Subsolidus area of the system CdO - V2O5 - Fe2O3

Phase diagrams in the subsolidus area of the systems FeVO₄ - CdO and FeVO₄ - Cd₂V₂O₇ have been deduced using the results of XRD and DTA analyses. On the basis of these diagrams and some additional verifying research, a projection of the subsolidus area of the CdO - V₂O₅ - Fe₂O₃ system onto the plane that comprises the components’ concentration triangle has been presented. The H-type phase is the only phase formed in this system. It co-exists at equilibrium with other phases in six subsidiary subsystems.      

Targeted synthesis ultrafine α- and γ-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> having different morphologies

Reactions of nitric acid solutions of bismuth with alkalis have been studied. The effect caused by coprecipitation conditions in the presence of additional agents (EG, PEG 400, or PEG 8000) and without on the phase composition and morphology of α- and γ-Bi₂O₃ has been determined.     

Solvent extraction of cerium/III/ with 1-/2-pyridylazo/-2-naphthol from perchloric acid media

A study on solvent extraction of cerium/III/ ion with 1-/2-pyridylazo/-2-naphthol /PAN or HL/ in chloroform from perchloric acid solution is described. The effect of equilibrium time, the pH of the aqueous phase and the concentration centration of extractant in organic phase on the extraction efficiency of cerium/III/ has been studied. The results show that the mechanism of extraction reaction is 3Ce _/aq/ ³⁺ + 3HL_/o/ CeL_3/o/ + 3H ₊ ^/aq/     

Studies on the behaviour of α-, β- and γ-cyclodextrins and some derivatives under reversed-phase liquid Chromatographic conditions

The separation processes of α-, β- and γ-cyclodextrins and their various methyl derivatives have been investigated with Knauer polarimetric (Chiralyser) and refractive index (RI) detectors. RP18 and RP8 hydrocarbon packings and an NH₂ bonded phase were applied as stationary phases. Aqueous methanolic or ethanolic solutions were used as mobile phases. It has been found that the Chiralyser detector response is approximately linear at low concentrations of solutes and that its detection capabilities are about 40 times better than those of the RI detector. Differences in the order of elution of α-, β- and γ-cyclodextrins have been observed for various stationary phases as well as for various mobile phase compositions. The optimal conditions for analytical determinations of cyclodextrins and their derivatives have been discussed.     

S<Subscript>(2)</Subscript>- or N<Subscript>(3)</Subscript>-Substituted 2-Mercapto-5-(4-pyridyl)-1,3,4-oxadiazoles

New S₍₂₎- or N₍₃₎-substituted 2-mercapto-5-(4-pyridyl)-1,3,4-oxadiazoles have been obtained and characterized. The direction of substitution depends on the structure of the initial reactants and the reaction conditions. The synthesis of several thiosemicarbazides has been effected from isonicotinic acid hydrazide.     

Novel oxorhenium complexes with 2-(2′-hydroxyphenyl)-2-benzothiazolinato ligand: X-ray studies,spectroscopic characterization and DFT calculations

The [ReOX₂(hbt)(EPh₃)] (X = Cl, Br; E = As, P) chelates have been prepared in the reactions of [ReOX₃(EPh₃)₂] complexes (X = Cl, Br; E = P, As) with 2-(2′-hydroxyphenyl)-2-benzothiazole (hbtH) in acetone. From the reactions of [ReOX₃(PPh₃)₂] with hbtH two kind of crystals [ReOX₂(hbt)(PPh₃)] · MeCN and [ReOX₂(hbt)(PPh₃)] with different arrangement of halide ions (cis and trans) were isolated, whereas the [ReOX₃(AsPh₃)₂] oxocompounds react with hbtH to give only cis-halide isomers. The complexes were structurally and spectroscopically characterised. The electronic structures of both [ReOBr₂(hbt)(PPh₃)] isomers have been calculated with the density functional theory (DFT) method. The TDDFT/PCM calculations have been employed to produce a hundred of singlet excited-states starting from the ground-state geometry optimized in the gas phase of cis- and trans-halide isomers of [ReOBr₂(hbt)(PPh₃)] and the UV–Vis spectra of these complexes have been discussed on this basis.     

Synthesis, Crystal Structure Determination, and Physicochemical Study of the Nickel(II) Complex of 4-(Pyridyl-2)-1,2,4-triazole

A new trinuclear nickel(II) complex with 4-(pyridyl-2)-1,2,4-triazole (pytrz), [Ni₃(pytrz)₆(H₂O)₆](NO₃)₆, has been synthesized, and its crystal structure has been determined. The compound was studied by X-ray phase analysis (XRPA), magnetochemical measurements, and electronic and IR spectroscopy.     

Solvent extraction of certain rare earth metal ions with 1-(2-pyridylazo)-2-naphthol (PAN)

The solvent extraction of Yb(III) by 1-(2-pyridylazo)-2-naphthol (PAN or HL) in carbon tetrachloride from aqueous—ethanol phase has been investigated as a function of thepH ^X of the polar phase and the concentrations ofPAN or ethanol (EtOH) in the organic phase. It was confirmed that the addition of ethanol to the aqueous phase causes an increase of the Yb(III) distribution coefficient. The equation for the extraction reaction has been suggested as: $$Yb(H_2 O)_{m(^p )}^{3 + } + 3H L_{(o)} + t Et OH_{(o)} \rightleftharpoons Yb L_3 \left( {EtOH} \right)_{t(o)} + 3H_{(^p )}^ + + mH_2 O$$ wheret changes from 0 to 3. The extraction equilibrium constant (K _ex ) and two-phase stability constants (β ₃ ^× ) for the YbL ₃ (EtOH)₃ complex have been evaluated. The formation of solvates YbL ₃ (EtOH) _t is probably the main reason of the synergistic effect which was observed.     

Molecular engineering of liquid crystalline polymers by “living” polymerization. XXXII. Synthesis and “living” cationic polymerization of 3-fluoro-4′-(ω-vinyloxyalkoxy)-4-biphenylyl (2r,3s)-2-fluoro-3-methylpentanoate with undecanyl and octyl alkyl groups

The synthesis and “living” cationic polymerization of 3-fluoro-4′-(11-vinyloxyundecany-loxy)-4-biphenylyl (2R,3S)-2-fluoro-3-methylpentanoate ( 12-11 ) and 3-fluoro-4′-(8-vi-nyloxyoctyloxy)-4-biphenylyl (2R,3S)-2-fluoro-3-methylpentanoate ( 12-8 ) are presented. Poly ( 12-11 )s and poly ( 12-8 )s with degrees of polymerization from 4.0 to 16.5 and poly-dispersities ≤ 1.13 have been synthesized and characterized by differential scanning cal-orimetry (DSC) and thermal optical polarized microscopy. Over the entire range of molecular weights poly ( 12-11 )s and poly ( 12-8 )s exhibit an enantiotropic S_A and an unidentified S_X phase. In addition, regardless of its molecular weight, poly ( 12-8 ) exhibits a S^*_c phase in between the S_A and S_x phases. Poly ( 12-11 ) and poly ( 12-8 ) show lower transition tem-peratures and broader temperature ranges of all their mesophases as compared to the corresponding polymers without a fluorine atom on the biphenyl group. The role of the connecting group between the biphenyl and chiral group of the mesogenic unit on the phase behavior of these polymers is also discussed. Copolymers of 12-8 with (2R,3S)-2-fluoro-3-methylpentyl 4′-(11-vinyloxyundecanyloxy)biphenyl-4-carboxylate ( 13-11 ) {i.e., poly-[( 12-8 )-co-( 13-11 )] (X/Y), where X/Y represents the molar ratio of monomer 12-8 to monomer 13-11 } with DP of ca. 11 and polydispersities lower than 1.23 were also syn-thesized and characterized. Their S_A and S^*_c mesophases exhibit continuous dependences of composition and this support the assignment of the mesophases exhibited by poly ( 12-8 ). © 1995 John Wiley & Sons, Inc.     

Novel oxorhenium complexes with 2-(2′-hydoxy-5′-methylphenyl)benzotriazolato ligand. X-ray studies,spectroscopic characterization and DFT calculations

The [ReOCl₂(hmpbta)(AsPh₃)] · MeCN, [ReOBr₂(hmpbta)(AsPh₃)] · MeCN, [ReOCl₂(hmpbta)(PPh₃)] · MeCN, [ReOBr₂(hmpbta)(PPh₃)] · MeCN, and [ReBr₂(hmpbta)(PPh₃)] · MeCN complexes have been prepared in the reactions of [ReOX₃(EPh₃)₂] (X = Cl, Br; E = P, As) with 2-(2’-hydoxy-5′-methylphenyl)benzotriazole in molar ratio 1:1. All the compounds were structurally and spectroscopically characterized. The electronic structure of [ReOCl₂(hmpbta)(AsPh₃)] has been calculated with the density functional theory (DFT) method. The TDDFT/PCM calculations have been employed to produce a hundred of singlet excited-states starting from the ground-state geometry optimized in the gas phase, and the UV–Vis spectrum of [ReOCl₂(hmpbta)(AsPh₃)] has been discussed on this basis. The paper reports also X-ray structure and DFT calculations for the disubstituted [ReOCl(hmpbta)₂] chelate.     

Zn(II) and Cu(II) complexes of 2-(2-hydroxy-5-methylphenyl)-1<Emphasis Type="Italic">H</Emphasis>-benzimidazole and crystal structure of 2-(2-hydroxy-5-methylphenyl)-1<Emphasis Type="Italic">H</Emphasis>-benzimidazolium chloride

2-(2-Hydroxy-5-methylphenyl)-1H-benzimidazole ligand (HL) and its complexes with Cu(NO₃)₂, Zn(NO₃)₂ have been synthesized and characterized. The structures of the compounds were confirmed on the basis of elemental analysis, molar conductivity, magnetic moment, FT-IR, ¹H- and ¹³C NMR. Cu(II) complex has 1: 2 metal: ligand ratio, while Zn(II) complex is 1: 1. Crystal structure of 2-(2-hydroxy-5-methylphenyl)-1H-benzimidazolium chloride (HL · HC1) was determined by single-crystal X-ray diffraction. It crystallizes in the orthorombic, space group P2₁2₁2₁and Z = 4.     

Rhenium(V) oxocomplexes incorporating 2-(2<Emphasis Type="Italic">H</Emphasis>-benzotriazol-2-yl)-4,6-di-<Emphasis Type="Italic">tert</Emphasis>-pentylphenolate ligand: X-ray studies,spectroscopic characterization and DFT calculations

Novel rhenium(V) oxocomplexes have been obtained in the reactions of [ReOX₃(EPh₃)₂] (X = Cl, Br; E = P, As) with 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (HL). All the compounds were identified by elemental analysis IR, UV–Vis spectroscopy and X-ray crystallography. The electronic structure and spectroscopic features of [ReOBr₂(L)(PPh₃)] have been further investigated by means of the density functional theory (DFT) and time-dependent DFT methods. Additional information about binding in the title compounds has been obtained by NBO analysis.     

Subsolidus phase relations in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Li<Subscript>2</Subscript>O-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> (Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>) systems

The phase composition has been studied and an equilibrium phase diagram has been designed for the Al₂O₃-Li₂O-R₂O₅ (R = Ta or Nb) systems in the subsolidus region up to 1000°C and 85 mol % Li₂O. New phases with the composition Li_1+x Al_1?x O_2?x , where x = 0–0.67, have been found.     

Solvent extraction of rare earth metal ions with 1-(2-pyridylazo)-2-naphthol (PAN)

The solvent extraction of Yb(III) and Ho(III) by 1-(2-pyridylazo)-2-naphthol (PAN or HL) in carbon tetrachloride from aqueous-methanol phase has been studied as a function ofpH ^× and the concentration ofPAN or methanol (MeOH) in the organic phase. When the aqueous phase contains above ～25%v/v of methanol the synergistic effect was increased. The equation for the extraction reaction has been suggested as: $$\begin{gathered} Ln(H_2 0)_{m(p)}^{3 + } + 3 HL_{(o)} + t MeOH_{(o)} \mathop \rightleftharpoons \limits^{K_{ex} } \hfill \\ LnL_3 (MeOH)_{t(o)} + 3 H_{(p)}^ + + m H_2 0 \hfill \\ \end{gathered} $$ where:Ln ³⁺=Yb, Ho; $$\begin{gathered} t = 3 for C_{MeOH in.} \varepsilon \left( { \sim 25 - 50} \right)\% {\upsilon \mathord{\left/ {\vphantom {\upsilon \upsilon }} \right. \kern-\nulldelimiterspace} \upsilon }; \hfill \\ t = 0 for C_{MeOH in.} \varepsilon \left( { \sim 5 - 25} \right)\% {\upsilon \mathord{\left/ {\vphantom {\upsilon \upsilon }} \right. \kern-\nulldelimiterspace} \upsilon } \hfill \\ \end{gathered} $$ . The extraction equilibrium constants (K _ex ) and the two-phase stability constants (β ₃ ^× ) for theLnL ₃(MeOH)₃ complexes have been evaluated.     

Spectral characterization and antibacterial effect of 2-methyl-6-(5-H-Me-Cl-NO <Subscript>2</Subscript>-1<Emphasis Type="Italic">H</Emphasis>-benzimidazol-2-yl)-phenols and some transition metal complexes

2-Methyl-6-(5-H-methyl-chloro-nitro-1H-benzimidazol-2-yl)-phenols( HL _x :x= 1-4)ligands and HL₁ complexes with Fe(NO₃)₃, Cu(NO₃)₂, AgNO₃, Zn(NO₃)₂ have been synthesized and characterized. The structures of the compounds were confirmed on the basis of elemental analysis, molar conductivity, magnetic moment, FT-IR, ¹H-and ¹³C-NMR. Antibacterial activity of the free ligands, their hydrochloride salts and the complexes were evaluated using the disk diffusion method in dimethyl sulfoxide as well as the minimum inhibitory concentration dilution method, against nine bacteria. While HL₁ ligand has not any activity, it’s Ag(I) complex show antibacterial effect toward almost to all the bacteria. Zn(II) complex has antibacterial effect on especially K. pneumoniae, S. epidermidis and S. aureus bacteria.     

Total Synthesis of (±)-2-Pupukeanone

(±)-2-Pupukenone ( 4 ) has been synthesized, the key step being the intramolcular Diels-Alder reaction of the intermediate 13 to 14 (42%) and 15 (14%). The bromodiene 12 has been obtained from the reaction of α-isopropylidene-γ-lactone (Scheme 2) 12 with sodium phenylselenide and subsequent esterification to 9 , oxidation and thermal elimination of which furnished 10 . Reduction of 10 with diisobutylaluminimum hydride and treatment of the resulting alcohol 11 with PBr₃ led to the required bromodiene 12 . Finally, hydrogenation of the 14 on Pt(C) in CH₃OH gave a 4:1 mixture of 2-pupukeanone ( 4 ) and epi-2-pupukeanone 16 .     

4-hydroxy-2-quinolones 196. synthesis and bromination of 1-allyl-3-(2-hydroxyethyl)-1<Emphasis Type="Italic">h</Emphasis>,3<Emphasis Type="Italic">h</Emphasis>-quinazoline-2,4-dione

The alkylation of 3-(2-hydroxyethyl)-1H,3H-quinazoline-2,4-dione and subsequent bromination of its 1-allyl derivative have been studied. The data obtained has been compared with the results of similar studies on a series of other, related compounds. A rule has been formulated which allows a prediction of 1-allyl-substituted 2-oxo azaheterocycles bromination route based upon the way in which their initial alkylation by allyl bromide in the system DMSO–K₂CO₃ occurs.     

Phase diagram of V<Subscript>2</Subscript>O<Subscript>5</Subscript>-MoO<Subscript>3</Subscript>-Ag<Subscript>2</Subscript>O system

The results concerning the synthesis, structure and thermal properties of V₂O₅-MoO₃-Ag₂O samples in the vanadium rich region of ternary system are presented in the form of quasi-binary phase diagrams in which at constant V₂O₅/MoO₃ molar ratios, equal 9:1, 7:3 and 1:1, the content of Ag₂O was variable. A new ternary phase isostructural with NaVMoO₆ has been detected in the investigated system.     

Phase equilibriums,ion association,and mechanisms of solvation in the LiN(CF<Subscript>3</Subscript>SO<Subscript>2</Subscript>)<Subscript>2</Subscript>-(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>SO<Subscript>2</Subscript> system

The phase diagrams, isotherms of the electrical conductivity, Raman spectra, and time correlation functions of vibrational dephasing are studied for the LiN(CF₃SO₂)₂-(CH₃)₂SO₂ system, which is promising for use as an electrolyte in medium-temperature lithium-ion batteries. The phase diagram of this system contains a broad supercooled region. It is shown that the concentration dependences of the electrical conductivity are typical for solutions of strong electrolytes. The Raman spectra and the time correlation functions of vibrational dephasing for the anion and the solvent indicate that in the supercooling range, cations are weakly solvated by solvent molecules and form ion pairs.     

Synthesis and luminescent properties of copper(I) complexes with 3-pyridin-2-yl-5-(4-R-phenyl)-1<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazoles

A series of heteroligand copper(I) complexes with 3-pyridin-2-yl-5-(4-R-phenyl)-1H-1,2,4-triazoles (R = H, CH₃, CH₃O) and PPh₃ of general composition CuIL(PPh₃) have been synthesized and studied. The compounds have been characterized by elemental analysis, IR spectroscopy, and diffusion reflectance spectra. The structure of the complex with 3-pyridin-2-yl-5-phenyl-1H-1,2,4-triazole has been determined by single-crystal X-ray diffraction analysis. The complex is mononuclear and has a tetrahedral environment of the central atom. The compounds exhibit strong visible photoluminescence (λ_max = 599–609 nm). Quantum-chemical calculations at the B3LYP/DGDZVP level have demonstrated that the short phosphorescence life-time of the CuIL(PPh₃) compounds is caused by intensity transfer from the S ₀–S ₂ transition through spinorbit coupling induced by the rotation of the iodine 5p orbital upon the T ₁–S ₂ transition.