bluuebunny/crossref_metadata_2025 huggingface dataset:
The Activation of Platinum Electrodes by Preoxidation
Authors: Shibata Shigeo
Published: July 2006

The decay of the activity of bright platinum electrodes activated by means both of electrolytic and chemical preoxidations have been studied under a hydrogen atmosphere.

The life of the activity has been shown to depend upon the extent of the oxidation of the surface in the pretreatment. The structural change of surfare caused by the preoxidation appears to be responsibe for the enhanced activity.
The Concentration of Molecular Hydrogen on the Platinum Cathode
Authors: Shibata Shigeo
Published: July 2006

The concentration of molecular hydrogen in the vicinity of the bright platinum cathode during electrolysis was determined as a function of current density by means of two different methods, the potential-time curve on the reversal of current from cathodic to anodic, and the concentration overpotential obtained by extrapolating the decay curve of the overpotential to zero time, free from other overpotentials. The agreement between the results for the concentration derived from the potential-time curve and from the concentration overpotential was satisfactory. It was found that the concentration of hydrogen increased with the increasing ik value and approached a limiting value of 11.6×10−2 mol./l. for cathodic currents exceeding about ik=300 mamp./cm2.
The Kinetics of Substitution Reactions Involving Metal Complexes. VIII. Reaction between Copper(II) and Ethylenediaminetetraacetatocobaltate(II) Complexes in Aqueous Solutions
Authors: Tanaka Nobuyuki , Osawa Hisao , Kamada Minoru
Published: July 2006

The kinetic study of the substitution reaction of copper(II) ions and cobalt(II)-EDTA complexes in acetate buffer solutions has been carried out with the same procedure as that reported previously. The reaction was found to proceed, under the experimental conditions, through three simultaneous reaction paths similar to those found in the substitution reaction of copper(II) ions and lead(II)-EDTA complexes. The rate constants for three elementary reactions of those reaction paths were determined at ionic strength 0.2 at 5 and 15°C. A reaction path in which the dissociation of cobalt(II)-EDTA complex is rate-determining was not observed in this substitution reaction.
The Angular Dependency of the ESR Proton Hyperfine Coupling Constant of the CH2 Group
Authors: Morokuma Keiji , Fukui Kenichi
Published: July 2006

Valence-bond calculations of the angular dependency of the proton coupling constants of the methylene group in the ESR spectra have been carried out. If the rotation of the group is the only type of deformation, the cos2θ rule by McConnell seems to be valid. If the rocking of the group takes place, however, the angular dependency is entirely different from the cos2θ rule, and the deformation angle based on the rocking model is much smaller than that derived by the cos2θ rule. This finding has been applied to the unequal coupling constants of the two methylene protons of the allyl-type radical in polyethylene.
The Dissolution and Anion Exchange Behavior of Rare Earth and Other Metallic Elements in Potassium Bicarbonate, Potassium Carbonate and Ammonium Carbonate Solutions
Authors: Taketatsu Tomitsugu
Published: July 2006

The amounts of rare earth ions dissolved in a potassium bicarbonate solution, as well as those of other metallic ions dissolved in potassium bicarbonate, potassium carbonate and ammonium carbonate solutions, have been measured. Moreover, the minimum concentrations of potassium bicarbonate, potassium carbonate and ammonium carbonate required to dissolve the precipitates of the metallic bicarbonate and carbonate completely has been determined, and the distribution coefficients, Kd, of the completely dissolved metallic ions between an anion exchange resin and a potassium bicarbonate, potassium carbonate or ammonium carbonate solution had been measured. On the basis of those findings, the dissolution and anion exchange behavior of the metallic ions has been discussed, and the applicability to an analytical separation has been described.
Formation of Ion-pair Cr3+–SO42− in Aqueous Solution
Authors: Tsuchiya Ryokichi , Umayahara Akira
Published: July 2006

1) By measuring the conductivity of the solution of hexa-aquochromium(III) sulfate and potassium-chrome alum, the formation constant of the ion-pair [Cr(H2O)6]SO4+ has been calculated.

2) By measuring the pH, ion exchange separation and electrical conductivity of the heated solution of potassium-chrome alum and of the solution of the alum heated in the solid state, their ion compositions have been deduced.

Appreciation is expressed to Messrs. Teruyoshi Fujishima and Tosuke Imamura for their help in the determination of the electrical conductivity.
The Radiolysis and Photolysis of Cycloheptatriene
Authors: Arai Shigeyoshi , Maemori Michio , Yamaguchi Kenji , Shida Shoji
Published: July 2006

1) In the photosensitized reaction of cycloheptatriene vapor, toluene was produced as the result of isomerization. The amount of toluene formation decreases as the pressure of cycloheptatriene increases. Isomerization to toluene proceeds through the excited molecule, which may be collisionally deactivated.

2) The ESR experiments at low temperatures show that cycloheptatrienyl radicals are formed by electron irradiation. However, the yield of the radical formation is low, nearly equal to that of benzene.

3) In the radiolysis of liquid cycloheptatriene the G values of the gaseous products and toluene are very small. The G value of the polymer seems to suggest the low yield of the radical formation at the initial step. We concluded that the major part of the absorbed energy results in the formation of the excited molecule, the electronic energy of which is readily converted to thermal energy.
The Polymerization Reaction of Sodium Phosphate
Authors: Nakagaki Masayuki , Inoue Hiroshi , Fujie Tadao , Ohashi Shigeru
Published: July 2006

Two kinds of polymerization reactions, the condensation polymerization of sodium dihydrogen orthophosphate anhydrate (NaH2PO4) and the ring-opening polymerization of sodium trimetaphosphate, have been compared by determining the average degree of polymerization of the whole molecule, \barn0, and of each branch, \barn∞, and the average number of branches, B, per molecule.

As a result, it has been concluded that the remarkable difference between these two reactions can be explained by simultaneous polymerization and depolymerization during the heating. In the case of the condensation polymerization, the polymerization process is more important because the removal of water needs much heating, while, in the case of the ring-opening polymerization, the depolymerization process is more important because the polymerization is completed almost immediately after the material is melted.
The Redetermination of the Crystal and Molecular Structure of Chloral Hydrate
Authors: Ogawa Kazuhide
Published: July 2006

The crystal structure of chloral hydrate has been redetermined by the two-dimensional Fourier method and the least-squares method on the NEAC-2203 computer. It is monoclinic and belongs to the P21/c space group, with four molecules in a cell of the dimensions a=11.50,b=6.04,c=9.60Å and β=120.0°. The molecular structure of chloral hydrate is of the gem-dihydroxy compound type with the two OH groups in the staggered gauche-position referred to the adjacent C–Cl3 group. The molecules of chloral hydrate in the crystal are held together mainly by the van der Waals attraction of Cl…Cl and by the bifurcated hydrogen bonds of (Remark: Graphics omitted.). As a result of differential thermal analysis, a high-temperature phase has been found between 53.6° and the melting point, which was ascertained by X-ray diffraction powder patterns. Some of the molecules of chloral hydrate appear to dissociate into water and chloral and attain equilibrium with them. This is inferred from infrared study and from the chemical reactivity with the Schiff reagent.
The Photochemical Decomposition of α, α-Diphenyl-β-picrylhydrazyl (DPPH) in Solution. I. A Kinetic Study of the Reaction
Authors: Suzuki Atuo , Takahasi Makoto , Shiomi Kengo
Published: July 2006

Studies of the photochemical decomposition of DPPH in solution have been made by the kinetic method.

1) The decomposition proceeds by means of the light in the region of the first absorption band of DPPH (λmax=520mμ), and the decomposition rate has a linear dependence on the amount of light absorbed.

2) A rate expression fitting the kinetic experiment has been obtained, and this expression has been compared with the rate expession derived on the basis of the possible reaction mechanism, which includes the process of the reaction of an excited DPPH with another, normal DPPH.

3) An increase in the rate with the reaction temperature has been observed in the temperature range10∼50°C, and the two constants determined in the experiment have been related to the rate constants of the elementary processes in the proposed reaction mechanism.
Studies of the Drawing of Polyamide Fibers. II. The Drawing of Heat-treated Nylon Monofilaments
Authors: Hattori Hiroshi , Takagi Yasuo
Published: July 2006

In order to investigate the influence of the structure of an undrawn sample on the change in physical properties upon drawing, undrawn nylon monofilaments were drawn to various draw ratios after having been heat-treated at several temperatures; some properties, such as tensile strength, shrinkage in boiling water and specific gravity, were then measured on these drawn samples. Although the minimum of tensile strength observed at the draw ratio near 2 had a tendency to disappear upon the heat-treatment of an undrawn sample, the strength did not increase in the range of a low draw ratio. When an undrawn sample was heat-treated above 150°C, a maximum appeared at a draw ratio near 2 in the plot of shrinkage in boiling water against the draw ratio. The higher the heat-treating temperature of an undrawn sample, the greater the maximum of shrinkage. The specific gravity decreased during drawing when the undrawn sample was of a rather high crystallinity, but it increased when the undrawn sample was of a low crystallinity. These results have been discussed, and it has been suggested that the polymer structure becomes most unstable at the intermediate stage of drawing.
Thermal and Radiation Oxidations of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. I. The Thermal Behavior of Iron Sulfate and Chloride in Aqueous Solutions without Benzene
Authors: Hotta Hiroshi , Suzuki Nobutake
Published: July 2006

The rate of the ferrous oxidation at 150°C is 6.10×10−4sec−1 for sulfate, and 2.78×10−4sec−1 for chloride at the oxygen pressure of 30 atm. The precipitation reaction of iron species is through hydrolyzed ferric ions even in the ferrous solution. The rate of precipitation for ferric sulfate is given in Fig. 7, with the activation energy of 12.5 kcal./mol. The precipitate is amorphous at 100°C and completely α-Fe2O3 at 200°C.
Decomposition of Peroxybenzoic Acid in Solution. IV. Decomposition in Solvents in the Presence of Radical-Generators
Authors: Tokumaru Katsumi , Inamoto Naoki , Simamura Osamu
Published: July 2006

The decomposition of peroxybenzoic acid in solvents was accelerated in the presence of radical-generators such as α,α′-azobisisobutyronitrile and isobutyryl peroxide. This acceleration was ascribed to the induced decomposition of peroxybenzoic acid by radicals formed directly or indirectly from these radical-generators.
Studies of the Solvent Extraction of Zirconium-95 in the Tribenzylamine-Hydrochloric Acid System
Authors: Omori Takashi , Suzuki Nobuo
Published: July 2006

The extraction process of zirconium-95 from hydrochloric acid solutions tribenzylamine is shown by the following reactions:

ZrCl62−+2RCl\ightleftharpoonsR2ZrCl6+2Cl−

followed by the reaction of the above species with TBA-Cl in a chloroform solution:

R2ZrCl6+2RCl\ightleftharpoonsR2ZrCl6·2RCl

The main extractable species of zirconium, ZrCl62−, is formed from the zirconyl ions:

Zr(OH)2Cln(2−n)++2H++(6−n)Cl−\ightleftharpoonsZrCl62−+2H2O

On the basis of the present results and of previously reported data on niobium extraction, some information with respect to the optimum conditions for the separation of zirconium and niobium have been given.
Studies on Antibiotics and Related Substances. XVIII. The Synthesis of 5-Methyl-2-methylenecyclopentanone-3-carboxylic Acid, an Antitumor Substance, and Related Mannich Bases
Authors: Kinoshita Mitsuhiro , Nakada Saburo , Umezawa Sumio
Published: July 2006

1) The Mannich reaction of 5-methylcyclopentanone-3-carboxylic acid with formaldehyde and dimethylamine hydrochloride gave a mixture of 2-(dimethylaminomethyl)-5-methylcyclopentanone-3-carboxylic acid (VI) and two kinds of geometrical isomers of 5-(dimethylaminomethyl)-5-methylcyclopentanone-3-carboxylic acid (IIa and IIb), from which IIa, an unstable methiodide (VII) of methyl ester of VI, and IIb were isolated.

2) Methyl 2-(dimethylaminomethyl)-5-methylcyclopentanone-3-carboxylate methiodide (VIII) was degraded to give methyl 5-methyl-2-methylencylopentanone-3-carboxylate (IX), which was then hydrolyzed to 5-methyl-2-methyleneclycopentanone-3-carboxylic acid (X), a homolog of sarkomycin.

3) The steric relation between IIa and IIb has been discussed.

4) The destructive distillation of methyl 2-(dimethylaminomethyl)-5-methylcyclopentan-one-3-carboxylate (VII), followed by hydrolysis, afforded 2,5-dimethylcyclopenten-1-one-3-carboxylic acid (XII), an isomer of X. It was found that the product was obtained also by the thermal decomposition of the methyl ester hydrochloride of IIa. This funding may be accounted for on the assumption that a rearrangement of the dimethylaminomethyl group occurred through a kind of retrograde Mannich reaction.

5) Some derivatives of the above-mentioned Mannich bases were described.

6) Both X and its methyl ester were found to possess antitumor and antibacterial activities.
Oxidation of Alcohols by Cerium(IV). II. Oxidation of Methanol by Ceric Sulfate
Authors: Muhammad S S , Rao K Vijayachander
Published: July 2006

The oxidation of methanol by cerie sulfate in sulfuric acid solutions was studied in the temperature range 40∼70°C. The rate of oxidation depended directly on the concentration of cerium(IV) and methanol. At constant ionic strength the rate was directly dependent on the concentration of sulfuric acid. But when the ionic strength is not maintained, the rate changes inversely with sulfuric acid. At constant acid concentration, a negative salt effect is observed. The reaction occurs without the intermediate formation of a complex. The activation energy was derived to be 26300 cal. mol−1. It has been shown that the mechanism of Waters for the oxidation of α-hydroxyacids by manganese pyrophosphate can be used to explain the present data.
The Synthesis and Ring-opening Polymerization of N-Substituted 2-Iminotetrahydrofurans
Authors: Mukaiyama Teruaki , Sato Kenichiro
Published: July 2006

Various N-substituted 2-iminotetrahydrofurans are prepared from 2,2-diethoxytetrahydrofuran and corresponding amines.

N-Substituted 2-iminotetrahydrofurans give N-substituted polyamides by ring-opening polymerization when treated with a catalytic amount of boron trifluoride etherate.

On the other hand, 2-methylenetetrahydrofuran undergoes mainly a vinyl-type polymerization.
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

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

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

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

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>styrene, 20>ethyl acrylate, 5>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

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

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

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

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

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

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

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.
The Solvolysis of Acid Chlorides. A Presentation of the Problem and a Proposal for the Mechanism
Authors: Minato Hiroshi
Published: July 2006

A mechanism has been proposed which seems to be consistent with all the experimental results obtained by various workers on the solvolyses of acid chlorides.
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

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

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 > anhydride > 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

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

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

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

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

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

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

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

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

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).
Phase Transition in the Ammonium Bromide Crystal: The Thermal Motion of the Ammonium Ion
Authors: Sorai Michio , Suga Hiroshi , Seki Syûzô
Published: July 2006

We have measured the heat capacities of the ammonium bromide crystal from 13°K to 305 °K and have found two phase transitions in this temperature region. From the results, the heat and entropy of transitions at the transition points, 107.5°K and 235.0°K, have been derived: for the lower transition, ΔHtr=29.29 cal. mol.−1 and ΔStr=0.271 cal. deg−1·mol−1; for the upper one, ΔHtr=156.1 cal.·mol−1 and ΔStr=0.714 cal. deg−1 mol−1. The values of the entropy and enthalpy function at 298.15°K are: S°=26.97 cal. deg−1 mol−1 and (H°–H°O)⁄T=13.56 cal. deg−1 mol−1. The torsional motions of the ammonium ions may well be represented in terms of a periodic potential function at the lowest temperature modification. The torsional frequency, 340±7 cm−1, and the potential barrier height, 4.00±0.16 kcal.mol−1, as determined on the basis of the thermal data, agree well with the values obtained in other experiments.

The infrared spectra of thin, non-scattering films of ammonium bromide have been obtained at 298°K, 100°K, 88°K, 40°K and 18°K. The torsional frequencies determined from the spectra by adopting Wagner-Hornig’s assignments have been found to be almost independent of the temperature in the lowest modification.
Studies of Antibiotics and Related Substances. XXI. The Synthesis of Deoxy and Chlorodeoxy Derivatives of Kanamycin
Authors: Tsuchiya Tsutomu , Umezawa Sumio
Published: July 2006

1) Deoxykanamycin has been synthesized in a four-stage sequence beginning with kanamycin. Kanamycin has been converted to tetra-N-carbobenzoxykanamycin, and this transformed in turn to tetra-N-carbobenzoxy-mono-O-tosylkanamycin (or the corresponding nasyl derivative), to tetra-N-carbobenzoxy-deoxyiodokanamycin, and finally to deoxykanamycin.

2) The above nasyl derivative has been transformed via tetra-N-carbobenzoxy-chlorodeoxy-kanamycin to chlorodeoxy-kanamycin.

3) 6-O-(3-Amino-6-chloro-3,6-dideoxy-α-d-glucosyl)-deoxystreptamine hydrochloride has been obtained by the controlled acid-hydrolysis of chlorodeoxy-kanamycin.

4) The hydrogenolysis of tetra-N-carbobenzoxy-bromodeoxy-kanamycin has given deoxykanamycin.

5) It has been found that deoxykanamycin and chlorodeoxy-kanamycin are strongly antibacterial and that their antibiotic spectra are essentially similar to that of kanamycin.
Studies of Peptide Antibiotics. II. Cyclo-l-valyl-l-ornithyl-l-leucyl-d-phenylalanyl-l-prolylglycyl
Authors: Kato Tetsuo , Kondo Michio , Ohno Motonori , Izumiya Nobuo
Published: July 2006

A cyclic hexapeptide, cyclo-l-valyl-l-ornithyl-l-leucyl-d-phenylalanyl-l-prolylglycyl, was synthesized for the purpose of comparing its antibacterial action, if any, with the cyclopeptide antibiotics, such as gramicidin S, with which it shares several common structural features.

Synthesis was achieved by condensation of p-methoxybenzyloxycarbonyl-l-valyl-δ- benzyl-oxycarbonyl-l-ornithine azide with l-leucyl-d-phenylalanyl-l-prolylglycine ethyl ester, followed by treatment of the resulting diacyl hexapeptide ester with alkali to remove the ethyl ester group. The diacyl hexapeptide so derived was converted to the p-nitrophenyl ester by the action of di-p-nitrophenyl sulfite, and after removal of the p-methoxybenzyloxycarbonyl group with trifluoroactetic acid, the hexapeptide p-nitrophenyl ester was transformed to the cyclic benzyloxycarbonyl-substituted hexapeptide by treatment with a large excess of pyridine. The cyclic benzyloxycarbonyl-substituted peptide was hydrogenated in the presence of palladium black to yield the desired cyclic hexapeptide hydrochloride.

The effects of the synthesized cyclic peptide on bacterial growth were examined. No antibacterial activities were observed against the microorganisms utilized here.
The Formation Constants of Chromium(III)-Glycinato and α-Alaninato Complexes
Authors: Matsukawa Hiroharu , Ohta Mitsuo , Takata Shichiro , Tsuchiya Ryokichi
Published: July 2006

The formation constants of chromium(III) glycinato and α-alaninato complexes have been determined by the pH method. The values Connected with these two complexes are so close to each other that no effect of the presence of a methyl group could be found.

The values of the first formation constants of these complexes are smaller than the mean value of those of ethylenediamine and oxalato complexes. These facts have been explained in terms of the finding that the decrease in the entropies of the formation of α-amino acid complexes is larger than that of ethylenediamine or oxalato complexes because the symmetry of the amino acid complexes is lower than of the ethylenediamine or oxalato complexes.
The Diamagnetic Study of the Nature of the Association of Acetic Acid. II. The Binary Systems of Acetic Acid with Triethylamine, Pyridine and Aniline
Authors: Sriraman S , Shanmugasundaram V , Sabesan R
Published: July 2006

The diamagnetic susceptibilities of three binary systems have been studied using the Gouy method. Deviations of the observed diamagnetic susceptibility values from Wiedemann’s additive law have been discussed in the light of the partial ionisation of acetic acid with the solvent bases.
Studies on Antibiotics and Related Substances. XX. The Synthesis of Adenine Nucleosides of 3-Amino-3-deoxyglucose and 6-Amino-6-deoxyglucose
Authors: Fukatsu Shunzo , Umezawa Sumio
Published: July 2006

1) The subject amino-nucleoside have been synthesized from blocked acetohalogeno amino-sugars and 6-benzamidopurine.

2) It has been shown that the α- and β- anomers of blocked acetohalogeno aminosugars (Ia, Ib and Via, VIb) both yield the same β- nucleosides (V, IX).

3) 9-(3-Amino-3-deoxy-β-d-glucopyranosyl)- adenine was found to possess a weak antitumor activity.
Vinyl Polymerization. CXVI. The Effects of Several Sulfides and Oxides on Radical Polymerization
Authors: Tsuda Kazuichi , Kobayashi Shigeru , Otsu Takayuki
Published: July 2006

A study has been made to see how some sulfides, such as diphenyl disulfide, diphenyl sulfide, dibenzyl disulfide, and dibenzyl sulfide, and such oxides as diphenyl ether and dibenzyl ether affect the radical polymerization of styrene or methyl methacrylate. None of these compounds acted effectively either as an initiator or as a retarder in the thermal polymerization at 60°C. When employed as photo-sensitizers, the disulfides have been proven to have a remarkable activity of initiation, the monosulfides acting less effectively as initiators. Moreover, the oxides showed no such activity at all. When sulfides were used as photo-sensitizers, the rate of polymerization did not obey the equation of the square root of the concentrations of the sulfides. This may be attributable to the participation of the sulfide radicals in the initiation and termination. The chain transfer constants of these compounds at 60°C were in the order of disulfides>monosulfides>oxides.
Quinoxaline Derivatives. VI. An Unusual Chlorine Substitution during the Reaction of 3-Hydroxy-2-phenylquinoxaline 1-Oxide with Acetyl Chloride
Authors: Ahmad Yusuf , Habib M S , Ziauddin  , Bashir Naz
Published: July 2006

3-Hydroxy-2-phenylquinoxaline 1-oxide (Ia), on being heated with acetyl chloride, instead of giving the acetyl derivative, gives a chloro compound (IIg), with a simultaneous loss of its N-oxide function. Ia, on being refluxed with a mixture of concentrated hydrochloric acid and acetic acid, undergoes the same transformation. Other derivatives (Ib–f) of Ia behave similarly and give the corresponding chlorine-substituted bases (IIh—1), the structure of which has been established by authentic syntheses.

A nucleophilic mechanism of this chlorination has been proposed, in which the presence of an oxygen function a position 3 of the 2-substituted quinoxaline 1-oxides seems to direct the chlorine substitution to position 6.
The Formation of Crystal Violet by the Reaction of N,N-Dimethylaniline with Aluminum Chloride
Authors: Sato Hiroyasu
Published: July 2006

The reaction of N,N-dimethylaniline with aluminum chloride in vacuo has given a deep blue solution. This blue solution turns violet because of moisture or the added methanol. The electronic spectra of these solutions seem to be identical with that of crystal violet. The finding that transient green species appear when the vacuum cell system is opened to air can be interpreted in terms of the color of crystal violet dissolved in hydrochloric acid. From these findings the formation of crystal violet has been concluded.