Thermal dehydration of 2-(4-aminophenyl)ethanol

The influence of inorganic nucleophilic agents on the liquid-phase process of thermal dehydration of 2-(4-aminophenyl)ethanol at 200–260°C was investigated. It was found that K₂CO₃, BaCO₃, BaO, CaH₂, and NaOH did not catalyze the dehydration, but the process takes place easily with the formation of 4-aminostyrene in high yield, using KOH in the range of 100–180 mol % with respect to 2-(4-aminophenyl)ethanol.     

Influence of H<Subscript>2</Subscript>O and SO<Subscript>2</Subscript> on the activity of deposited cobalt oxide catalysts in the processes of reduction of nitrogen(I), (II) oxides with carbon monoxide and C<Subscript>3</Subscript>-C<Subscript>4</Subscript> alkanes

It is shown that palladium–cobalt oxide–cerium catalyst deposited on cordierite catalyzes the reduction of nitrogen(II) oxide with carbon monoxide, and cobalt–iron catalysts in simultaneous reduction of NO + N₂O with C₃-C₄ alkanes retained high activity in the presence of water vapor and sulfur dioxide. The Pd-Co₃O₄/cordierite catalyst exceeds the Pt-Co₃O₄/codierite catalyst in the conversion of NO and CO in the reaction mixture CO + NO + O₂ + H₂O + SO₂. Modification of the Pd-Co₃O₄/cordierite with cerium oxide considerably increases its sulfur resistance.     

Synthesis and structure of <Emphasis Type="Italic">N</Emphasis>-(2-(1-adamantyl)-2-hydroxyethyl)cytisine diastereomers

Diastereomers of N-(2-(1-adamantyl)-2-hydroxyethyl)cytisine were synthesized by reduction of N-(2-(1-adamantyl)-2-oxoethyl)cytisine with NaBH₄. Their structures were established using x-ray structure analysis. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 244–247, May–June, 2007.     

Aqueous sol–gel processing of precursor oxides for ZrW<Subscript>2</Subscript>O<Subscript>8</Subscript> synthesis

This paper describes the synthesis of ZrW₂O₈ by the use of an aqueous citrate-gel method in order to prepare a fine, pure and homogeneous oxide mixture suitable for ceramic processing. The thermal expansion coefficient thus obtained for α-ZrW₂O₈ is −10.6 × 10⁻⁶ °C⁻¹ (50–125 °C) whereas for the β-ZrW₂O₈ a value of −3.2 × 10⁻⁶ °C⁻¹ (200–300 °C) is obtained. The advantages of the use of a sol–gel method is expressed in the very homogeneous end-products. The paper describes crystallographic data, morphological structure and the thermal expansion properties of the ZrW₂O₈ material. Moreover, photoluminescence and photochromic properties specific to the precursor gel are described and analyzed. These effects support our views that the precursors show homogeneity up to nanometer level.     

Steric distortion of planar NiP<Subscript>2</Subscript>N<Subscript>2</Subscript> chromophores: a spectral,cyclic voltammetric and single crystal X-ray structural study

The complexes trans-[Ni(4-MP)₂(NCS)₂]·MeCN (1) and trans-[Ni(3-MP)₂(NCS)₂] (2) (4-MP = tri(4-methylphenyl)phosphine, 3-MP = tri(3-methylphenyl)phosphine) were prepared and characterized by IR, UV–visible, NMR spectra, CV, TGA and single crystal X-ray crystallography. Both the complexes have planar geometry and are diamagnetic. The Ni–P distances in both complexes are relatively short as a result of strong back donation from nickel to phosphorus. The phenyl rings in the 3-MP analogue (2) show increased pitching with reference to the plane formed by the ipso carbons due to increased steric effects. For complex (2), the N–Ni–N and P–Ni–P angles are significantly lower than the almost linear N–Ni–N and N–Ni–P angles observed for both complex (1) and trans-[Ni(PPh₃)₂(NCS)₂]. This observation indicates that the 3-methylphosphine ligand forces complex (2) to distort towards a tetrahedral geometry. IR spectra of both complexes show strong bands around 2,090 cm⁻¹ due to N-coordinated thiocyanate, while the electronic spectra contain d–d transitions around 452 nm. Cyclic voltammograms show that the irreversible one-electron reduction potentials increase in the following order: trans- [Ni(PPh₃)₂(NCS)₂] < trans- [Ni(3-MP)₂(NCS)₂] < trans-[Ni(4-MP)₂(NCS)₂], revealing the electron releasing effect of the methyl groups. The planar complexes exhibit interallogony in coordinating solvents.     

Molecular Structure and Conformational Composition of 1-[(Methylthio)methyl]-2-nitrobenzene (MTMNB): A Theoretical and Experimental Study

The conformational composition of gaseous MTMNB and the molecular structures of the rotational forms have been studied by electron diffraction at 130^∘C aided by results from ab initio and density functional theory calculations. The conformational potential energy surface has been investigated by using the B3LYP/6-31G(d,p) method. As a result, six minimum-energy conformers have been identified. Geometries of all conformers were optimized using MP2/6-31G(d,p), B3LYP/6-31G(d,p), and B3LYP/cc-pVTZ methods. These calculations resulted in accurate geometries, relative energies, and harmonic vibrational frequencies for all conformers. The B3LYP/cc-pVTZ energies were then used to calculate the Boltzmann distribution of conformers. The best fit of the electron diffraction data to calculated values was obtained for the six conformer model, in agreement with the theoretical predictions. Average parameter values (r_a in angstroms, angle α in degrees, and estimated total errors given in parentheses) weighted for the mixture of six conformers are r(C–C) = 1.507(5), r(C–C)_{ring, av} = 1.397(3), r(C–S)_av = 1.814(4), r(C–N) = 1.495(4), r(N–O)_av = 1.223(3), ∠(C–C–C)_ring = 116.0–122.5, ∠ C6–C4–C7 = 118.2(4), ∠ C–C–S = 113.6(6), ∠ C–S–C = 98.5(12), ∠ N–C–C4 = 121.9(3), ∠(O–N–C)_av = 116.8(3), ∠ O–N–O = 127.0(4). Torsional angles could not be refined. Theoretical B3LYP/cc-pVTZ torsional angles for the rotation about C–N bond, φ_C−N, were found to be 30.5–36.5^∘ for different conformers. As to internal rotation about C–C and C–S bonds, values of φ_C−C = 68–118^∘ and φ_C−S = 66–71^∘ were obtained for the three most stable conformers with gauche orientation with respect to these bonds. Some conclusions of this work were presented in a short communication in Russ. J. Phys. Chem. 2005, 79, 1701.     

Conformational properties of <Emphasis Type="Italic">ortho</Emphasis>-nitrobenzenesulfonamide in gas and crystalline phases. Intra- and intermolecular hydrogen bond

A combined gas-phase electron diffraction and quantum chemical (B3LYP/6-311+G**, B3LYP/cc-pvtz, MP2/cc-pvtz) study of molecular structure of 2-nitrobenzenesulfonamide (2-NBSA) was carried out. Quantum chemical calculations showed that 2-NBSA has four conformers, two of which are stabilized by intramolecular hydrogen bond. The latter (with the S–N bond in a close to orthogonal position around the phenyl ring and differing from each other by staggered or eclipsed positions of the N–H and S=O bonds in the SO₂NH₂ group) presented in a saturated vapor over 2-NBSA at T = 433 (3) K in commensurable amounts. Experimental internuclear distances (Ǻ) for the staggered conformer are (?): r _h1(C–H)_av. = 1.071(9), r _h1(C–C)_av. = 1.390(4), r _h1(C–S) = 1.789(8), r _h1(S=O)_av. = 1.427(6), r _h1(S–N) = 1.644(6), r _h1(N–O)_av. = 1.221(4), r _h1(C′–N) = 1.487(8), r _h1(N–H)_av. = 1.014. Calculations at B3LYP/cc-pvtz level were performed to determine the structure and the energies of the transition states between conformers. It was shown that the conformer structures of free molecule differ from those of a molecule stabilized by intermolecular hydrogen bonds in a crystal. Influence of a substituent X (X = –CH₃, –NO₂) on conformational features of the ortho-substituted benzenesulfonamide was established.     

Synthesis,Spectra and Electrochemistry of Dinitro-bis-{1-alkyl-2-(arylazo) imidazole} Ruthenium(II). Nitro-nitroso Derivatives and Reactivity of the Electrophilic {Ru-NO}<Superscript>6</Superscript>System

Ag⁺ assisted aquation of blue cis-trans-cis-RuCl₂(RaaiR′)₂ (4–6) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH₂)₂(RaaiR′)₂](ClO₄)₂ [Raai R′=p-R-C₆H₄ N=N–C₃H₂–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), OMe (b), NO₂ (c) and R′ = Me (1/4/7/10), CH₂CH₃ (2/5/8/11), CH₂Ph (3/6/9/12)] that have been reacted with NO₂⁻in warm EtOH resulting in violet dinitro complexes of the type, Ru(NO₂)₂(RaaiR′)₂ (7–9). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the compounds, (7b–9b) with conc. HClO₄ nitro-nitrosyl derivatives, [Ru(NO₂)(NO)(OMeaaiR′)₂](ClO₄)₂ (10b–12b) are isolated. The solution structure and stereoretentive transformation in each step have been established from ¹H n.m.r. results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display one metal-centred oxidation and successive ligand-based reductions. The redox potentials of Ru(III)/Ru(II) (E_1/2^M) of (10b–12b) are anodically shifted by ∼ ∼0.2 V as compared to those of dinitro precursors, (7b–9b). The ν(NO) >1900 cm⁻¹ strongly suggests the presence of linear Ru–NO bonding. The electrophilic behaviour of metal bound nitrosyl has been proved in one case (12b) by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group, and the heteroleptic tris chelates thus formed have been characterised.     

Comparative determination of uranium in rock phosphates and columbite by ICP-OES,alpha &; gamma spectrometry

During this work selective separation of uranium from rock phosphate and columbite mineral was done before its quantitative estimation by using Inductively Coupled Plasma Optical Emission Spectrometery (ICP-OES). Uranium from the rock phosphate and columubite was extracted by sodium peroxide fusion followed by leaching in 2 M HNO₃. To avoid spectral interference in the estimation of uranium by ICP-OES, the selective separation of uranium from the leachate was carried out by using two different extractants, 30% Tributyl Phophates (TBP) in CCl₄ and a equi-volume mixture of Di(2-ethylhexyl) phosphoric acid (D2EHPA) & TBP in petrofin. Uranium was stripped from the organic phase by using 1 M ammonium carbonate solution. Determination of uranium by ICP-OES was done after dissolving the residue left after evaporation of ammonium carbonate solution in 4% HNO₃. The concentration of the uranium observed in the rock phosphates samples was 40–200 μg g⁻¹ whereas in columbite samples the concentration range was 100–600 μg g⁻¹. Uranium concentration evaluated by ICP-OES was complimented by gamma & alpha spectrometry. Concentration of uranium evaluated by gamma spectrometry in case of rock phosphate and coulmbite was in close agreement with the uranium content obtained by ICP-OES. Uranium determination by alpha spectrometry showed only minor deviation (1–2%) from the results obtained by ICP-OES in case of rock phosphates whereas in case of coulmbites results are off by 20–30%.     

Electrical conductivity studies in the system Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript>-Li<Subscript>1.33</Subscript>Ti<Subscript>1.67</Subscript>O<Subscript>4</Subscript>

Electrical conductivity in the monoclinic Li₂TiO₃, cubic Li_1.33Ti_1.67O₄, and in their mixture has been studied by impedance spectroscopy in the temperature range 20–730 °C. Li₂TiO₃ shows low lithium ion conductivity, σ₃₀₀≈10^–6 S/cm at 300 °C, whereas Li_1.33Ti_1.67O₄ has 3×10^–8 at 20 °C and 3×10^–4 S/cm at 300 °C. Structural properties are used to discuss the observed conductivity features. The conductivity dependences on temperature in the coordinates of 1000/T versus log_e(σT) are not linear, as the conductivity mechanism changes. Extrinsic and intrinsic conductivity regions are observed. The change in the conductivity mechanism in Li₂TiO₃ at around 500–600 °C is observed and considered as an effect of the first-order phase transition, not reported before. Formation of solid solutions of Li_{2– x} Ti_{1+ x} O₃ above 900 °C significantly increases the conductivity. Irradiation by high-energy (5 MeV) electrons causes defects and the conductivity in Li₂TiO₃ increases exponentially. A dose of 144 MGy yields an increase in conductivity of about 100 times at room temperature. Electronic Publication     

Effect of Er<Subscript>2</Subscript>O<Subscript>3</Subscript> on thermal stability of oxyfluoride glass

Glasses have been synthesized in the system SiO₂–Al₂O₃–Na₂O–AlF₃–LaF₃–Er₂O₃. A base glass (in mol% 67SiO₂–9Al₂O₃–20Na₂O–Al₂F₆–3La₂F₆) was modified by 0.5, 0.75, 1, 1.25, 1.5, 2 and 5 mol% Er₂O₃, respectively. Glasses were prepared by conventional fusion method from 20 g batches. The glass transition temperature (T _g), the jump-like changes of the specific heat (ΔC _p) accompanying the glass transition and the enthalpy of crystallization (ΔH) were calculated. DTA measurements clearly reveal that the increase of the Er₂O₃ content in the glass changes the effects of crystallization and diminishes the thermal stability of the glassy network. In the same time the changes in the transition temperature are observed. The formation of NaLaF₄ and Na_1.45La_9.31(SiO₄)₆(F_0.9O_1.1) as a main phase was confirmed. The diminishing of the thermal stability was connected with erbium which incorporated into Na_1.45La_9.31(SiO₄)₆(F_0.9O_1.1) structure.     

Kinetics of formation of barium tungstate in equimolar powder mixture of BaCO<Subscript>3</Subscript> and WO<Subscript>3</Subscript>

The formation of Barium monotungstate (BaWO₄) particles in equimolar powder mixtures of BaCO₃ and WO₃ was examined under isothermal and non-isothermal conditions upon heating in air at 25–1200 °C, using thermogravimetry. Concurrence of the observed mass loss (due to the release of CO₂) to the occurrence of the formation reaction was evidenced. Accordingly, the extent of reaction (x) was determined as a function of time (t) or temperature (T). The x–t and x–T data thus obtained were processed using well established mathematical apparatus and methods, in order to characterize nature of reaction rate-determining step, and derive isothermal and non-isothermal kinetic parameters. Moreover, the reaction mixture quenched at various temperatures (600–1,000 °C) in the reaction course was analyzed by various spectroscopic and microscopic techniques, for material characterization. The results obtained indicated that the reaction rate may be controlled by unidirectional diffusion of WO₃ species across the product layer (BaWO₄), which was implied to form on the barium carbonate particles. The isothermally determined activation energy (118–125 kJ/mol) was found to be more credible than that (245 kJ/mol) determined non-isothermally.     

CCl<Subscript>4</Subscript> Decomposition in RF Thermal Plasma in Inert and Oxidative Environments

The decomposition of carbon tetrachloride was investigated in an RF inductively coupled thermal plasma reactor in inert CCl₄–Ar and in oxidative CCl₄–O₂–Ar systems, respectively. The exhaust gases were analyzed by gas chromatography-mass spectrometry. The kinetics of CCl₄ decomposition at the experimental conditions was modeled in the temperature range of 300–7,000 K. The simulations predicted 67.0 and 97.9% net conversions of CCl₄ for CCl₄–Ar and for CCl₄–O₂–Ar, respectively. These values are close to the experimentally determined values of 60.6 and 92.5%. We concluded that in RF thermal plasma much less CCl₄ reconstructed in oxidative environment than in an oxygen-free mixture.     

Synthesis of ammonia from natural gas at atmospheric pressure with doped ceria–Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>–K<Subscript>3</Subscript>PO<Subscript>4</Subscript> composite electrolyte and its proton conductivity at intermediate temperature

A new type of oxide–salt composite electrolyte, yttrium doped ceria YDC–Ca₃(PO₄)₂–K₃PO₄, was developed and demonstrated for its promising use for ammonia synthesis. Using this composite electrolyte, ammonia was synthesized from nitrogen and natural gas at atmospheric pressure in the solid-state proton conducting cell reactor, and the optimal condition for ammonia production was determined . The evolved rate of ammonia is up to 6.95×10⁻⁹ mol s⁻¹ cm⁻².     

Nickel-copper-chromium catalyst for selective methane oxidation to synthesis gas at short residence times

Data on the selective oxidation of methane to synthesis gas on a 9% NiCuCr/2% Ce/(ϑ + α)-Al₂O₃ catalyst in dilute mixtures with Ar at short residence times (2–3 ms) are presented. The composition, structure, morphology, and adsorption properties of the catalyst with respect to oxygen and hydrogen before and after reaction were studied using XRD, BET, electron microscopy with electron microdiffraction, TPR, TPO, and TPD of oxygen and hydrogen. The following optimum conditions for the preparation and pretreatment of the catalyst for selective methane reduction were found: the incipient wetness impregnation of a support with aqueous nitrate solutions; drying; and heating in air at 873 and then at 1173 K (for 1 h at either temperature) followed by reduction with an H₂-Ar mixture at 1173 K for 1 h. At a residence time of 2–3 ms (space velocity to 1.5 × 10⁶ h⁻¹) and 1073–1173 K, the resulting catalyst afforded an 80–100% CH₄ conversion in mixtures with O₂ (CH₄/O₂ = 2: 1) diluted with argon (97.2–98.0%) to synthesis gas with H₂/CO = 2: 1. The selectivity of CO and H₂ formation was 99.6–100 and 99–100%, respectively; CO₂ was almost absent from the reaction products. The catalyst activity did not decrease for 56 h; carbon deposition was not observed. A possible mechanism of the direct oxidation of CH₄ to synthesis gas is considered.     

A kinetic study of the thermal degradation of 3-methylaminopropylamine inside AlPO<Subscript>4</Subscript>-21

Kinetics of the thermal decomposition of 3-methylaminopropylamine which was used as a structure-directing agent in the synthesis of AlPO₄-21 has been studied under isothermal and non-isothermal conditions. The decomposition is a single-step reaction occurring in the 573–663 K range. It is a phase-boundary-controlled process, described by the ‘F2/3, R3’ kinetic model. The activation energy values obtained under the non-isothermal and isothermal conditions lie in the 173–151 kJ mol^–1 range.     

Synthesis,structure, and properties of <Emphasis Type="Italic">N</Emphasis>-(nitramino)phthalimide

N-(Nitramino)phthalimide R₂N-NHNO₂ (R₂NH is phthalimide) was synthesized by nitration of N-aminophthalimide with nitronium tetrafluoroborate. The structure of this compound was established by X-ray diffraction and confirmed by ¹H, ¹³C, and ¹⁴N NMR spectroscopy. The methylation of this compound with diazomethane affords a mixture of N-methyl (R₂N-NMeNO₂) and O-methyl (R₂N-N=N(O)OMe) isomers. The latter compound contains the previously unknown high-nitrogen-oxygen fragment. The thermal decomposition of N-(nitramino)phthalimide in vacuo at 80–100 °C gives 2H-3,1-benzoxazine-2,4(1H)-dione (isatoic anhydride) as the major product. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 625–630, March, 2008.     

Oxygen- versus carbon-coordination of the alpha-stabilized phosphorus ylide Ph<Subscript>3</Subscript>P=C(H)R in palladacycles bearing secondary amines

The ortho-metalated complex [Pd(x){κ ² (C,N)-[C₆H₄CH₂NRR′ (Y)}] (2a–4a and 2b–3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc)₂ and secondary benzylamine [a, EtNHCH₂Ph; b, t-BuNHCH₂Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){κ ² (C,N)-[C₆H₄CH₂NRR′ (Y)}] (2a–4a and 2b–3b) with a stoichiometric amount of Ph₃P=C(H)COC₆H₄-4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C₆H₄C=CHPPh₃){κ ² (C,N)-[C₆H₄CH₂NRR′(Y)}] (5a–9a, 4b–6b, and 4b′–6b′), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an “end-on carbonyl”. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a–9a, 4b–6b, and 4b′–6b′) were characterized by elemental analysis as well as various spectroscopic techniques.     

Thermochemistry of Bu<Subscript>4</Subscript>NBr solutions in binary solvents containing formamide

The heats of solution of tetrabutylammonium bromide have been measured in mixtures of formamide (FA) with methanol (MeOH) and ethylene glycol (EG) at 313.15 K by calorimetric method. The standard enthalpies of solution in binary mixtures have been extrapolated to infinite dilution by Redlich–Rosenfeld–Meyer type equation using the literary data at 298.15 K and the present paper data at 313.15 K. The Debye–Hückel limiting law slope A _H required for calculation of the ∆_sol H ⁰ value has been obtained with application the new additive scheme of determination of the physic-chemical characteristics of binaries. The scheme is tested on the example of Bu₄NBr solutions in FA–MeOH mixture at 298.15 K. Its application yields the ∆_sol H ⁰ value very closed on the ones determined with the real (non-additive) characteristics of binaries. The standard enthalpies of solution extrapolated by Redlich–Rosenfeld–Meyer type equation are in a good agreement with the ones computed in terms of the Debye–Hückel theory in the second approximation. The heat capacities characteristics of Bu₄NBr have been calculated in H₂O–FA, MeOH–FA and EG–FA mixtures using the literary and present data. The sequence of solvents H₂O > FA > EG > MeOH located on their ability to solvophobic solvation found by us earlier for enthalpic characteristics is confirmed by the ∆C _p ⁰ values. The comparison of thermochemical characteristics of Bu₄NBr solutions in aqueous and non-aqueous mixtures containing FA has been carried out. The own structure of water remains in the region of small additions of formamide to co-solvents. It considerably differs the H₂O–FA mixture from the investigated non-aqueous systems.     

Determination of Cd, Co, Cr, Cu, Fe, Ni and Pb in Milk, Cheese and Chocolate

 Combined analytical procedures consisting of wet digestion step followed by instrumental determination – differential pulse cathodic stripping voltammetry (DPCSV) or electrothermal atomic absorption spectrometry (ETAAS) – as well as a direct analysis method – slurry sampling ETAAS – for the determination of Cd, Co, Cr, Cu, Fe, Ni and Pb in milk, cheese and chocolate are described and compared. Wet digestion using a mixture of HNO₃-HClO₄-H₂O₂ is proposed for complete matrix decomposition prior to trace analyte determinati on by DPCSV or ETAAS. A mixture of HNO₃-H₂O₂ is used for slurry preparation. Optimal instrumental parameters for trace analyte measurements are presented. The reliability of the procedures has been verified by analyzing standard reference materials. Results obtained are in good agreement with the certified values and the relative standard deviations (for these results) are in the range 5–10% for wet digestion DPCSV or ETAAS and 3–9% for slurry sampling ETAAS in the range of 2 μgċg⁻¹ (Cd) to 12 μgċg⁻¹ (Fe). Received August 24, 1999. Revision January 20, 2000.