bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Dehalogenation of Haloalkanes on SiO2-supported Metals
Authors: Anju Yasuhide , Mochida Isao , Yamamoto Hiroko , Kato Akio , Seiyama Tetsuro 
Published: July 2006

Abstract
The dehalogenations of haloethanes and halopropanes over metals (Cu, Ag, Au, Fe, Co, Ni, Pd, and Pt) supported by silica gel were studied by means of the microcatalytic pulse technique in order to elucidate the mechanism of dehalogenation. The dechlorination reactivities of cis- and trans-1,2-dichloroethylenes and the dechlorination products from dl- and meso-2,3-dichlorobutanes were observed from the viewpoint of stereoselectivity. The order of catalytic activities among the metals for the dehalogenation of haloethanes was: Pt&gt;Cu≈Ni&gt;Ag≈Co≈Pd&gt;Fe≈Au. Dehalogenation proceeded exclusively in the 1,2-dihaloethanes. However, dehydorhalogenation took place in the 1,2-dihalopropanes to an appreciable extent when the product distributions of dehydrohalogenation were similar to those on solid acids. Both 1,1,2-trichloroethane and 1,2-dichloropropane were more reactive than 1,2-dichloroethane. 1,2-dichloroethylenes from 1,1,2,2-tetrachloroethane and 2-butenes from dl- and meso-2,3-dichlorobutanes were nearly in an equilibrium ratio of cis/trans forms. From a comparison of these results with those of the dehydrohalogenation on solid acids, it is concluded that the dehalogenation of haloalkanes on metals proceeds through a radical-step-by-step mechanism.
Studies on Microcapsules. XIII. Effect of Span 85 and pH of Aqueous Phase on the Formation of Polyamide Microcapsules
Authors: Ogawa Tomoharu , Takamura Kouichi , Koishi Masumi , Kondo Tamotsu 
Published: July 2006

Abstract
The effects of the pH of aqueous phase containing piperazine and the concentration of Span 85, a nonionic surfactant with chemical description of sorbitan trioleate (Atlas Power Co., U.S.A) on the formation of polyphthalamide microcapsules were systematically investigated by the interfacial polycondensation method in the organic phase containing p-phthaloyl dichloride. The presence of Span 85 facilitated the formation of microcapsules by increasing the transfer of undissociated diamine molecules into the organic phase in the pH range 9.0–12.0, outside of which Span 85 did not significantly contribute to the formation of microcapsules. An increase in the pH in this range gives rise to an increase in the number of undissociated diamine molecules, promoting the transfer of diamine.
Behavior of Positive Hole in a γ-Irradiated 3-Methylpentane Glass at 77°K
Authors: Irie Masahiro , Yoshida Hiroshi , Hayashi Koichiro , Okamura Seizo 
Published: July 2006

Abstract
In order to elucidate the behavior of a positive hole in irradiated alkane glasses, the effect of solutes having ionization potential lower than that of a glass matrix molecule upon the decay of a trapped electron was examined in a 3-methylpentane glass at 77°K by means of electron spin resonance. The decay was found to be explained in terms of the superposition of two exponentially decaying processes, as in the absence of a solute. Although the fast process was not affected by a solute, the slow process was further slowed by the addition of a solute. The effect of a solute is described by the empirical relation, k⁄k0=1⁄(1+fN), where k and k0 are the rate constants of the slow decay in the presence and in the absence of a solute, respectively. N is the mole fraction of a solute. The observed values of the slowing-down efficiency, f, increase in parallel with the decreasing values of ionization potential of solutes: 2-methyltetrahydrofuran, diethylether, methylvinylether, 2-methylpentene-1 and n-butylvinylether. The results are interpreted in terms of trapping of a positive hole by a solute molecule and positive hole tunneling from a hole trap to a trapped electron.
The Structural Transformation of Ferric Oxyhydroxides and Their Activity to Sulfur Dioxide
Authors: Ishikawa Tatsuo , Inouye Katsuya 
Published: July 2006

Abstract
α-, β-, and γ-FeOOH calcined at various temperatures up to 500°C have been examined by determining adsorption isotherms in order to relate the reactivity to SO2 with the structural transformation. For each ferric oxyhydroxide, the amount of chemisorbed SO2 per unit surface area (Ac), a measure of reactivity to SO2, decreases with the progress of transformation into α-Fe2O3. At temperatures of calcination below 200°C the Ac value of β-FeOOH is larger than that of α-FeOOH or γ-FeOOH. It is shown by thermogravimetric analysis that the weight loss of β-FeOOH caused by heating is larger than the theoretical value corresponding to the dehydration of hydroxyl groups; 2FeOOH→Fe2O3+H2O. Changes in the X-ray diffraction patterns and Cl content of β-FeOOH with calcination indicate that β-FeOOH is transformed into α-Fe2O3 with elimination of inherently contained Cl at a higher temperature than other oxyhydroxides. The high reactivity to SO2 and large weight loss of β-FeOOH caused by heating have been discussed with respect to the particular crystal structure of β-FeOOH containing Cl and molecular H2O, in addition to hydroxyl groups.
Studies of Built-up Films by Means of the Polarized Infrared ATR Spectrum. III. Elaidic Acid Films
Authors: Takenaka Tohru , Nogami Kazuko 
Published: July 2006

Abstract
Attenuated total reflection studies with polarized infrared radiation have been made of multilayers of elaidic acid built up on a germanium plate by the Blodgett technique. It is concluded that the built-up films prepared from the tap-water substrate are made of calcium elaidate monohydrate. From the intensity changes in the regularly-spaced peaks (progression bands) in the region from 1350 to 1180 cm−1, the planarity of the chain segment between the carboxylate group and the double bond is found to be dependent upon the surface pressure applied in the process of monolayer transfer onto the germanium plate. Studies of the anisotropy of the absorption index in the films show that the molecules assume a uniaxial orientation with respect to the axis normal to the germanium-sample interface (the z-axis), with an angle from 30° to 33° (in average) between the z-axis and the molecular axes. Furthermore, from the changes in the reflectivity with the number of layers, the film thickness per layer is estimated to be ca. 21.9 Å, a value which is in good agreement with the half-value of the long spacing, 44.16 Å, of the films as determined by X-ray diffraction studies. This apparently indicates that the films appear as the Y type.
Vibrational Spectra of Propionamide and Its C- and N-Deuterated Compounds
Authors: Kuroda Yoshihiro , Saito Yutaka , Maghida Katsunosuke , Uno Toyozo 
Published: July 2006

Abstract
The infrared and Raman spectra of CH3CH2CONH2, CH3CD2CONH2 and their N-deuterated compounds in the solid state have been measured. The normal coordinate analysis has been made by assuming the molecular symmetry of Cs. A Urey-Bradley force field was used for the in-plane vibrations and a valence force field for the out-of-plane vibrations of the amide group. The ethyl group was treated by a Urey-Bradley type force field as well as a valence type force field. The assignments of the fundamental frequencies have been made by referring to the infrared and Raman intensities, isotopic frequency shift and the calculated frequencies by using the force constants which were taken from n-paraffins and acetamide. The agreement between the observed and the calculated frequencies in the initial calculation was good for the CH3 and the amide group vibrations but was not good enough for some vibrations involving the α-carbon atom. Only the force constants related to these vibrations were refined by the least squares method in order to obtain the best fit. The calculated frequencies in this way fit to the observed satisfactorily.
On the Mechanism of H-Atom Formation by Reaction of Electrons in Frozen Acidic Solutions at 77°K
Authors: Ohno Shin-ichi , Sasaki Teikichi , Koike Mitsuru 
Published: July 2006

Abstract
A model for the reaction of radiation-produced electrons in frozen acidic solutions is presented to explain anomalies. It does not assume the inertness of the hydrogen ion as an electron scavenger in the solid phase but involves a process in which an H-atom, the product of the (e−+H+) reaction, is transferred to an adjacent water molecule through an H-bonded network until it finds a suitable site where it can be trapped or a species with which to react. Results from ESR-measurements on photolysed frozen solutions of ferrocyanide ions in the presence of nitrate ions and 2-propanol as well as the data on H/D isotope effects were used as evidence supporting the model.
The Kinetics and Mechanism of the Photo-oxidation of N,N′-Diphenyl-p-phenylenediamine. Electron-transfer from the Upper Excited Singlet State to Oxygen
Authors: Shizuka Haruo , Sawaguri Yasuyoshi , Morita Toshifumi 
Published: July 2006

Abstract
The photo-oxidation of N,N′-diphenyl-p-phenylenediarnine (DPPD) has been studied spectrophotometrically. The quantum yield for the diimine formation, Φ, in aerated cyclohexane at 2537 Å and 20°C did not change with variations of the irradiation time, the concentration of DPPD, or the light intensity. However, the Φ values increased, as did the decrease in the fluorescence quantum yields, as the excitation energies increased. The dissolved oxygen had the optimum concentration (1.2×10−4m), giving the maximum value of Φ in aerated cyclohexane at 2537 Å, and none of the product, the diimine, was obtained in the degassed system. When about 0.13m of ethanol or methanol was added to aerated cyclohexane, the maximum value of Φ was measured, and the addition of a highlypolar solvent, acetonitrile or H2O, decreased regularly in Φ. On the basis of these results, it can be said that the photo-oxidation of DPPD originates from the Franck-Condon state of the upper excited singlet state, 1(RH2)n. It seems that, in the primary processes of the reaction, the electron transfers take place from the Franck-Condon state of 1(RH2)n directly to the oxygen molecule (3Σg−) and to the solvent, resulting in a trapped electron which immediately jumps into the oxygen molecule. Then, the (RH2)+O2− ion pair may be formed, and subsequently the intermediate, (RH2)+O2−, may be converted to the product or the starting materials. The dissolved oxygen and the polar solvents are responsible for the electron-transfer processes, but they deactivate the ion pair, resulting in the decrease in Φ.
Stereochemical Studies of Monoterpene Compounds. XIII. The Conformational Analysis of the Acetyl Group of 4-Methyl-10-nor-8-oxomenthols by Circular Dichroism
Authors: Suga Takayuki , Watanabe Satoru 
Published: July 2006

Abstract
The conformational analysis of the acetyl group of a stereoisomeric pair of 4-methyl-10-nor-8-oxomenthols was made by means of the temperature-dependent circular dichroism. (1R:3S:4R)-(+)-4-Methyl-10-nor-8-oxoneomenthol (1) exhibited a double-humped Cotton effect at a low temperature. This phenomenon seems to indicate the existence of a conformational equilibrium among 1b, 1c, and 1d, but not 1a. On the other hand (1R:3R:4R)-(−)-4-methyl-10-nor-8-oxomenthol (3) exhibited an inversion in the sign of the Cotton effect when the solvent and the temperature were changed. This phenomenon was interpreted in terms of the conformational equilibrium among 3a, 3b, and 3c. These phenomena were interpreted in terms of the competition of the steric factor and the intramolecular hydrogen bonding.
The Crystal Structure of μ-Oxo-bis{pentamminechromium(III)} Chloride Monohydrate, [(NH3)5Cr-O-Cr(NH3)5]Cl4·H2O
Authors: Urushiyama Akio 
Published: July 2006

Abstract
The crystal structure of μ-oxo-bis{pentamminechromium(III)} chloride (basic rhodochromic chloride) monohydrate, [(NH3)5Cr–O–Cr(NH3)5]Cl4·H2O, has been determined from the three-dimensional X-ray data. The crystals are orthorhombic. The cell dimensions are: a=11.94±0.01, b=11.71±0.01, and c=13.40±0.02 Å. The space group is Pbca, with four formula units in a unit cell. The structure was refined by the least-squares method, with anisotropic temperature factors, to R=0.14. A bridging oxygen atom of the basic rhodochromic complex ion is situated on the inversion center. Therefore, the complex has a center of symmetry and, accordingly, a linear Cr–O–Cr system. The N–Cr–O angles are nearly 90° or 180°, and the Cr–N bond distances are in the range from 2.09 to 2.14 Å (average 2.11 Å). The complex ion has approximately a D4h symmetry. The Cr–O distance is 1.80 Å, which is quite short compared with that found in the other Cr(III) complexes. The linear Cr–O–Cr system and its short bond distance suggest the presence of an extensive π-bonding in this system. The single-crystal polarized absorption spectra in the visible and ultraviolet regions were also measured. It was found that the characteristic sharp absorption bands of the basic rhodochromic complex ion are all polarized along the fourfold rotation axis of the complex.
Dipole Moment Functions of CO and HCl
Authors: Suzuki Isao 
Published: July 2006

Abstract
A general formalism is presented for the least-squares determination of dipole moment functions of diatomic molecules in which the radial part wave functions obtained as numerical solutions of vibration and vibration-rotation Hamiltonian matrix are used. Although this approach is purely numerical, the advantage of using orthonormal basis and perturbed wave functions is retained. Attempts have been made on the determination of the cubic dipole moment functions for the CO and HCl molecules. All the available data of dipole as well as transition moments and the Herman-Wallis factors for these molecules are considered in the refinement process. The following cubic dipole moment functions are obtained (in Debye): M(Δr)=0.1243–3.0722(Δr)+0.1909(Δr)2+2.1856(Δr)3 for CO and M(Δr)=1.093+0.949(Δr)+0.034(Δr)2–0.78(Δr)3 for HCl.
Self-Diffusion Coefficients and Interdiffusion Coefficient in Acetone–Benzene System
Authors: Kamei Yoshinobu , Oishi Yasumichi 
Published: July 2006

Abstract
Self-diffusion coefficients of acetone and benzene have been determined in the whole composition range of the binary system at 25°C by a capillary-cell method using the 14C-marked tracer. The results were in a good agreement with those determined by the NMR spin-echo method by McCall and Douglass. The products of the respective self-diffusion coefficients and the viscosity of this system showed a relatively constant compositional dependence. Bearman’s relation was shown to hold between the self-diffusion coefficients and the partial molar volumes for the system. The validity of Darken’s equation was confirmed for the self-diffusion coefficients and the interdiffusion coefficient of the system.
Temperature Dependence of Corona-charging Properties on TiO2-Polymer Dispersion Layers
Authors: Iida Takeaki , Nonaka Toyokazu , Nozaki Hiroshi 
Published: July 2006

Abstract
The corona-charging properties of TiO2-polymer dispersion layers were determined in the dark at temperatures 0°–35°C by the turn-table method. Dispersion layers of TiO2 (rutile) and polyvinyl acetate, coated on an aluminum foil to about 15 μ thickness, were used. The results showed the rising rate of the surface potential has a maximum at around 20°C. The saturation potential decreases slightly with a rise in temperature. The decay potentials were represented by the plot logV vs. \sqrtt. The relation between logV and \sqrtt is linear in certain range of the surface potential, and the gradient increases in proportion to the rise in temperature. This is discussed with the use of an equivalent-circuit model.
Fluorinated Ligands. I. Chelating Behavior of 1-Amino-3,3,3-trifluoro-2-propanol with Copper(II) Ion and Preparation of Copper(II)-, Cobalt(III)-, and Nickel(II) Complexes
Authors: Yoshida Isao , Kobayashi Hiroshi 
Published: July 2006

Abstract
In the reaction of 1-amino-3,3,3-trinuoro-2-propanol (LOH) with cupric ion in aqueous solutions two kinds of complex species were found to be formed: One was a complex ion of [Cu(LO)(H2O)2]+1, which was of major abundance in the solutions where mole ratio of the ligand to the metal ion was less than 3, and the other was an inner complex of [Cu(LO)2] predominating in the solutions which contained a large excess of the ligand or a small amount of alkali. The structures of the species in the solution phases were assigned by the spectral data. Chelate compounds of inner complex type, [Cu(LO)2(H2O)], [Co(LO)3], and [Ni(LO)2], were synthesized from the present ligand and corresponding metal ion. These are insensitive to moisture in the air. Structures of the chelates are discussed on the basis of spectroscopic observations.
Schiff Bases Derived from Heptane-2,4,6-trione and Ethylenediamine, and Its Copper(II) and Oxovanadium(IV) Chelates
Authors: Yano Tairoku , Ushijima Tetsuaki , Sasaki Masaomi , Kobayashi Hiroshi , Ueno Keihei 
Published: July 2006

Abstract
The copper(II) and oxovanadium(IV) complexes of a new Schiff base derived from heptane-2,4,6-trione and ethylenediamine were prepared. Of a macrocyclic two-to-two and an open jaw-shaped two-to-one (trione to diamine) condensation product, only the latter gave mononuclear copper (II) and oxovanadium(IV) complexes. The coordinating sites to the metal ion in each complex are discussed referring to the spectroscopic results.
Polarographic Behavior of Nickel(II) in Propionitrile and Benzonitrile in the Presence of Thiocyanate Ions
Authors: Itabashi Eiki 
Published: July 2006

Abstract
The effect of the cation of the supporting electrolyte on the electrode reaction of nickel(II) in propionitrile and benzonitrile solutions containing thiocyanate ion was investigated by DC polarography and i-t curve analysis. In the absence of thiocyanate ion, a propionitrile solution of nickel(II) gives a single irreversible wave in LiClO4 and NaClO4 supporting electrolytes and a double wave in Et4NClO4 and n-Bu4NClO4, and a benzonitrile solution of nickel(II) gives a double wave in alkali metal and quaternary ammonium perchlorates. Nickel(II) in these nitrile solvents in the presence of thiocyanate ion exhibits a catalytic pre-wave in alkali metal perchlorates and a catalytic maximum wave in quaternary ammonium perchlorates. The double wave of nickel(II) in the absence of thiocyanate ion is due to the inhibition of the charge transfer process by the relatively weak adsorption of quaternary ammonium cations and not to the presence of two electroactive species. A mechanism which involves the cyclic regeneration of adsorbed thiocyanate ion for the catalytic pre-wave and the catalytic reduction of thiocyanate ion with the electroreduced metallic nickel for the maximum wave has been presented.
Mixed Solvent Deuterium Isotope Effects on the Hydrolysis of UO22+ and Be2+ Ions
Authors: Maeda Masunobu , Amaya Toshihiko , Ohtaki Hitoshi , Kakihana Hidetake 
Published: July 2006

Abstract
Stability constants of the hydrolysis species of UO22+ ion were determined in pure light water and 80% heavy water containing 3m NaClO4 as an ionic medium at 25°C, and the results were compared with those in pure heavy water. The decrease of the stability constants in hydrolysis reactions of UO22+ ion, as well as of Be2+ ion, was discussed in terms of the equilibrium theory of the solvent deuterium isotope effects, which is based on the assumptions that activity coefficients of chemical species in isotopic exchange equilibria remain unchanged with the change in the deuterium atom fraction in the solvent, that the solvated hydrogen ion possesses three equivalent lyons, and that the isotopic equilibria are subject to the rule of the simple geometric mean. Satisfactory agreements were found between the observed and calculated values for the relative stability constants of the hydrolysis species of UO22+ and Be2+ in water of various hydrogen isotopic compositions.
Some Metal Complexes Containing Ethyl Acetoacetate or Ethyl Malonate as a Neutral Ligand
Authors: Morita Hideyoshi , Nakamura Yukio , Kawaguchi Shinichi 
Published: July 2006

Abstract
The following metal complexes containing ethyl acetoacetate (etacH) or ethyl malonate (etmalH) as a neutral ligand have been prepared: CoCl2L, CoBr2L, ZnCl2L (L=etacH or etmalH), and MnBr2(etmalH). These compounds are all hygroscopic and unstable, releasing the ester ligand below 100°C in vacuo or in donor solvents. The infrared spectra show that the ratio of keto and enol tautomers in etacH complexes is similar to that for the free ligand. The ν(C=O) band attributable to the enol tautomer of etmalH is observed in the complexes, though not in the free ligand. The electronic spectra measured in Nujol suggest that the cobalt(II) complexes are tetrahedral. The structure of MnBr2(etmalH) is not yet certain.
The Reaction of Hydrosilanes with Chlorosilanes in the Presence of Grignard Reagents. A New Method of Silicon-Silicon Bond Formation
Authors: Hosomi Akira , Sakurai Hideki 
Published: July 2006

Abstract
A new method has been developed for the formation of a silicon-silicon bond. Hydrosilanes having at least one phenyl or one trimethylsilyl group on a silicon atom were subjected to reaction with chlorosilanes to give unsymmetrically substituted disilanes in the presence of secondary or tertiary Grignard reagent which was inert to both chlorosilanes and hydrosilanes. The method was extended to the preparation of benzyl, allyl, and alkylsilanes.
Magnetic Circular Dichroism of Nickel(II) and Copper(II) Complexes with 1,4,8,11-Tetraazacyclotetradecane Derivatives
Authors: Kobayashi Hiroshi , Korybut-Daszkiewicz Bohdan 
Published: July 2006

Abstract
The magnetic circular dichroism (MCD) spectra of nickel(II) and copper(II) complexes with 1,4,8,11-tetraazacyclotetradecane derivatives were measured. An anomalous MCD dispersion was observed in a (d, d*) band at 22000 cm−1 for the copper(II) complexes and at 22000–23000 cm−1 for the nickel(II) complexes. In the ultraviolet region, the nickel(II) complexes show a normal MCD dispersion in the 35500 cm−1 band which appears only for the ligands with &gt;C=N- double bonds, while the copper(II) complexes show an anomalous dispersion in the 39000 cm−1 band which appears even if the ligand lacks &gt;C=N- double bonds. The 35500 cm−1 band of the nickel(II) complexes is assigned to a “metal to ligand” charge-transfer transition leg→π* and the 39000 cm−1 band of the copper(II) complexes to a “ligand to metal” charge-transfer transition leu→2b1g. In the nickel(II) complex of a ligand with two isolated and two conjugated double bonds shows a normal MCD dispersion in the 25000 cm−1 band. The absorption band is assigned to a “metal to ligand conjugated double bonds” charge-transfer transition rather than a (d, d*) transition.
The Autoxidation of Phenols Catalyzed by Phthalocyanine-Fe(II) and Salcomine-pyridine
Authors: Tada Masaru , Katsu Takashi 
Published: July 2006

Abstract
The autoxidation of 2,4,6-tri-t-butylphenol (1), 2,6-di-t-butylphenol (2), and 2,4-di-t-butylphenol (3) is catalyzed by phthalocyanine-Fe(II) (PC-Fe(II)) and salcomine-pyridine (SAL-Py). PC-Fe(II) gives, preferentially, the coupling product of such phenoxy radicals as 4, 7, and 8. SAL-Py, on the other hand, gives o-and p-benzoquinones, such as 5 and 6, resulting from the coupling of the phenoxy radical and the hydroperoxy radical. Metal phthalocyanines including Mn(II), Co(II), Ni(II), or Cu(II) as the central metal ion are inactive as catalysts for the oxidation. PC-Fe(II) does not catalyze the autoxidation of phenol itself and mono-alkylated phenols.
Restricted Rotation in Aromatic Ketones. I. Substituent Effects on the Barrier to Rotation about the Benzene-to-Carbonyl Bond
Authors: Nakamura Nobuo , Oki Michinori 
Published: July 2006

Abstract
Several aryl isopropyl ketones and aryl benzyl ketones were synthesized and their NMR spectra were recorded at various temperatures. Their temperature dependence was accounted for in terms of the restricted rotation about the benzene-to-carbonyl bond, whose free energies of activation at the coalescence temperatures varied from 9 to 15 kcal/mol according to the steric effect of ortho substituents, the buttressing effect of meta substituents, and the steric effect of the side-chain groups.