2) cleavage reaction of monosubstituted alpha-diketones 9 furnished the potential bridged bicyclic lactones 10in a highly regio- and stereoselective manner. The radical-mediated, intermolecular bridgehead C-C bond formation of the versatile bridged lactones 10 with acrylonitrile followed by LAH reduction of the adduct 13 intriguingly leads to the formation of novel spirolactam building blocks 1.     

PHTHALOCYANINE-INDUCED PHOTOHEMOLYSIS: STRUCTURE-ACTIVITY RELATIONSHIP AND THE EFFECT OF FLUORIDE

Abstract— Phthalocyanine (Pc) containing AI, Ga or Zn as central metal ligand and substituted with a varying number of sulfonic acid residues as well as additional benzene rings were synthesized and their photodynamic activity was assayed using photohemolysis of human erythrocytes as an endpoint. The Pc derivatives vaned > 300-fold in their photodynamic activity. Activity corrclated with binding of the dye to the cell, with the exception of some of the amphiphilic dyes where cell uptake was an order of magnitude higher than expected from the observed activity. Fluoride was shown to inhibit AIPcS_n-induccd photohemolysis. This effect occurred also with other AlPc and GaPc derivatives, but the concentration of F required to slow photohemolysis by a factor of two (K_i) varied between 4 μ M and 10 mM. Fluorescence spectral studies indicated complex formation between F⁻ and the dye, which was stronger for AlPc than GaPc derivatives. Ultrastructural studies using scanning electron microscopy showed that the photosensitized cells were converted to spherocytes and that F⁻ prevented this to a large extent.     

Synthesis and Reactions of 5-Amino-3-(3-methyl-5-oxo-1-phenyl-2-pyrazolin-4-yl)-7-phenyl-7 H -thiazolo[3,2- a ]pyrimidine-6-carbonitrile

5-Amino-3-(3-methyl-5-oxo-1-phenyl-2-pyrazolin-4-yl)-7-phenyl-7H-thiazolo[3,2-a]pyrimidine-6-carbonitrile was synthesized via the reaction of 4-(2-aminothiazol-4-yl)-3-methyl-1-phenyl-2-pyrazolin-5-one with benzylidene malononitrile and was then transformed to related fused heterocyclic systems. The antifungal and antibacterial studies revealed in some cases excellent biocidal properties.     

Determining molecular structures and conformations directly from electron diffraction using a genetic algorithm.

A global optimization strategy, based upon application of a genetic algorithm (GA), is demonstrated as an approach for determining the structures of molecules possessing significant conformational flexibility directly from gas-phase electron diffraction data. In contrast to the common approach to molecular structure determination, based on trial-and-error assessment of structures available from quantum chemical calculations, the GA approach described here does not require expensive quantum mechanical calculations or manual searching of the potential energy surface of the sample molecule, relying instead upon simple comparison between the experimental and calculated diffraction pattern derived from a proposed trial molecular structure. Structures as complex as all-trans retinal and p-coumaric acid, both important chromophores in photosensing processes, may be determined by this approach. In the examples presented here, we find that the GA approach can determine the correct conformation of a flexible molecule described by 11 independent torsion angles. We also demonstrate applications to samples comprising a mixture of two distinct molecular conformations. With these results we conclude that applications of this approach are very promising in elucidating the structures of large molecules directly from electron diffraction data.     

Thermal synthesis and characterisation of N,N'-di(chlorobenzyl) ureas

The thermal stability of the Schiff base ethylacetoacetate-o-chlorobenzylamine (bdII), N-o-chlorobenzyl-C-benzoyl acetamide (bdIII), and N-p-chlorobenzyl-C-benzoyl acetamide (bdIV) were studied by thermogravimetric analysis. II Gave N,N'-di(o-chlorobenzyl) urea (bdIa) at 60° C, whereas the thermogravimetric curves of III and IV indicate that reactions other than formation of I may occur. The urea derivatives (I) have also been prepared from benzylamines and the corresponding β-ketoester and identified.