bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photoconductive Properties of Organic Polyiodides
Authors: Sano Toshihiko , Okamoto Kenichi , Kusabayashi Shigekazu , Mikawa Hiroshi 
Published: July 2006

Abstract
The photoconductive properties of (CH3)4N+I5−, (CH3)3(C6H5)N+I5−, N-methylacridinium pentaiodide and N-methylquinolinium pentaiodide were investigated by both a sandwich type cell and a single crystal cell. In the former arrangement, the photoresponse observed was the overlap of photoconductive response and photovoltaic response. The single crystal gave pure photoconductive response. Tetramethylammonium pentaiodide was the most photoconductive among the polyiodides. Spectral dependence of the photocondutcivity of this compound revealed that the threshold is at about 1000 mμ (1.24 eV). This value is in good agreement with the band gap energy 1.36 eV obtained from the temperature dependence of the dark current and 1.20–1.26 eV from calculation. Semiconductive properties of the organic polyiodides are explained by applying the band model.
Kinetics of Multidentate Ligand Substitution Reactions. VI. The Substitution Reaction of Diethylenetriaminepentaacetic Acid with the Nitrilotriacetato Nickelate(II) Chelate
Authors: Kodama Mutsuo 
Published: July 2006

Abstract
The kinetics of the substitution reaction of diethylenetriaminepentaacetic acid (DTPA) with the nitrilotriacetato nickelate(II) chelate have been studied polarographically in both acid and alkaline media. The reaction was found to be first-order with respect to DTPA and also first-order with respect to the nitrilotriacetato nickelate(II) chelate with 1-to-1 composition. In an acid solution the reaction proceeds mainly through tervalent and quadrivalent DTPA anions. On the other hand, in an alkaline solution the reaction proceeds through quadrivalent and quin-quevalent DTPA anions. The heat of activation and the entropy of activation for the three elementary reactions were estimated, and the effect of the protonation of the quinquevalent DTPA anion on the reaction rate was discussed.
Metal Complexes of Schiff Bases Obtained from Substituted Salicylaldehydes and 2-Aminopyridine Derivatives
Authors: Yamada Shoichiro , Yamanouchi Kuniko 
Published: July 2006

Abstract
Numerous metal complexes (abbreviated as M(X-SAL·R)2·nH2O) of Schiff bases obtained from substituted salicylaldehydes and 2-aminopyridine derivatives were prepared as crystals, where X=H, 5,6-benzo, 5-Cl, 5-Br, 5-NO2 and 3-CH3O, R=2-pyridyl, 2-(3-methylpyridyl), 2-(4-methylpyridyl) and 2-(6-methylpyridyl), and M=Co(II), Ni(II), Cu(II), Zn(II) and Pd(II). It is concluded, mainly from the electronic absorption spectra, that the cobalt (II) complexes are tetra-hedral, with one exception, which has an octahedral configuration with two water molecules coordinated to the cobalt(II) ion. The nickel(II) complexes are octahedral, and the copper(II) and the palladium(II) complexes are planar. In these metal complexes, the Schiff bases are bidentate, except bis(N-2-(6-methylpyridyl)-salicylideneiminato)nickel(II), in which the ligand functions as a terdentate.
Metal-Containing Initiator Systems. XVI. Radical Polymerization with Metal Carboxylates
Authors: Aoki Shuzo , Matsumura Seitaro , Otsu Takayuki 
Published: July 2006

Abstract
The polymerization of vinyl monomers with metal carboxylates has been investigated in benzene at 60°C. Gobalt(III) cyclohexanecarboxylate behaved as an effective initiator of the polymerization, and its activity was higher than that of corresponding salts of manganese (III) and copper(II), and than that of cobalt (III) acetylacetonate in the polymerizations of styrene (St) and methyl methacrylate (MMA). It was found that the overall rate of polymeriaztion (Rp) of MMA with cobalt (III) cyclohexanecarboxylate was expressed by the following equation, indicating that the polymerization proceeded through a free redical intermediate:
Rp=k[MMA]1.4[Co(III)]0.5
The free radical propagation of this polymerization was also supported by the results of the copolymerizations of St with MMA and with vinyl acetate; i.e., the resulting copolymer composition curves agreed with the typical free radical ones. It was assumed that the initiation of polymerization occurred by means of a radical produced by the homolysis of the metal-oxygen bond in the carboxylate. The reaction order with respect to MMA in the above equation, which was higher than unity, suggested the participation of the MMA molecule in initiating the radical formation.
The Absolute Configuration of Isopropylidenecamphor Oxide
Authors: Katsuhara Jun 
Published: July 2006

Abstract
The conversion of (+)-isopropylidenecamphor derived from (+)-camphor into (1R:2S:4S)-isopropylideneborneol and (1R:2R:4S)-isopropylideneisoborneol was described. In light of this configurational correlation, it was concluded that (+) -isopropylidenecamphor oxide derived from isopropylideneborneol has (1R:3R:4S)-, and (−)-isopropylidenecamphor oxide derived from isopropylideneisoborneol, (1R:3S:4S)-configurations.
Coumarins. VII. The Acid-catalyzed Reaction of Aromatic Compounds with β-Chlorocarboxylic Acids
Authors: Sato Kikumasa , Lin Yau-Shin , Amakasu Takeshi 
Published: July 2006

Abstract
The aluminum chloride-catalyzed reaction of aromatic compounds, such as benzene and phenols, with β-chlorocarboxylic acids was investigated. Although the reactions of benzene, toluene, and chlorobenzene with β-chloropropionic acid were found to give the corresponding dihydrocinnamic acids in high yields, attempts to prepare dihydrocoumarin by a similar reaction of phenol were unsuccessful. Similarly, β-arylbutyric acids were obtained in good yields by means of the aluminum chloride-induced reaction of aromatic hydrocarbons with β-chlorobutyric acid (Ib). In contrast, phenols, such as phenol, o- and m-cresols, reacted with Ib under similar conditions to provide the corresponding β-(p-hydroxyphenyl)butyric acids in 22–60% yields, while a 51% yield of β-(5-hydroxy-2-methylphenyl) butyric acid was obtained upon a similar treatment of p-cresol with the acid Ib.
Argentation Constants of Styrene Derivatives
Authors: Inaki Yoshiaki , Nozakura Shun-ichi , Murahashi Shunsuke 
Published: July 2006

Abstract
Equilibrium constants for the formation of silver ion complexes (argentation constants) of styrene derivatives in water were measured at 0 and 25°C by Andrews and Keefer’s solubility method. The argentation constants for the 1 : 1 complex (K1) decreased in this order: cis-β-alkylstyrene&gt;α-alkylstyrene&gt;trans-β-alkylstyrene, for a given alkyl group. This order was related to differences in the resonance stabilization of the double bond. The K1 values of the α- and β-alkylstyrene series did not seem to correlate with Taft’s steric substituent constant, Es, within the respective series. However, when the hyper conjugation effect of alkyl substituents was considered, a good linearity between logK1 and Hancock’s parameter, Esc, was obtained. Thus, the steric effect was separated from the hyperconjugation effect, and it was found that the steric effects for the three series are nearly identical. Thermodynamic data indicated that an isokinetic relationship holds between ΔH and ΔS and that the argentation equilibrium is controlled mainly by the entropy factor. The degree of methyl substitution at the double bond of styrene slightly influenced the K1 values, although 1,2-dihydronaphthalene had an abnormally large K1 value.
Sulfilimine. I. Synthesis and Formation Mechanism
Authors: Tsujihara Kenji , Furukawa Naomichi , Oae Keiko , Oae Shigeru 
Published: July 2006

Abstract
The kinetics of the reaction of sulfide and chloramine T was investigated. The reaction was very much affected by pH, and the rate reached the maximum at pH 5.5. The reaction was found to be facilitated by the substitution of an electron-releasing group in phenyl rings of aryl methyl sulfides. From these observations the rate-determining step appears to involve the formation of the sulfonium cation intermediate. From the mechanistic study of this reaction, an effective procedure for the synthesis of sulfilimine was devised.
Amine Derivatives of 1-(1′-Phenyl-2′-bromoethyl)-5-methyltetrazole
Authors: Terada Akira , Hassner Alfred 
Published: July 2006

Abstract
As part of search for a potential new type of antimalarial, several 1-(1′-phenyl-2′-aminoethyl)-5-methyltetrazoles were prepared by the amination of 1-(1′-phenyl-2′-bromoethyl)-5-methyltetrazole using various amines, such as mono- and diamines of aliphatic and alicyclic. The reaction in the presence of a large excess of amine occurred smoothly on heating at 100–130°C, and it gave the title product without any significant by-product such as the bistetrazole compound, even though a primary amine was used.
The Adsorption of Cobaltous Ions on Glass Beads from Extremely Dilute Aqueous Solutions
Authors: Seimiya Tsutomu , Kozai Hisako , Sasaki Tsunetaka 
Published: July 2006

Abstract
The adsorption of cobaltous ions on fine glass beads was measured for dilute aqueous 60CoCl2 solutions with pH values from 2 to 10 and with concentrations from 10−6 to 10−10 mol/l. The amount of the adsorption of cobaltous ions on glass showed a maximum at pH near 9, and it was zero at both ends of the pH region for all the initial concentrations studied. This fact is considered to confirm the theory of radiocolloid formation by the so-called adsorption method. The mechanism of radiocolloid formation was further discussed in detail. The formation of radiocolloids was explained by the adsorption of cobaltous ions on foreign particles, while the formation of insoluble cobaltous hydroxide was ruled out. It was estimated from these measurements that a very minute amount of foreign particles is sufficient to adsorb cobaltous ions and to change a large franction of the solute to radiocolloid. It was emphasized that such an estimation can be made only by the measurement of the adsorption, expressed by the unit of mol/cm2 as in the case of the present experiment, instead of the conventional unit of cpm/g or percent adsoiption.
Radical Conversions in γ-Irradiated 3-Methylpentane-Isobutene Systems
Authors: Tsuji Kozo , Okamura Seizo 
Published: July 2006

Abstract
Radical conversions in γ-irradiated 3-methylpentane-isobutene systems were observed by means of the electron spin resonance method after keeping the sample at −196°C for a few days, or by subjecting it to ultraviolet irradiation. One of the changes was caused by hydrogen atom abstraction from neighboring molecules by original free radicals. The other change was attributed to dissociation of the free radicals from 3-methylpentane by ultraviolet irradiation.
Nitrosyl Complexes of Bis(acetylacetone)-, and Bis(benzoylacetone)-ethylenediimine Cobalt(II)
Authors: Tamaki Motonori , Masuda Isao , Shinra Koichiro 
Published: July 2006

Abstract
Square, planar bis(acetylacetone)-, and bis(benzoylacetone)-etylenediimine-Co(II) chelates with a low-spin d7 electron structure yield nitrosyl complexes with the chelate : NO molar ratio of 1 : 1. On the basis of the IR spectra and the NMR spectra, and on the basis of molecular-weight determinations, these nitrosyls have been considered as being penta-coordinate cobalt complexes with square-pyramidal configuration. The nitrosyls are diamagnetic, indicating an electron-pairing bond between the central Co(II) and the NO molecule. The NO groups in these nitrosyls have been postulated to be predominantly neutral. In the electronic spectra, these penta-coordinate, diamagnetic Co(II) complexes show a characteristic absorption band at 18–20×103 cm−1 with logε\doteqdot3.
Pyrolysis-Gas Chromatographic Determination of Chlorine in Chlorine-Containing Synthetic Polymers
Authors: Tsuge Shin , Okumoto Tadaoki , Takeuchi Tsugio 
Published: July 2006

Abstract
A new, simple and rapid method for determining chlorine in chlorine-containing polymers was investigated by means of pyrolysis-gas chromatography. Hydrogen chloride evolved during the thermal degradation of the polymers was eliminated by a NaOH precut column, and only the organic compounds sensitive to flame ionization detector were separated to record the pyrograms. Chlorine content of the polymers was calculated from the relative yield of the degradation products using a theoretical equation deduced from the degradation mechanisms of the polymers. This unique method permits very rapid determination of chlorine with the use of about 0.1 mg of the sample without either the use of calibration curves or weighing of the samples.
A Partial Asymmetric Synthesis via a Cyclic Oxyphosphorane
Authors: Muroi Motoo , Inouye Yuzo , Ohno Minoru 
Published: July 2006

Abstract
A partial asymmetric synthesis was achieved in the carbon-carbon condensation which involved the reaction of (−)-menthyl pyruvate with trimethyl phosphite, followed by alkaline hydrolysis of the intermediate cyclic oxyphosphorane to yield (−)-(S:S)-2,3-dimethyltartaric acid. With knowledge of absolute configurations of both the chiral center and the predominant enantiomer of the product, an ex post facto interpretation of the steric course was made on the basis of relative steric stability of transition state conformations of the addition step of III to I.
Synthetic Studies of Cobalt Carbonyl by Noble Metal Catalysts. I. The Effects of the Form of Cobalt Feed and Noble Metal Catalysts
Authors: Usami Seiji , Kondo Takayoshi , Nishimura Kotaro , Koga Yuzo 
Published: July 2006

Abstract
A novel method of synthesizing cobalt carbonyl was investigated by using noble metal catalysts. It has been observed that the materials containing palladium, i. e., palladium black, palladium chloride, palladium acetylacetonate, bistriphenylphosphine dichloropalladium, and palladium-on-carriers, have a catalytic effect on the cobalt carbonylation reaction, and that palladium-on-carbon (Pd-C) is the most active catalyst. The reactivity of cobalt compounds in the cobalt carbonylation reaction catalyzed by noble metals increases in this order: CoSO4&lt;&lt;CoO\lesssimCo(OAc)2\lesssimCo-oleate&lt;Co(OH)2. When the Pd-C catalyst is used, cobalt hydroxide reacts with synthesis gas of 150 kg/cm2 to give cobalt carbonyl almost quantitatively, even at from 50 to 55°C. The catalytic activities of noble metals were shown to be, in the order of decreasing activity: Pd&gt;Au&gt;Pt&gt;&gt;Ag. The effect of the catalyst concentration and the activity of noble-metal catalysts were also compared with those in the case of dicobalt octacarbonyl, as an autocatalyst.
Photolysis of Aromatic Oxime Benzoates
Authors: Okada Taiichi , Kawanisi Mituyosi , Nozaki Hitoshi 
Published: July 2006

Abstract
Irradiation of aromatic oxime benzoates, R1R2C=N–OCOPh, in benzene solution gives the corresponding azines, (R1R2C=N–)2, and ketones, R1R2C=O, along with PhCO2NH4. PhCO2H and Ph2 are also obtained in all cases. The reaction course can be explained by assuming a radical fission of excited R1R2C=N–OCOPh which gives radicals R1R2C=N· and ·OCOPh in the initial step. Sensitization experiment establishes the fact that a triplet state of the oxime benzoate is involved as a chemically reactive species.
Magnetic and Optical Properties of Aromatic Hydrocarbon Cation Radical Salts
Authors: Sato Yoichiro , Kinoshita Minoru , Sano Mizuka , Akamatu Hideo 
Published: July 2006

Abstract
Stable cation radical salts were prepared by oxidation of perylene, 9,10-diphenylanthracene, 9,10-dimethylanthracene, and 9,10-dichloranthracene with antimony pentachloride. Perylene perchlorate was also obtained in a stable form. From the temperature variations of their paramagnetic susceptibilities, the exchange coupling constants for these salts were found to increase in the sequence of above listing ranging from ∼0 to 8.5×10−2 eV. The absorption spectra of these solid compounds were compared with those observed with solutions. While the absorption bands of each salt in the visible region were found to correspond to those of the solution spectrum of the respective compound, an extra absorption band was observed in the near-infrared region for compounds with larger exchange coupling constants. The appearance of the new absorption band was reasonably ascribed to charge-transfer interaction between the radicals. These observations are considered to support further our previous suggestion that the magnitude of the exchange coupling constant obtained through magnetic measurements is basically determined by the stabilization energy due to the charger-transfer configurational interaction.
Anomalous Viscosity of Bitumen Solutions and the Agglomeration of “Molecules”
Authors: Inouye Katsuya , Tatsuta Junichi , Sakabe Tsutomu 
Published: July 2006

Abstract
The flow property of catechol and phenol solutions of 14 bitumen fractions was examined by means of a horizontal viscometer to compare with the molecular weight values of the fractions determined in each solvent. The catechol solutions showed Newtonian flow which corresponds to the homogeneous solutions containing molecules of a limited value of molecular weight. The molecular weight from phenol solutions varies with the fractions, and all fractions showed non-Newtonian (structural) viscosity. The experimental results indicated that bitumens in phenol agglomerate to different extent particular to each fraction. It was presumed that the stress destroys the agglomerated state to a monodisperse state, which is gradually recovered to the original state on standing. It was noted however that the unit particle (or molecule) composing each fraction is not identical in the apparent size in phenol, but varies with fractions.
The Radiolysis of Liquid Nitrogen Containing Hydrocarbons. I. Ethylene and Propylene
Authors: Oka Takefumi , Suda Yoshikazu , Sato Shin 
Published: July 2006

Abstract
The γ-radiolysis of liquid nitrogen containing ethylene and propylene has been investigated. As the nitrogenous products, hydrogen cyanide (0.18) and acetonitrile (0.04) were observed in the case of ethylene, and acetonitrile (0.12), in the case of propylene. The values in the parentheses are the G-values estimated on the basis of the energy absorbed by liquid nitrogen. In order to elucidate the mechanism of the reaction between nitrogen atoms and propylene, the mixture of C3H6 and C3D6 and the CD3CH=CHD compound have also been used as solutes. The acetonitrile obtained was mainly CH3CN and CD3CN in the former case, and CD3CN in the latter. These results suggest that a nitrogen atom produced in the system attacks the carbon atom in the middle of propylene and produces acetonitrile, leaving a methyl radical, the carbon atom in which was originally attached to the double bond.
Radiolysis of Methylcyclohexane. II. The Effect of Cumene on Hydrogen Formation from γ-Irradiated Methylcyclohexane
Authors: Kimura Toyoaki , Fueki Kenji , Kuri Zen-ichiro 
Published: July 2006

Abstract
The effect of cumene on the hydrogen yields from methylcyclohexane γ-irradiated at 100, 20, −72, −120 and −196°C has been investigated. Cumene did not compete with N2O for capturing electrons in methylcyclohexane and the yield of thermal H atoms in methylcyclohexane, determined by use of ethylene as an H atom scavenger, was smaller than the decrease in hydrogen yield in methylcyclohexane-cumene systems. Therefore, the decrease in hydrogen yield in methylcyclo-hexane-cumene systems can be ascribed mainly to positive charge transfer from methylcyclohexane to cumene. Further, the evidence of charge transfer from methylcyclohexane to cumene was found by the optical absorption method. The effect of cumene on the hydrogen yield from methylcyclohexane was similar in the temperature range from 100 to −196°C, especially at high cumene concentration. The effect of an electron scavenger at high concentrations was also examined with n-butyl chloride. In the present work, we have found that although the effect of a positive ion scavenger on the hydrogen yield from methylcyclohexane in the liquid state differs little from that in the glassy state, the effect of electron scavengers on the former differs considerably from that on the latter.
Group Interactions in Polyelectrolytes. II. Kinetics of Alkaline Hydrolysis of Polymethyl Acrylate
Authors: Kawabe Hiroshi , Yanagita Masaya 
Published: July 2006

Abstract
The second-order rate constant of the alkaline hydrolysis of polymethyl acrylate in an aqueous acetone solution decreases as the reaction proceeds. The plot of the logarithmic term of the second-order rate equation against the reaction time is divided into four lines; this suggests that the reaction proceeds in four steps. The rate equation of the reaction can be derived by assuming that the reactivity of ester groups is electrically affected mainly by a few neighboring hydrolyzed groups. The kinetic behavior is compared with the titration data of polyacrylic acid; the sets of data can be correlated through a simple equation containg two constants, k0, the intrinsic rate constant, and pK0, the intrinsic ionization constant.
The Electronic Structures of Glycine in the Isolated State and in Water
Authors: Imamura Akira , Fujita Hiroko , Nagata Chikayoshi 
Published: July 2006

Abstract
The electronic structures of glycine have been calculated for the dipolar-ion form and the neutral form by means of the CNDO method. The relative stability of both the dipolar-ion form and the neutral form in the gas state was reproduced by our calculation. The geometry of the glycine was also reproduced by the CNDO method, indicating the validity of our calculation. In addition, the relative stability of the two tautomeric forms of glycine was proved to be independent of its geometrical modifications. The experimental fact that the dipolar-ion form is more stable than the neutral form in an aqueous solution was well explained by the calculation of the interaction energy between the solute and the solvent.
Effect of Halogens and Oxygen on the Emission of Thermal Positive Ions from the Tungsten Surface
Authors: Kodera Kumasaburo , Kita Yoshifumi , Kusunoki Isao , Kishi Hiroshi , Sakiyama Atsuhiro 
Published: July 2006

Abstract
The effect of chlorine, bromine, and oxygen on the emission of thermal positive ions from tungsten filaments has been studied. When a tungsten filament is heated in a vacuum, positive ion emission is always observed, and it cannot be removed completely by flashing the filament at high temperatures. This background ion emission increases greatly in halogen or oxygen. Main positive ions are K+ and Na+. The increase cannot be explained by the increase of the work function of tungsten by the formation of adsorbed layer of halogen or oxygen atoms. It is ascertained that the tungsten surface reacts with these gases and the reaction products evaporate as neutral particles. As the reaction proceeds, tungsten surface is removed successively and alkali metal atoms in the bulk are exposed to the surface and contribute to the positive ion emission.
Investigations on the Kinetics and Mechanism of the Reduction of Mercuric Chloride by Malic Acid, Induced by Potassium Peroxodisulphate
Authors: Kumar Krishna , Saxena L K 
Published: July 2006

Abstract
The S2O82− induced reduction of mercuric chloride by malic acid has been studied by estimating the precipitated calomel. Kinetic measurements reveal the reduction rate to be independent of the acid concentration and first order in peroxodisulphate, but only to up an optimum concentration, whereafter further increase in inductor concentration decreases the reduction rate. A fractional order dependence in mercuric chloride concentration is encountered. The reaction is characterized by an initial of period induction. The initial rapid consumption of the acid results in lowering of the rate beyond a particular stage of the reaction. Increase of temperature and concentration of reactants is found to effect the period of induction. H+ ions and oxygen inhibit the reduction rate. Products identified are mainly calomel, carbon dioxide and malonic acid. A chain mechanism in which radical ion chain carriers participate, has been suggested.