bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kinetics of the Formation of MoO3−x at Elevated Temperatures from a Mixture of MoO3 and α-Al2O3
Authors: Kotera Yoshihide , Ueno Akifumi 
Published: July 2006

Abstract
The kinetics of the formation of MoO3−x from a mixture of MoO3 and α-Al2O3 was studied by means of high temperature X-ray diffraction. The species of MoO3−x formed in the temperature range 600–700 °C were identified as MoO2.88(Mo8O23),(MoO2.76(MoO17O47), and MoO2.75(Mo4O11). The activation energies of their formation were estimated to be 18.4 kcal/mol for Mo8O23, 23.0 kcal/mol for Mo17O47 and 29.2 kcal/mol for Mo4O11. Other types of species of MoO3−x observed above 800 °C were MoO2.89(Mo9O26) and MoO2. Little effect of water vapor, oxygen or nitrogen on the formation of the species was observed. No MoO3−x. was observed in the mixture of MoO3, with SiO2 or α-Fe2O3.
The Fluorination of Carbonyl Sulfide
Authors: Nagase Shunji , Baba Hajime , Kodaira Kazuo , Abe Takashi 
Published: July 2006

Abstract
The electrochemical fluorination of carbonyl sulfide has been carried out. Garbonyl fluoride and sulfur hexafluoride were obtained as the principal products. The influence of the operating conditions on the reaction has been examined. In addition, a method has been developed for the production of sulfur hexafluoride. This involves the passage of carbon monoxide and sulfur over a catalyst; the resultant gas formed is subsequently introduced into a current-carrying anhydrous hydrogen fluoride in an electrolytic cell. Sulfur hexafluoride was thus obtained in a good yield.
Trimethylenediamine Complexes. III. cis-trans Isomeric Pairs of Diazido- and Dicyano-bis(trimethylenediamine)cobalt(III) Complexes
Authors: Kawaguchi Hiroshi , Kawaguchi Shinichi 
Published: July 2006

Abstract
trans-Diazido- and dicyano-bis(trimethylenediamine)cobalt(III) complexes have been prepared by the ligand substitution reactions of trans-dichlorohis(trimethylenediamine)cobalt(III) complexes in methanol. The corresponding cis isomers were obtained by similar reactions in aqueous solutions. The structural assignment of these isomeric pairs was made on the basis of electronic, infrared and nuclear magnetic resonance spectra.
A New Catalyst for Ethylene Polymerization Containing Nickel Oxide
Authors: Maruya Ken-ichi , Ozaki Atsumu 
Published: July 2006

Abstract
A new catalyst for ethylene polymerization NiO–NiSO4, was found from a study of NiO–SiO2, and NiCl2 catalysts. The Ni–NiSO4 catalyst prepared from mixtures of formate and sulfate is much less active than NiO–NiSO4 prepared from mixtures of hydroxide and sulfate. Poisoning behavior of carbon monoxide and water is quite similar to NiO–SiO2 catalyst. An equimolar mixture of NiO–NiSO4 gives maximum activity. The active species is postulated to be hydroxy sulfate of nickel. The structure of the active site is discussed.
(1,3-Dithiolan-2-yl)trimethylammonium Iodide. An Electrophilic Dithiolanylating Reagent
Authors: Hiratani Kazuhisa , Nakai Takeshi , Okawara Makoto 
Published: July 2006

Abstract
The reactions of (1,3-dithiolan-2-yl)trimethylammonium iodide (5), readily obtained by methylation of 2-dimethylamino-1,3-dithiolane (2), with aromatic amines were studied. It was found that 5 served as an electrophilic 1,3-dithiolanylating reagent; the reactions with aniline, N-methylaniline, and benzylamine gave N-dithiolanylated products while those with N,N-dimethylaniline and indole yielded exclusively C-dithiolanylated products via aromatic substitutions. Furthermore, C-dithiolanylated compounds were hydrolyzed to aldehydes using HgO–BF3·OEt2. The present aldehyde synthesis has been compared with an alternative electrophilic formylation method the Vilsmeier reaction.
Reduction of gem-Bromofluorocyclopropanes with Organosilicon Hydrides
Authors: Ando Teiichi , Hosaka Hirokazu , Funasaka Wataru , Yamanaka Hiroki 
Published: July 2006

Abstract
7-Bromo-7-fluoronorcarane, 1-bromo-1-fluoro-2-phenylcyclopropane, and 7-bromo-7-fluoro-2-oxanorcarane were reduced with tri-n-butylsilane or di-n-butylsilane at 100–145 °C in the presence of a small amount of radical initiator, to afford the corresponding monofluorocyclopropanes. It has been found, by examining the stereochemistry of the reduction, that the extent of stereospecificity is dependent on the reaction temperature as well as on the kind of the silicon hydride used. Comparison of these results with those of the tri-n-butyltin hydride reduction shows that the reactivity of metal hydrides as a reducing agent of gem-dihalocyclopropanes is in the order Bu3SnH&gt;Bu2SiH2&gt;Bu3SiH. These observations are well explained by postulating that the α-fluorocyclopropyl radical has a pyramidal configuration and that the extent of stereospecificity is determined by the relative rates of its inversion of configuration and its hydrogen abstraction from the tin or silicon hydride. The reduction of 7,7-dibromonoracrane with tri-n-butylsilane or di-n-butylsilane gave a mixture of the two geometrical isomers of 7-bromonoracrane, whose composition (endo-Br/exo-Br\fallingdotseq3.0) was nearly identical irrespective of the reaction temperature and of the reactivity of silicon hydride.
Cycloaddition Reaction of Cycloheptatriene and Nitrosobenzene Derivatives
Authors: Itô Shô , Narita Sen-ichi , Endo Katsuya 
Published: July 2006

Abstract
Structures of the cycloaddition products obtained from cycloheptatriene and para-substituted nitrosobenzene have rigorously been established by NMDR experiments and by degradation of the representative member, the cycloheptatriene-nitrosobenzene adduct, to 3-anilinocycloheptanone. All the adducts were found to be of [6+2] type. The ionic mechanism has been proposed for the cycloaddition in order to account for the substitution effect on the benzene ring.
The Synthesis of 3-Methyl-5-(2-aminoalkyl)isoxazoles
Authors: Kashima Choji , Tsuda Yoshihiko 
Published: July 2006

Abstract
The reaction of 3,5-dimethylisoxazole with Scruff bases gave 3-methyl-5-(2-aminoalkyl)isoxazole derivatives in the presence of sodium amide in liquid ammonia. The N-alkylation on the anilino group of 3-methyl-5-(2-anilino-2-phenylethyl)isoxazole resulted in deamination, thus giving 3-methyl-5-styrylisoxazole. The reaction of 3,5-dimethylisoxazole with benzonitrile gave 3-methyl-5-(2-aminostyryl)isoxazole, which was then reduced to 3-methyl-5-(2-amino-2-phenylethyl)isoxazole.
Generalized Method for Calculating Löwdin Orbitals
Authors: Suzuki Kazuya , Maruyama Shinsaku , Araki Kunio 
Published: July 2006

Abstract
A generalized method for numerically calculating Löwdin orbitals is proposed, the method being an application of Frobenius’ theorem in algebra. Löwdin transformation matrix T=S−1⁄2 (S is overlap matrix) is calculated as T=US0−1⁄2 Ut, where S0 is a diagonal matrix whose diagonal elements are eigen values of S, U is a matrix whose column vectors are eigen vectors of S and Ut is the transposed matrix of U. It is proved that the eigen values of the overlap matrix of S are always positive for any choice of linearly independent atomic orbitals and that S−1⁄2, the inverse square-root of S, exists within the range of real numbers. This method is useful for computer calculation by applying Jacobi’s method.
The Selective Hydrogenation of α-Methylcinnamaldehydes Catalyzed by Cobalt Carbonyl in the Presence of Amines
Authors: Kogami Kunio , Kumanotani Ju 
Published: July 2006

Abstract
The selective hydrogenation of α-methylcinnamaldehydes to the hydrocinnamaldehydes, catalyzed by cobalt carbonyl and a limited amount of amines, has been investigated. The addition of such amines as diisopropylamine, diethanolamine, tributylamine, triethylamine, and pyridine showed a remarkable selectivity and gave the desired α-methylhydrocinnamaldehydes in 96.4–91.5% theoretical yields. Especially, diisopropylamine gave the best selectivity, in it the yields of p-t-butyl-α-methylhydrocinnamaldehyde and cyclamenaldehyde amounted to 96%. The optimum amount was found to be 1.0–1.3 equivalents of cobalt carbonyl.
Group Interactions in Polyelectrolytes. VII. Amination Kinetics of Chloromethylated Polystyrene with Butylamine Isomers
Authors: Kawabe Hiroshi , Yanagita Masaya 
Published: July 2006

Abstract
The amination of chloromethylated polystyrene (CMPS) and benzyl chloride with butylamine isomers and diethylamine was investigated kinetically in dioxane, methyl ethyl ketone (MEK), and N,N-dimethylformamide (DMF). Although the amination of i- and s-butylamine conformed to the ordinary second-order kinetics in all the solvents, deceleration was observed during the course of the amination of CMPS with n-butylamine in MEK as well as in dioxane, with t-butylamine in DMF, and with diethylamine in both dioxane and DMF. The intrinsic rate constants of the amination of CMPS were generally almost the same as those of benzyl chloride. The magnitudes of the rate constants in each solvent were in this order; n-butyl&gt;i-butyl&gt;s-butyl&gt;t-butyl; it was in the order of DMF&gt;&gt;MEK≈dioxane with all the amines investigated. These results were interpreted in terms of both the structures of the amines and the interaction between the amine and the solvent molecules.
An Investigation of the Gas-Solid Interface Reaction
Authors: Katsumoto Masayuki , Fueki Kazuo , Mukaibo Takashi 
Published: July 2006

Abstract
The isotopic exchange between H2S and D2 on molybdenum disulfide and manganese sulfide has been studied kinetically between 420° and 500 °C. The reaction proceeded via these steps:
& H_2S+D_2=D_2S+H_2
& H_2+D_2=2HD
From the analysis of the kinetic data, the rate constant of the sulfurization of both metal sulfides by “hydrogen sulfide,” ki, and that of their reduction by “hydrogen,” ki′, were calculated. The dependence of these rate constants on the sulfur activity was determined. A possible mechanism of the reaction at the surface of the sulfides is discussed in this paper.
Raman Spectra and Internal Rotation of Ethyl Methyl Ether
Authors: Kitagawa Teizo , Kusaki Kazuo , Miyazawa Tatsuo 
Published: July 2006

Abstract
The Raman spectra of ethyl methyl ether in the liquid state were measured at various temperatures from 298 K to 195 K. The energy difference between the gauche and trans isomers in the liquid state was found to be 1.1 kcal/mol. This value is appreciably higher than the value 0.77 kcal/mol for n-butane. The tendency of assuming the trans form is higher for the CH2–O bond than for the CH2–CH2 bond. The infrared intensity of the band at 465 cm−1 (gas) is largely due to the gauche isomer but the Raman intensity of the line at 471 cm−1 (liquid) is largely due to the trans isomer.
On the Decomposition of C6H5CO+ Ions Produced from Several Alkyl Phenyl Ketones by Electron Impact
Authors: Tajima Susumu , Wasada Nobuhide , Tsuchiya Toshikazu 
Published: July 2006

Abstract
The decomposition of C6H5CO+ ions produced by electron impact from seven alkyl phenyl ketones, C6H5COR (R=H, CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, n-C5H11), has been studied. By determining the heats of formation, the C6H5CO+ ions produced from the different precursors in the vicinity of the threshold are shown to have the same structure, and it is also shown that there is a linear relationship between the heat of formation of the activated complex for the reaction C6H5CO+→C6H5++CO and the vibrational degrees of freedom of the neutral fragment, R.
Effects of Inorganic Salts on the Dissociation of a Complex of β-Cyclodextrin with an Azo Dye in an Aqueous Solution
Authors: Mochida Kazuo , Kagita Akio , Matsui Yoshihisa , Date Yoshio 
Published: July 2006

Abstract
The apparent dissociation constant (Kapp) of a complex between β-cyclodextrin and an azo dye, sodium p-(4-hydroxy-1-naphthylazo)benzenesulfonate, was determined by spectrophotometry in a phosphate buffer solution (pH 5.91) in the absence and in the presence of various inorganic salts at 25 °C. The cyclodextrin and the azo dye formed a 1 : 1 complex with the Kapp value of 2.44×10−3 M in a 0.1 M phosphate buffer. Kapp decreased with an increase in the concentration of the phosphate buffer and with the addition of some inorganic salts, such as Li2SO4, Na2SO4, K2SO4, LiIO3, NaIO3, KIO3, and KF. These results were explained mainly in terms of the decrease in the activity of water, which takes part in the dissociation reaction of the inclusion complex, with an increase in the concentration of the inorganic salts. On the other hand, Kapp increased with the addition of such salts as KCl, KBr, KI, KNO3, KSCN, and KClO4. These results were attributed mainly to the formation of the inclusion complexes of the cyclodextrin with the anions of these salts, competing with the azo dye for the cyclodextrin-binding site.
Electron-diffraction Investigation of the Molecular Structure of Tetramethyltin
Authors: Nagashima Makoto , Fujii Hideji , Kimura Masao 
Published: July 2006

Abstract
The structure parameters of tetramethyltin have been determined by gas-phase electron diffraction to be as follows: rg(Sn–C)=2.1436±0.0030 Å, rg(Sn···H)=2.7642±0.0125 Å, rg(C–H)=1.1179±0.0090 Å, l(Sn–C)=0.0496±0.0098 Å, and l(Sn···H)=0.1532±0.0132 Å. The experimental molecular intensity has been well reproduced by the molecular model in which the methyl groups are rotating freely, or nearly freely. The scattering factors, based upon the relativistic Hartree-Fock-Slater or the Hartree-Fock atomic potential, have given a theoretical background in better agreement with the experimental one and have led to a more reasonable Sn–C mean amplitude than did the scattering factors based upon the Thomas-Fermi-Dirac or the Thomas-Fermi atomic potential.
Self-diffusion of a Cation through Cation Exchange Membrane and Membrane Permeability
Authors: Kaibara Kozue , Saito Keiji , Kimizuka Hideo 
Published: July 2006

Abstract
The self-diffusion coefficient of an ion and the membrane permeability were studied with a system consisting of two identical electrolyte solutions separated by a cation exchange membrane. The membrane permeability to cation was estimated from the membrane conductance data. The result indicated that the membrane permeability increased with a decrease in electrolyte concentration. The self-diffusion coefficients and the concentrations of Na+, Cs+, and Ca2+ in the membrane were also measured by the radiotracer method. At concentrations less than 0.1 M, the self-diffusion coefficients more or less increased with increasing concentrations, while the concentrations within membrane remained almost constant. The membrane permeability to ion estimated from the conductance data was in excellent agreement with that calculated by the relation in which the membrane permeability is given as the self-diffusion coefficient times the partition coefficient divided by the membrane thickness.
Ionic Equilibria in Mixed Solvents. X. Hydrolysis of Nickel(II) Ion in Dioxane-Water Mixtures
Authors: Kawai Takayoshi , Otsuka Haruko , Ohtaki Hitoshi 
Published: July 2006

Abstract
The hydrolytic reactions of nickel(II) ion were studied at 25 °C in water and dioxane-water mixtures containing 3 M (Li)ClO4 as an ionic medium. Emf measurements were carried out in the range of the total nickel(II) ion concentration of 0.02469–0.7891 M in water, 0.02488–0.7996 M in a 0.1 mole fraction (35.21% w/w) dioxane-water mixture and 0.05170–0.9016 M in a 0.2 mole fraction (55.01% w/w) dioxane-water mixture, respectively. Some supplementary measurements were performed in a 0.5 mole fraction (83.02% w/w) dioxane-water mixture. Only the Ni4(OH)44+ complex was found in all solvent systems and its formation constant in log*β44 was −27.32±0.08 (in water), −27.11±0.08 (in a 0.1 mole fraction dioxane-water mixture), and −27.04±0.05 (in a 0.2 mole fraction dioxane-water mixture). In order to test the relative change of the formation consatnt of the Ni4(OH)44+ complex over the whole solvent composition examined, the variation of the formation constant was measured with the continual change of solvent composition at constant Z. Approximate values of the solubility products of Ni(OH)2 and NiOHClO4 precipitates were estimated from maximum values of Z.
The Separation of Silver, Bismuth, Cadmium, and Zinc as Their Trioctylamine Complexes by Extraction Chromatography
Authors: Honjo Takaharu , Ushijima Shigeru , Kiba Toshiyasu 
Published: July 2006

Abstract
The behavior of milligram amounts of silver, bismuth, cadmium, and zinc in liquid-liquid extraction has been studied with 20% trioctylamine (TOA) in carbon tetrachloride. The results have also been applied to the separation of the four metals as their TOA complexes by extraction chromatography. After passing a sample solution of 2 M HCl through a column (φ1cm×1 30 cm) consisting of a stationary phase of TOA–CCl4 on Kel-F, the metal ions were retained and then eluted with 5.5 M HCl at the rate of 0.5–1 ml/min at 20±1 °C. Silver was found in 90–180 ml of the effluent; Bi was flowed down in 200–500 ml of the same effluent. The cadmium and Zn were held so firmly on the column that they could not be removed under the above conditions. Therefore, water was passed through to release these metals. Zinc was first flowed down with 0–50 ml, and then Cd, with 200–500 ml of water. When 5M HNO3 was used as the eluting solution instead of water, the Cd was immediately removed from the column. The percentage recovery of these metals in the extraction chromatography was estimated as 101% (Ag), 99% (Bi), 97% (Cd), and 94% (Zn) respectively. The distribution ratios of these metals, as obtained by the extraction chromatography of the TOA–carbon tetrachloride (Kel-F)–HCl system, were in quite good agreement with those obtained by the batch extraction.
The Analytical Application of Sulfur Analogues of β-Diketones. V. Some Aspects of the Extraction Behavior of STTA (1,1,1-Trifluoro-4-(2-thienyl)-4-mercapto-3-buten-2-one) Complexes and Their Adducts with TOPO
Authors: Honjo Takaharu , Yashima Satoshi , Kiba Toshiyasu 
Published: July 2006

Abstract
The solvent extraction of trace amounts of various metal ions with STTA (1,1,1-trifluoro-4-(2-thienyl)-4-mercapto-3-buten-2-one) in the presence or in the absence of TOPO (tri-n-octylphosphine oxide) has been investigated. The results are as follows: (a) The apparent extraction constant of each metal–STTA chelate in cyclohexane, logK, increases, and their pH 1⁄2 values decrease, in the order of: Cd(II)-In(III)-Zn(II)-Fe(III)-Ni(II)-Ag(I)-Bi(III)-Co(II)-Pb(II)-Cu(II)-Hg(II). This order was found to hold also in the back-extraction, except for cobalt, which was not back-extracted even with 1–12 M HCl. The other metals, Au(III), and Pd(II), could also be extracted as their STTA chelates. (b) The kind of the solvent has an effect to the lowest pH value where the metal STTA chelates begin to be extracted; the lowest pH is shifted to a higher value in the order of: C6H12, CCl4, MIBK, C6H6 and CHCl3. (c) The distribution coefficient, Pr, and the enol dissociation constant, Ka, of STTA were logPr=2.99 (10−3 M STTA in cyclohexane-0.1 M NaClO4-pH 1.0) and logKa=−4.38 (10−4 M STTA in 0.12 M HCl, 0.1 M CH3COOH (pH 4.5) and 0.1 M NaOH-C2H5OH (1/5, v/v) solution) at 20 °C. (d) The extraction equilibrium of Zn seemed to be rapid, that of Ni showed its rate-determining step to be the formation of Ni(STTA)+, and that of Co seemed to be accompanied by a transformation of Co(STTA)2 to Co(STTA)3. (e) In the metal–STTA(0.001 M)-TOPO(0.01 M)–cyclohexane system, the |ΔpH1⁄2| was found to be 0.45 for Ni, 1.95 for Zn, and 0.25 for Co. The Co–STTA–TOPO chelate could be back-extracted to some degree with 1 M HCl. The extracted species were ascertained to be Zn(STTA)2, Zn(STTA)2TOPO, Ni(STTA)2, Co(STTA)2, Co(STTA)3, and Co(STTA)2TOPO. The stability constant of Zn(STTA)2 TOPO was found to be 6.05.
Polarographic Behavior of 9-Nitroanthracene and 9,10-Dinitroanthracene in Dimethylformamide
Authors: Kitagawa Toyokichi , Ichimura Akio 
Published: July 2006

Abstract
The polarographic behavior of 9-nitroanthracene and 9,10-dinitroanthracene has been studied in dimethylformamide. 9-Nitroanthracene shows consecutive two one-electron diffusion-controlled reduction waves followed by fast chemical reactions. 9,10-Dinitroanthracene, however, shows only one reversible two-electron diffusion-controlled wave. The effect of the supporting electrolyte cation on these reduction waves was also investigated. In alkali metal or alkaline earth metal perchlorate as a supporting electrolyte, the half-wave potentials shift to the anodic side. The relationship between the half-wave potential and the ionic potential of the cation was discussed.
Group Interactions in Polyelectrolytes. VI. Animation Kinetics of Chloromethylated Polystyrene in N,N-Dimethylformamide and Dimethyl Sulfoxide
Authors: Kawabe Hiroshi , Yanagita Masaya 
Published: July 2006

Abstract
Although the apparent second-order rate constant of the amination of chloromethylated polystyrene with n-butylamine or with 2-aminobutanol decreased or increased, respectively, during the course of the amination in dioxane, as has been reported previously, both animations as well as the aminations of benzyl chloride have been found to conform to the ordinary second-order kinetics in DMF and DMSO. The viscometric measurements have indicated that the viscosity of the reaction mixture decreased during the amination with n-butylamine and increased slightly during the amination with 2-aminobutanol, but no relation between the kinetic behavior and the viscometric changes in the reaction mixtures could be found. The magnitude of the rate constants was comparable to that of the amination of benzyl chloride, and it increased with an increase in the dielectric constant of the solvents in this order: dioxane&lt;&lt;DMF&lt;DMSO. The effects of the solvents on both the kinetic behavior in the aminations of the polymer and the magnitude of the rate constants have been discussed in terms of the interactions between the solvent and the solute molecules.
Oxidation by Transition Metal Complexes. VI. Oxidation of Cyclohexenes Catalyzed by Rhodium Complexes
Authors: Kaneda Kiyotomi , Itoh Takashi , Fujiwara Yuzo , Teranishi Shiichiro 
Published: July 2006

Abstract
Rhodium complexes can cause the catalytic oxidation of cyclohexene to give ketone, alcohol, and epoxide. The product distribution is dissimilar to that of the metal-catalyzed decomposition of cyclohexene hydroperoxide(V). Ketone and alcohol are derived from the decomposition of the intermediate hydroperoxide (V) but epoxide is not formed by the oxygen transfer reaction from V. Oxidation of methylcyclohexenes was also studied and discussed in relation to the effect of methyl substituent.
An Addition Reaction of Diethylamine to Styrene Catalyzed by Lithium Diethylamide
Authors: Narita Tadashi , Yamaguchi Teruo , Tsuruta Teiji 
Published: July 2006

Abstract
An addition reaction of diethylamine to styrene catalyzed by lithium diethylamide was found to proceed stoichiometrically to produce 1-diethylamino-2-phenylethane. The rate of the reaction was expressed by the equations: υ=k[Styrene][Et2NLi]1.3 and υ=k[Styrene][Et2NLi], the ratios of [Et2NH]0 to [Et2NLi]0 being 3.0 and 10 respectivly. On the basis of the kinetic studies, the mechanism of the addition reaction was elucidated. The nucleophilic character of this reaction was clearly demonstrated by the σ–ρ Hammett plot. The second-order rate constant for the addition reaction of styrene was found to be of the same order of magnitude as that of butadiene. The presence of butadiene in the reaction system showed no effect on the reactivity of styrene.