bluuebunny/crossref_metadata_2025_split huggingface dataset:
Influence of Substituent Groups on Nuclear Reactivity in the Formation of Substituted Biphenyls by Reaction of Aromatic Diazo and Related Compounds with Aromatic Liquids. VIII. Phenylation and p-Methylphenylation. The Separation of the Polar and the Conjugative Effect
Authors: Itô Ryôichi , Migita Toshihiko , Morikawa Naotake , Simamura Osamu 
Published: July 2006

Abstract
N-Nitrosoacet(anilide-14C) and N-nitroso-(p-methyl-14C)acetanilide have been decomposed at 20.0°C in mixtures of benzene and monosubstituted benzenes, and the reaction products have been analyzed for biphenyl and substituted biphenyls by the isotope dilution method. From the results of these competitive experiments, the partial rate factors for the phenylation and p-methylphenylation have been calculated (Tables I and II).
The values of the partial rate factor for the meta position give a satisfactory Hammett plot with a slope of +0.05 for the phenylation and one with a slope of +0.03 for the p-methylphenylation, suggesting that the p-methylphenyl radical has little, if any, measure of polar character.
The correlation of the ρ values for various arylations with the inductive constant for the substituent group on the arylating radical indicates that the effect of the substituent group in the radical is purely inductive in nature.
The partial rate factor for the para position, kp/k, is found to be related to Hammett’s substituent constant by the following equation:
log(kp⁄k)=ρσp+τp
where ρ is the Hammett reaction constant for this arylation as determined from the Hammett plot of the partial rate factors of the meta position. τp is found to be tolerably constant for each substituted benzene, irrespective of the nature of the attacking aryl radical, and represents that part of the conjugative effect of the substituent which is independent of the polar nature of the attacking radical.
Molecular orbital calculations have given results which rationalize the trend found in the τp values.
The Reaction Rate in Binary Mixed Solvents
Authors: Kondo Yasuhiko , Tokura Niichiro 
Published: July 2006

Abstract
The reaction rate in binary mixed solvents have been discussed and following facts confirmed :
1) A linear relation does not hold between logk and the molar fraction of the components in most cases.
2) The deviation from linearity is usually positive, and the maximum deviation is found at xA≤0.5, xA is the molar fraction of a component in which the rate is faster than in another component.
3) The experimental results may be expressed with good accuracy by the formula:
logk=xAlogkA+xBlogkB+xAxBa
+b(xA–xB)+c(xA–xB)2+d(xA–xB)3
4) The parameter a depends upon the type of reaction and the solvent system, but it does not depend on the nature of the reactants.
5) The additivity of has been proved theoretically and confirmed a for the Menschutkin reaction in various solvent mixtures.
The Preparation and the Co-ordination Chemistry of Cobalt Complexes with Schiff Bases Derived from Salicylaldehyde and Alkyl Amines
Authors: Nishikawa Hiroaki , Yamada Shoichiro 
Published: July 2006

Abstract
A novel method has been described for preparing bis(N-n-alkyl-salicylideneiminato)cobalt-(II), where n-alkyl represents methyl, ethyl, n-propyl, n-butyl and higher alkyls. Bis(N-α-branched alkyl-salicylideneiminato)cobalt(II)-complexes have been prepared by a simpler method, where α-branched alkyl denotes isopropyl, 1-ethylpropyl, s-butyl, t-butyl and cyclohexyl. The benzyl derivative has also been prepared. Tris(N-n-alkyl-salicylideneiminato) cobalt(III) complexes have been prepared.
On the basis of electronic absorption spectra, it has been concluded that bis(N-alkyl-salicylideneiminato)cobalt(II)-complexes have a tetrahedral configuration, whether the alkyl used as a substituent represents an n-alkyl or an α-branched alkyl.
The relative stability and the configuration of cobalt(II)-complexes have been discussed.
Studies of the Organic Reaction of Metal Carbonyl. V. The Reaction of Cobalt Hydrocarbonyl with Olefin—The Effects of the Reaction Conditions and of the Structure of Olefin
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa , Masada Hiromitsu , Okuda Yasukazu 
Published: July 2006

Abstract
It has been observed that the reaction of 1-olefin with cobalt hydrocarbonyl is remarkably affected by the reaction conditions and by the structure of olefln.
Some functional groups, such as the ester, n-butoxy and phenyl groups, adjacent to a C= C bond increase the reactivity of the C=C bond; the order of the reactivity is n-butyl vinyl ether, 103&gt;styrene, 20&gt;ethyl acrylate, 5&gt;pentene-1. (The numbers indicate the relative reactivities, which have been roughly calculated from the gas absorption curve.)
At a relatively low temperature (below 0°C), the α-carbon atom of the C=C bond of all these olefins except pentene-1 is selectively carbonylated; the reaction scheme may be considered to be as follows; suggesting that cobalt hydrocarbonyl is acting as an acid:
(Remark: Graphics omitted.)
However, these acylcobalt carbonyls with the branched structure isomerize to those with the straight one:
(Remark: Graphics omitted.)
A relatively high temperature (25°C) and a nitrogen atmosphere promote this isomerization considerably. The reverse isomerization seems to occur only with difficulty. On the other hand, these olefins mainly give the β-carbon carbonylated product at 25 °C, the formation of which seems to result from the two successive reactions, the carbonylation of the α-carbon atom and the isomerization of the corresponding acylcobalt carbonyl. However, the distribution of the products from pentene-1 is not affected by the reaction temperature.
A relatively high pressure of carbon monoxide is advantageous for this reaction. Under a nitrogen atmosphere, some reaction other than the carbonylation seems to occur very rapidly, consuming a large part of the cobalt hydrocarbonyl used; a nitrogen atmosphere has an inhibitory effect on the carbonylation.
The Reduction of Isothiocyanato-ammine Complexes of Chromium(III) at the Dropping Mercury Electrode
Authors: Tanaka Nobuyuki , Ito Tasuku , Tamamushi Reita 
Published: July 2006

Abstract
The reduction of a series of isothiocyanato-ammine chromium(III) complexes [Cr(NCS)p-(NH3)6−p](3−p)+ at the dropping mercury electrode has been studied. The direct current, the alternating current and the Kalousek polarograms of these complexes have been measured in various supporting electrolyte solutions. The nature of the reduction waves, corresponding to the one-electron reduction of chromium(III) to chromium(II), has been discussed.
Transported Entropies and Conventional Eastman Entropies of the Transfer of Some Univalent Ions in Aqueous Solutions at 25°C
Authors: Ikeda Toshio 
Published: July 2006

Abstract
Absolute ionic transported entropies, conventional ionic Eastman entropies of transfer, and conventional ionic heats of transfer, using the same convention (S°H+≡0) as that adopted in assigning conventional standard ionic entropies, have been recalculated for ten univalent ions from the most accurate data now available on the initial thermoelectric powers and the Soret coefficients.
The Synthesis of Methacrylic Esters by Carboxylation Reaction of Methylacetylene. I. Methyl Methacrylate; Reaction Conditions and Products
Authors: Sakakibara Yasumasa 
Published: July 2006

Abstract
The synthesis of methyl methacrylate (MMA) by the carboxylation reaction of methylacetylene has been investigated.
Stoichiometric process: The carboxylation reaction was carried out under atmospheric pressure by premixing a 25∼50 vol.% of acetylene in methylacetylene and under pressure (heating to 80°C). The total yields of MMA and MAA (methacrylic acid) were 45% (based on the methylacetylene consumed) under atmospheric pressure and 49% (66% (based on the nickel carbonyl used)) under pressure. Small amounts of methyl trans-crotonate, methyl isobutyrate, acetone, etc., were obtained as by-products, together with considerable amounts of high-boiling materials (not investigated).
Catalytic process: The reaction proceeded comparatively smoothly at 170∼180°C and under about a 10 atm. partial pressure of carbon monoxide when triphenylphosphine nickel bromide complexes and nickel carbonylconcentrated hydrochloric acid were used as catalysts. A triphenylphosphine nickel bromide catalyst, (Ph3P)2NiBr2, gave the best total yield, 47%. It was found that, without the addition of acid, nickel carbonyl exhibits a catalytic action in the presence of water at 170∼180°C. The total yield of MMA and MAA by this method was 46%. Fortunately, scarcely any acetone or methyl ether were formed. In view of this series of experimental results, it may be supposed that the poor total yield of MMA and MAA is chiefly due to the loss of methylacetylene by polymerization.
The Solvent Effects of Esterification: The Reaction of l-Menthol with Acetyl Chloride in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Akiyama Fuminori 
Published: July 2006

Abstract
The solvent effects of the esterification of l-menthol with acetyl chloride in various solvents have been examined polarimetrically. In liquid sulfur dioxide, the rate of the esterification was the fastest among the solvents used. A bare carbonium ion formation in liquid sulfur dioxide may be the reason for this. The comparably large rate in dimethylformamide has also been discussed, along with the solvent effects in various other solvents.
Chronopotentiometry of Hexamminechromium(III) Ions in Acetate Buffer Solutions
Authors: Tanaka Nobuyuki , Yamada Akifumi , Tamamushi Reita 
Published: July 2006

Abstract
The reduction of hexamminechromium(III) ions at the dropping mercury electrode has been studied chronopotentiometrically in acetate buffer solutions. The electrolysis at constant cathodic current gives a well-defined chronopotentiogram which corresponds to the one-electron reduction of chromium(III) to chromium(II), but the anodic chronopotentiogram which is obtained by the electrolysis at constant anodic current is clearly separated from the cathodic one.
A general treatment for a chronopotentiometric potential-time curve for the electrode process with the following chemical reaction has been developed by the application of Lagrange’s theorem. The results indicate that hexamminechromium(III) ions are irreversibly reduced at the dropping mercury electrode without any preceding chemical reactions prior to the more or less irreversible electron-transfer process, followed by the rapid aquation of the reduced species.
Polarographic and Coulometric Studies of cis-Dioxalatodiaquochromate(III)
Authors: Tanaka Nobuyuki , Itabashi Eiki , Tamamushi Reita , Satô Gen 
Published: July 2006

Abstract
The current-voltage curves of cis-dioxalatodiaquochromate (III) have been recorded at the dropping mercury electrode in various supporting electrolyte solutions. A well-defined wave with a half-wave potential of −1.522 V. vs. SCE was obtained in 0.3 m potassium chloride solutions containing 0.005% gelatin. The limiting current in this case was proved to be diffusion-controlled from its dependence on the effective pressure of mercury on the dropping mercury electrode and from the characteristics of the current-time curve during the life of a mercury drop. The electrode reaction of the complex was found to be irreversible by a study of both the characteristics of the Kalousek polarogram and the relation of log{\bari⁄\barid–\bari)} against E.
The number of electrons involved in the reduction was determined by the controlled-potential coulometric method. The coulometric investigation showed that cis-dioxaloto-diaquochromate(III) is reduced to the metal at the dropping mercury electrode. This conclusion was also supported by the detection of chromium from the surface of the mercury pool electrode used in the controlled potential electrolysis. The value of the diffusion coefficien t of cis-dioxalatodiaquochromate (III), calculated for a three-electron reduction, was also reasonable in comparison with those of other chromium (III) complexes.
The Synthesis of Oxygenated Organic Compounds from Methanol and Carbon Monoxide-Hydrogen Mixtures in the Presence of a Mixture of Cobalt Acetate and an Iodide Used as the Catalyst
Authors: Mizoroki Tsutomu , Nakayama Mikitake 
Published: July 2006

Abstract
The reaction of methanol with carbon monoxide-hydrogen mixtures has been carried out in the presence of a mixture of cobalt acetate and an iodide as catalyst. The extent of methanol conversion into C2-oxygenated compounds (acetaldehyde, ethanol and acetic esters) was 40 to 60% when the catalyst concentration (Co(CH3COO)2·4H2O+an iodide) range was form 1.0 to 20 mol%; the temperature range was from 180 to 220°C; the pressure range was from 300 to 500 kg./cm2 (the H2/CO values in synthesis gases were 1.0 to 1.5), and the reaction time was 90 min. The amount of free acetic acid, C3- and higher oxygenated compounds in the liquid product was small. The use of iodine instead of an iodide as an additive for the cobalt acetate catalyst is disadvantageous for this reaction. From the detailed investigation of the influence of the catalyst concentration on the extent of the conversion of methanol into C2-oxygenated compounds, it has been shown that the formation of acetaldehyde is favored in the presence of a relatively large amount of an iodide and that an increase in cobalt acetate results in an increase in the yield of ethanol. It has been postulated that, under these conditions, methanol reacted with carbon monoxide and hydrogen to form acetaldehyde, which subsequently was hydrogenaled to ethanol or dimerized to other oxygenated compounds.
A New Method for the Colorimetric Determination of Hypophosphate Ions with the Molybdenum(V)-Molybdenum(VI) Reagent
Authors: Yoza Norimasa , Ohashi Shigeru 
Published: July 2006

Abstract
It was found that hypophosphoric acid reacts with the molybdenum(V)-molybdenum(VI) reagent at room temperature as well as at 95°C to form a blue complex, the absorption spectrum of which has maximums at 590 and 670 mμ. Although orthophosphoric acid reacts with this reagent at 95°C to form a blue complex, it gives only a faint blue color at room temperature. Hypophosphorous and phosphorous acid do not give any colored products when treated with this reagent. Therefore, the reaction of hypophosphoric acid with this reagent at room temperature can be applied to the colorimetric determination of hypophos-phate ions in the presence of hypophosphite, phosphite, and orthophosphate ions. The differences in the absorption spectra and solvent extraction behavior between the two blue complexes due to hypophosphoric and ortho-phosphoric acid (“hypophosphoric heteropoly blue” and “orthophosphoric heteropoly blue”) have been described. The mole ratios of molybdenum to hypophosphoric and orthophosphoric acid in the blue complexes were found to be approximately 9 and 12 respectively.
The Polymerization and Polymers of Itaconic Acid Derivatives. VI. The Polymerization and Copolymerization of Itaconic Anhydride
Authors: Nagai Susumu 
Published: July 2006

Abstract
The copolymerization of itaconic anhydride and vinyl chloride has yielded copolymers with itaconic anhydride much richer than that in the feed. The rate of the homopolymerization of itaconic anhydride has been compared with the rates of itaconic esters, obtaining the following order: di-2-ethylhexyl ester &gt; anhydride &gt; dimethyl ester. The infrared spectra and solubility character of the polymer have been shown in comparison with those of the monomer. Further, polyitaconic acid has been obtained by the hydrolysis of polyitaconic anhydride with some ease.
The Reactions of Lower Oxo Acids of Phosphorus with the Molybdenum(V)-Molybdenum(VI) Reagent
Authors: Yoza Norimasa , Ohashi Shigeru 
Published: July 2006

Abstract
The reaction of twelve lower oxo acids of phosphorus and orthophosphoric acid with the molybdenum(V)-molybdenum(VI) reagent have been carried out under the conditions prescribed by three different procedures : (1) the reactions for 30 min. at room temperature, (2) the reactions for 1 hr. at 95°C, and (3) the reactions in the presence of sodium hydrogen sulfite for 1 hr. at 95°C. The absorption spectra of the reaction products have been measured. It has been found that the blue products obtained by these reactions are orthophosphoric heteropoly blue and/or hypophosphoric heteropoly blue in all cases and that mechanisms of these reactions are closely related to the structural units of the lower oxo acids of phosphorus and their hydrolysis reactions.
The Electrokinetic Potential of Sparingly Soluble Salts
Authors: Morimoto Tetsuo 
Published: July 2006

Abstract
1) The ζ-potentials of such sparingly soluble salts as barium sulfate, barium chromate, lead (II) sulfate and lead (II) chromate have been measured in water by means of the streaming potential method. Most samples prepared by using either lattice ion in excess have a charge of the same sign as that of the ion. This suggests that the lattice ions occupy many more lattice points on the surface than do other ones, and that it is difficult to remove them by washing. One exception is lead (II) sulfate, in which the ζ-potentials of the two samples are positive. This seems to depend on the surface hydrolysis of lead (II) sulfate.
2) The ζ-potentials vary widely also when the lattice ions are added to water. The effect of both lattice ions are the greatest on lead (II) chromate and the least on lead (II) sulfate. The solubility of the solids is an important factor affecting the variation of ζ-potentials when the lattice ions are added.
3) In order to investigate the effect of the mixed electrolyte solution on the ζ-potential of barium sulfate, sodium citrate, which has a remarkable effect by itself, has been mixed with sodium sulfate or barium nitrate. The resultant ζ-potential curves show a definite minimum, which demonstrates that, although the adsorption of citrate ions excels that of sulfate or barium ions at smaller concentrations, the latter become comparable to the former at larger concentrations.
4) The surface chemical action of triphosphate and orthophosphate ions has been tested. As expected, the higher the polymerization degree of phosphates, the larger the effect on the charge of solid surfaces.
The Heat of Immersion of Aluminum Oxide in Water
Authors: Morimoto Tetsuo , Shiomi Koichi , Tanaka Hiroshi 
Published: July 2006

Abstract
1) The surface properties of two kinds of alumina have been studied by measuring the immersion heats and the water contents. The heat of immersion of alumina showed a maximum at about 600∼650°C, which is considerably higher than the 200∼300°C of silica, and the heat values were much greater than those of silica.
2) It has been concluded that the rehydration process of dehydrated sites plays an important role in the case of the immersion of alumina in water. The heats of hydration calculated from the immersion heats of α- and γ-alumina were 15.8 and 9.60 kcal./mol. water respectively.
Spectrochemical Study of Microscopic Crystals. XXIV. The Structure and Light Absorption of Copper(II) Complexes of Benzoic and Substituted Benzoic Acids
Authors: Yamada Shoichiro , Nishikawa Hiroaki , Miki Seiko 
Published: July 2006

Abstract
Cupric complexes of benzoic and substituted benzoic acids have been prepared, and their configurations in the solid state and in dioxan examined. The substituents have included methyl, chloro, methoxy, nitro and hydroxy groups.
These cupric complexes in dioxan all consist of binuclear cupric complexes with the copper-to-copper bond. Crystal absorption spectra show that Cu(benz)2·C2H5OH and Cu(benz)2·(benzH)·0.5H2O in the crystalline state consist of the binuclear complexes, whereas Cu·(benz)2·3H2O has no such complexes with the copper-to-copper bond. The absorption spectra of several substituted benzoates of copper (II) in the solid state have also been determined, and the structure of the complexes discussed.
It has been found that the maxima of Band I of substituted benzoates of copper (II) in dioxan are linearly dependent upon the pK values of the substituted benzoic acids themselves.
A Note on the Solid Chemisty of the NiO-Li2O Solid Solution
Authors: Iida Yoshio , Hayashi Naoyoshi 
Published: July 2006

Abstract
In the NiO-Li2O solid solution, it has been certified by a chemical analysis that the amount of Ni3+ formed in the solid solution was the same as that of Li+ dissolved. The NiO-Li2O solution can be expressed by a molecular formula, Ni1−2x2+ Lix+ Nix3+ O. The solubility limit of lithium to nickel oxide is 25 atomic per cent at 800°C, which is an optimum temperature for the formation of the solid solution.
The lattice parameter of nickel oxide decreases with the increase in the amount of lithium dissolved. From Vegard’s law, the ionic radius of Ni3+ has been calculated to be 0.60 a. u.
The Formation Constant of Chromium (III)-Ethylenediamine Complexes
Authors: Ohta Mitsuo , Matsukawa Hiroharu , Tsuchiya Ryokichi 
Published: July 2006

Abstract
1) The formation constants of chromium (III) complexes with ethylenediamine, the simplest bidentate ligand material coordinated by two nitrogen atoms, have been spectrophotometrically determined.
2) It has been shown that the dependence of the formation constant of the first step upon the ionic strength is small.
3) The formation constants of the chromium (III) complexes with ethylenediamine have been found to be remarkably higher than those of the corresponding chromium (II) complexes and a little lower than those of the corresponding cobalt (III) complexes.
4) The difference between the formation constants of the chromium (III) and cobalt (III) ethylenediamine complexes has been qualitatively explained with reference to the crystal-field stabilization energy and to Racah’s electrostatic repulsive parameter.
Asymmetric Hydrogenation with Modified Raney Nickel. III. Studies of the Modified Hydrogenation Catalyst. IV
Authors: Tatsumi Susumu , Imaida Masami , Fukuda Yoshio , Izumi Yoshiharu , Akabori Shiro 
Published: July 2006

Abstract
1) The asymmetric activities of R-Ni catalysts modified with l-2-hydroxyisovaleric acid, l-2-hydroxyisocaproic acid, l-2-hydroxy-3-methylvaleric acid and l-2-hydroxy-3-phenylpropionic acid have been compared with those of catalysts modified with the corresponding l-amino acids, which had the same stereochemical configurations.
2) On modification with l-2-hydroxycarboxylic acids, the greatest asymmetric activities are obtained when the catalysts are treated at pH values below the pH jump of the titration curves of the acids.
3) Catalysts modified with l-2-hydroxycarboxylic acids have asymmetric activities the reverse of those modified with l-amino acids with the same configurations.
4) The modifying effects of O,O′-diacetyl-d-tartaric acid and O-monobenzoyl-d-tartaric acid upon the R-Ni catalyst are entirely different from that of d-tartaric acid.
A Cobalt (III) Complex with Trimethylenediaminetetraacetate
Authors: Tanaka Nobuyuki , Ogino Hiroshi 
Published: July 2006

Abstract
The synthesis of a new cobalt(III) complex, K[Cotrdta]·2H2O (trdta, (−OOCH2C)2N(CH2)3N(CH2COO−)2), has been carried out. The infrared, visible and ultraviolet absorption spectra indicate that a quadrivalent trdta anion in this complex is hexadentate. The infrared, visible and ultraviolet absorption spectra of the cobalt(III) complexes with ethylenedi-aminetetraacetate, propylenediaminetetraacetate and trans-1,2-cyclohexanediaminetetraacetate have also been observed and discussed.
Switch-over of the Mechanism of the Primary Processes in the Photo-oxidation of Xanthene Dyes as Revealed by the Oxygen Consumption Experiments
Authors: Usui Yoshiharu , Itoh Keiko , Koizumi Masao 
Published: July 2006

Abstract
The oxygen up-take of irradiated aqueous solutions of xanthene dyes has been investigated by means of Warburg’s apparatus, and evidence for a switch-over from a D–O to a D–D mechanism is obtained from the variation of dye-concentration. This view is supported by the photobleaching rate and the oxygen concentration effect at high eosine concentrations (∼10−4m).
The quautum yields (γo2) of the consumption are estimated and it is found that γo2(D–D) is larger than γo2(D–O).