New Method of Synthesis of β-Haloalkyl Alkynyl Sulfides: Reaction of Alkynesulfenamides with Olefins in the Presence of Phosphoryl Halides

Reactions of alkynelsufenamides with olefins (such as cyclohexene, norbornene, 1-hexene, 1-octene, allylbenzene, and styrene) in the presence of phosphoryl halides (POCl₃, POBr₃) afforded 70–95% of β-halo-substituted alkyl alkynyl sulfides. The reactions with cyclohexene and norbornene are characterized by trans stereoselectivity. Alkynylsulfenylation of terminal alkyl- and benzylacetylenes occurs in a regioselective fashion with predominant formation of the corresponding anti-Markownikoff adducts, while the addition to styrene yields halogen-containing sulfides according to the Markownikoff rule.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005, pp. 977–982.Original Russian Text Copyright © 2005 by Beloglazkina, Belova, Dubinina, Garkusha, Buryak, Zyk.     

Improved Synthesis of Thiofluorescein

Thiofluorescein was synthesized in a preparative yield by successive demethylation of 3,3′-dimethoxydiphenyl sulfide to 3,3′-dihydroxydiphenyl sulfide and condensation of the latter with phthalic anhydride in H₂SO₄. The title compound was also obtained in a higher yield from 3,3′-dimethoxydiphenyl sulfide directly in a one-pot process combining the condensation in H₂SO₄ and demethylation in 2 Py · H₂SO₄.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 60–63.Original Russian Text Copyright © 2005 by Russkikh, Konstantinova, Berezhnaya, Gerasimova, Shelkovnikov.     

Complexation processes in KF-SbF<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system studied by calorimetric titration

Complexation in a KF-SbF₃-H₂O system is studied in a range of molar ratios of fluorides KF : SbF₃= (0.1–2) : 1 by calorimetric titration. The equilibrium formation constants of complexes KSb₂F₇, KSbF₄, and K₂SbF₅ (5.8×10⁵±800, 3.3×10⁴±500, and 1.9×10⁶± 950, respectively) and the changes in enthalpy (–31.75± 0.74, –28.15±0.44, and –25.5±0.64 J mol^–1, respectively) and entropy (4±7, –8±5, and –35±9 J mol^–1 K^–1, respectively) are determined. The thermodynamic stability of the antimony(III) fluoride complexes is found to increase on going from KSb₂F₇ to K₂SbF₅.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 3, 2005, pp. 168–171.Original Russian Text Copyright © 2005 by Kovaleva, Zemnukhova, Lebedeva, Fedorishcheva.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

New Catalytic Reactions in the Presence of Mo-V-Phosphoric Heteropoly Acid Solutions

The possibility of performing new catalytic reactions in the presence of solutions of H _x+3PMo_12−x . V_xO₄₀ Mo-V-phosphoric heteropoly acids was examined.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 5, 2005, pp. 772–778.Original Russian Text Copyright © 2005 by Zhizhina, Simonova, Russkikh, Matveev.     

Electrochemical Precipitation of Dispersed Ni-Ag Powders in Ammonia Electrolytes

The electrochemical precipitation of a dispersed Ni-Ag powder from aqueous systems [Ni(NH₃)₆]²⁺-[Ag(NH₃)₂]⁺-(NH₄)₂SO₄−NH₃ ⋂ H₂O was studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 4, 2005, pp. 563–565.Original Russian Text Copyright © 2005 by Kuntyi, Olenych.     

Behavior of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-ZrO<Subscript>2</Subscript> System at High Temperatures

The system Al₂O₃-ZrO₂ at temperatures of up to 2100°C was studied by differential thermal analysis.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 353–356.Original Russian Text Copyright © 2005 by Kamaev, Archugov, Mikhailov.     

Hydrothermal Synthesis of Magnesium Silicate Montmorillonite for Polymer-Clay Nanocomposites

Conditions of hydrothermal synthesis of magnesium silicate montmorillonite Mg₃Si₄O₁₀(OH)₂·nH₂O with a particle size of 50–100 nm are optimized, including the temperature, initial chemicals, reaction medium, and run duration.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1, 2005, pp. 28–35Original Russian Text Copyright © 2005 by Golubeva, Korytkova, Gusarov.     

Temperature dependence of the polarization resistance of the O<Subscript>2</Subscript>,Au/La<Subscript>0.88</Subscript>Sr<Subscript>0.12</Subscript>Ga<Subscript>0.82</Subscript>Mg<Subscript>0.18</Subscript>O<Subscript>2.85</Subscript> electrode system

The impedance of a porous gold electrode in contact with solid electrolyte La_0.88Sr_0.12Ga_0.82Mg_0.18O_2.85 and the effect of the manufacture conditions on its polarization resistance are studied at 600–800°C in air. The overall oxygen reaction rate on a gold electrode is described as the sum of two partial constituents, namely, the oxygen exchange at the gas/electrolyte interface at the gold/gas/electrolyte triple-phased boundary.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 190–197.Original Russian Text Copyright © 2005 by Shkerin, Sokolova, Khlupin, Beresnev.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Ionic Mobility, Phase Transitions, and Superionic Conduction in Solid Solutions (100 ? x)PbF2-xZrF4 and Crystals K2ZrF6, (NH4)2ZrF6, KSnZrF7, and M(NH4)6Zr4F23 (M = Li, Na)

Methods of (¹⁹F, ¹H) NMR and impedance spectroscopy are used to investigate the internal mobility and ionic conduction in solid solutions arising in the system PbF₂-ZrF₄ and polycrystals KSnZrF₇, Li(Na)(NH₄)₆Zr₄F₂₃, and M₂ZrF₆ (M = K, NH₄). Factors responsible for the form of ionic motions and their energetics at 170–550 K are considered. It is established that the phase transitions in these compounds are connected with the crystal transition to a superionic state and that the high ionic (superionic) conductivity of beta phases is due to the diffusion of fluoride ions, ammonium cations, and possibly alkali metal cations. The obtained data testify to a substantial role of chainlike aggregation of anionic groupings and a variableness of structural mechanisms of formation of such chains in fluorozirconates for the development of translational diffusion in these compounds.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 573–582.Original Russian Text Copyright © 2005 by Kavun, Uvarov, Slobodyuk, Goncharuk, Kotenkov, Tkachenko, Gerasimenko, Sergienko.     

Preparation of Titanium Phosphate Sorbents from Products of Processing Sphene Concentrate and Properties of These Sorbents

Procedures for the preparation and granulation of sorbents based on TiO(HPO₄)·nH₂O from the products of processing of sphene concentrate were developed. The sorption and hydrodynamic characteristics of the sorbents were determined.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1, 2005, pp. 66–72.Original Russian Text Copyright © 2005 by Ivanenko, Lokshin, Vladimirova, Avsaragov.     

Interaction of Cl<Subscript>2</Subscript> and SO<Subscript>2</Subscript> with Finely Divided In<Subscript>2</Subscript>O<Subscript>3</Subscript>

The effect of O₂, Cl₂, and SO₂ on electrophysical and sorption properties of powdered In₂O₃ with a large specific area is studied at 23–200°C. The specimen is most sensitive to Cl₂ and SO₂ at near-room temperatures.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 529–536.Original Russian Text Copyright © 2005 by Vinokurova, Derlyukova.     

Impedance of the Ag|Nd0.95Sr0.05F2.95 Crystal|Ag System

Electrochemical studies of the Ag|Nd_0.95Sr_0.05F_2.95 crystal|Ag system at 94 to 1072 K are carried out using impedance measurements over the 10⁻¹ to 10⁷ Hz frequency range. Contributions of conduction and bulk and electrode polarization are distinguished in the impedance spectra of the Ag| Nd_0.95Sr_0.05F_2.95|Ag cell. Anionic conductivity of the Nd_0.95Sr_0.05F_2.95 crystal varies from 3 × 10⁻¹³ to 0.4 S/cm. The mechanism of anionic conduction and models for the electrode and bulk polarization are discussed.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 1005–1009.Original Russian Text Copyright © 2005 by Sorokin.     

Conductivity of Lanthanum-Strontium Cuprate LaSrCuO<Subscript>4−δ</Subscript> and Ionic Reversibility of Relevant Electrodes

A single-phase sample of the LaSrCuO_3.58 composition is prepared by solid-state synthesis at 1473 K in air. The conductivity of LaSrCuO_3.58 is measured by a four-probe method at direct current in the temperature range from 298 to 1173 K at oxygen partial pressures from 28 to 2.1 × 10⁴ Pa. Heating samples above ∼670 K is shown to result in a changeover of the conduction type from semiconducting (p-type) to metallic. Exchange currents at the LSCuO/YSZ interface are measured by impedance spectroscopy. The measurements are carried out in high-density symmetrical cells LSCuO|YSZ|LSCuO, fabricated by hot pressing of powders under a pressure of 3.5 × 10⁹ Pa at 773 K. Experimental exchange currents i ₀ (varying from 10⁻³ to 10⁻⁴ A/cm² in the temperature interval from 800 to 1173 K) are comparable with such of materials based of lanthanum-strontium manganite.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 516–522.Original Russian Text Copyright © 2005 by Mazo, Savvin, Mychka, Dobrovol’skii, Leonova.     

Azo derivative of 2-thenoyltrifluoroacetone as a reagent for the photometric determination of copper(II)

1-(2-Thenoyl)-4-trifluoro-2-[2-hydroxy-3-sulfo-5-nitrophenylazo]butadione-1,3 (H₂L) was synthesized from 2-thenoyltrifluoroacetone. The formation of a copper(II) complex of the synthesized reagent was studied in the presence and absence of 8-hydroxyquinoline (HR). Monoligand [Cu(HL)₂] and mixed-ligand [Cu(HL)₂HR] compounds were obtained at pH 4 and 3, respectively. The ratio of components in the monoligand and mixed-ligand compounds were 1 : 2 and 1 : 2 : 1, respectively. Beers law was obeyed in the ranges of copper concentrations from 0.20 to 2.56 and from 0.25 to 2.56 µg/mL, respectively. The dissociation constants of the reagent were .K₁ = 4.25µ0.01 and .K₂ = 8.20µ0.01 . The stability constants of [Cu(HL)₂] and [Cu(HL)₂HR] complexes were K₁ = 4.96µ0.03 and 4.92µ0.01, respectively. A procedure was developed for the photometric determination of copper(II) in rocks.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 2, 2005, pp. 157–161.Original Russian Text Copyright © 2005 by Alieva, Chyragov, Makhmudov.This revised version was published online in April 2005 with corrections to the author names and book review format.     

Chemistry of 2-hetarylbenzimidazoles. 10. Synthesis and properties of 2-(3′-furyl)-1-methyl-1H-benzimidazole

A study was carried out on the electrophilic substitution reactions such as chloromethylation, bromination, sulfonation, nitration, and acylation of 2-(3′-furyl)-1-methyl-1H-benzimidazole in acid media. All these reactions proceed at C₍₂₎ and C₍₅₎ of the furan ring. Quantum-chemical calculations of the three-dimensional structure of such heterocyclic systems are given. Communication 9, see ref. [1]. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1815–1820, December, 2005.     

Photoinduced Transformations in Low-Temperature Matrices Containing Radical Cations of Organotin Compounds

Charge transfer to matrix molecules was found to be the principal photochemical reaction of the radical cations Me₄Sn^+· and Me₆Sn ₂ ^+· . It was shown that the difference in the localization of positive charge in the ground state of these radical cations (at the Sn-C bond in Me₄Sn^+· and at the Sn-Sn bond in Me₆Sn ₂ ^+· ) did not affect the pathways of their photochemical reactions.__________Translated from Khimiya Vysokikh Energii, Vol. 39, No. 4, 2005, pp. 267–274.Original Russian Text Copyright © 2005 by Belokon’, Pergushov, Tyurin, Egorov, Mel’nikov.     

Kinetics of Low-Temperature Oxidative Chlorination of Benzene in Aqueous Acetic Acid

The kinetics of chlorination of benzene with a mixture of sodium peroxide with hydrochloric acid in aqueous acetic acid at 298 K was studied. The chlorination rate is the highest when the AcOH concentration in the binary solvent is 49.4-40.6 mol % and the ratio of the initial cocentrations of water and sodium peroxide, 18.5–20.2. The linear dependences of logk _app on the AcOH concentration and [H₂O]₀/[Na₂O₂]₀ ratio were obtained.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 792–794.Original Russian Text Copyright © 2005 by Rudakova, Erykalov.     

The Mechanism of Action of a Multicomponent Co-Mo-Bi-Fe-Sb-K-O Catalyst for the Partial Oxidation of Propylene to Acrolein: II. Changes in the Phase Composition of the Catalyst under Reaction Conditions

The structures of a complex multicomponent Co-Mo-Fe-Bi-K-Sb-O catalyst for the oxidation of propylene to acrolein and simpler catalysts from which some catalyst components were absent were studied by X-ray diffraction analysis. The phases of α-CoMoO₄, β-CoMoO₄, Fe₂(MoO₄)₃, Bi₂O₃ ⋅ MoO₃, Bi₂O₃ ⋅ 2MoO₃, Bi₂O₃ ⋅ 3MoO₃, oxidized molybdenum oxide, and reduced molybdenum oxide are the main components of the catalyst. Ternary compounds were not detected. Under catalytic reaction conditions, the relative amounts of the phases changed; this change suggests the occurrence of redox transformations with the participation of these phases, probably, at the interface.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 580–584.Original Russian Text Copyright © 2005 by Shashkin, Udalova, Shibanova, Krylov.     

A Diffusion-Kinetic Model for Radiation-Chemical Transformations of Oxalic Acid and Oxalate Ions in Aqueous Solutions

A diffusion-kinetic model for the radiation-chemical degradation of oxalic acid and oxalates in aqueous solutions was developed. The model adequately describes published data on the formation of H₂, H₂O₂, and CO₂ over wide ranges of acid concentrations and pH values.__________Translated from Khimiya Vysokikh Energii, Vol. 39, No. 4, 2005, pp. 250–254.Original Russian Text Copyright © 2005 by Gordeev, Ershov, Kosareva.     

Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XL. Nature of Salt Effects in Dehydrobromination of 3-Bromocyclohexene in γ-Butyrolactone. Role of Solvation Effects of Dipolar Aprotic Solvents

The influence of neutral salts on the rate of heterolysis of 3-bromocyclohexene at 31°C in γ-butyrolactone was studied by the verdazyl method; ν = k[C₆H₉Br], E1 mechanism. Additions of lithium picrate do not affect the reaction rate; those of LiClO₄ and Et₄NClO₄ increase it; and those of LiCl, Et₄NCl, and KNCS decelerate the reaction. The nature of salt and solvation effects in the heterolysis of 3-bromocyclohexene in γ-butyrolactone, MeCN, and PhNO₂ is discussed.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 937–944.Original Russian Text Copyright © 2005 by Ponomarev, Stambirskii, Dvorko.