bluuebunny/crossref_metadata_2025 huggingface dataset:
The Polarography of Terephthalaldehydic Acid
Authors: Nishiyama Masataka , Maruyama Masao , Hamaguchi Hiroshi
Published: July 2006

The d. c. and a. c. polarography of terephthalaldehydic acid has been investigated in buffered solutions containing no ethanol over the pH range from 1 to 13.

D.C. Polarography.–Terephthalaldehydic acid gives a pre-wave and three reduction waves. The pre-wave, which is due to the adsorption of the reduced form of undissociated molecules, is followed by wave I below pH 4.4. Our results above pH 4.4 accord approximately with Holleck and Marsen’s. The half-wave potential for the wave I is pH-dependent, and the E01⁄2 is −0.69 V. vs. SCE. The half-wave potentials of waves II and III, both pH-independent, are −1.30 and −1.60 V. vs. SCE under the conditions studied. The sum of the wave heights has been kept constant in the pH range from 4.4 to 13.2, and it corresponds to the two-electron reduction of the carbonyl group. The two-step waves, in which wave I is due to the reduction of the undissociated molecule and wave II, to that of its anion, in the pH range from 5.5 to 7.5 form a system of kinetic recombination currents. The recombination and dissociation rate constants have been calculated as kr=1.5×1081. (mol. sec.)−1 and kd=5.2×103 sec−1. The double waves above pH 8.2 have been explained by the carbinolate-free radical dissociation theory.

A.C. Polarography.–A. c. waves have been obtained to corresponding to the d. c. waves. The heights of the a. c. pre-wave and wave I are depressed below pH 5. This depression has been attributed to the strong adsorption of undissociated molecules at the dropping mercury electrode. The relationship between the a. c. wave height and concentration below pH 5 is non-linear. It has been noted that the a. c. kinetic current should be taken into account for the a. c. wave formation.

The electrode process for wave III is irreversible, and a. c. wave III is ill-defined.

A reduction mechanism over the pH range studied has been proposed.
Studies of Isocyanide. II. The Reaction of Isocyanide with Some Radical Sources
Authors: Shono Tatsuya , Kimura Masatoshi , Ito Yoshihiko , Nishida Kiyoto , Oda Ryohei
Published: July 2006

The reactions of cyclohexyl isocyanide with some radical sources, such as perbenzoic acid, benzoyl peroxide, t-butyl perbenzoate, N-nitrosoacetanilide, potassium phenylazoformate and di-t-butyl peroxide, have been studied. The isocyanide does not contribute kinetically to the mechanism of the decomposition of benzoyl peroxide, but the lone pair electrons existing on the carbon atom of isocyanide react very easily with free radicals, especially with acyloxy radicals.

In the reaction with benzoyl peroxide, t-butyl perbenzoate or the N-nitrosoacetanilide acyloxy radical chiefly contributes to the reaction. With potassium phenylazoformate, the phenyl radical is the main reacting species. However, in the case of perbenzoic acid, the reaction is heterolytic, and the main product is cyclohexyl isocyanate.
Synthetic Studies Starting from β-Cyanopropionaldehyde. I. The Synthesis of Adipic Dialdehyde
Authors: Motoki Shinichi , Satsumabayashi Sadayoshi , Tajima Isao
Published: July 2006

A detailed study has been made of the synthesis of adipic dialdehyde starting from β-cyanopropionaldehyde. The hydrolysis of the acetal of this cyanoaldehyde gave β-formylpropionic acid acetal, to which Kolbe’s electrolytic reaction was applied. The intermediate acetal acid has been successfully isolated in the case of ethylene acetal, whereas ethyl or butyl acetal decomposed by distillation into ethoxy or butoxy-γ-butyrolactone, the structure of which has been established by analysis, infrared spectra and conversion to β-formylpropionic acid. Methyl acetal was also readily hydrolyzed to free aldehydic acid during the course of the isolation. Electrolysis of the ethylene acetal of β-formylpropionic acid in methanol gave adipic dialdehyde as its diethylene acetal.
Synthetic Ammonia Iron Catalysts Containing Magnesia as Its Principal Promoter. I. The Catalysts’ Performances
Authors: Uchida Hiroshi , Terao Iwao , Ogawa Kiyoshi
Published: July 2006

A catalyst promoted singly by magnesia can be as active as one promoted singly by alumina. The activity of the former catalyst is increased by a succeeding reduction at 650°C to a higher level; the increased level is preserved even after the prolonged heating at this temperature. Potash, lime, and silica added as second promoters behave in their respective peculiar manners. Among the catalysts under investigation, a triply-promoted catalyst performs in nearly the same way as one of the catalysts of the alumina-promoted type in current use in industrial ammonia synthesis, provided the amounts of such kinds of promoters as magnesia, potash, and silica are appropriate.

The activity or the rate constant is expressed as a function of the temperature-independent parameters, which are the bed density, the specific surface area, activation energy, the frequency factor per unit of the catalyst surface area, and the reaction temperature. The effects of individual promoters have been discussed in view of the changes in magnitude of each parameter which result from their additions.

The catalysts of the magnesia-promoted type can be reduced much more easily than the catalysts of the alumina-promoted, type, but the reduction rate is only a little below that of the unpromoted catalyst.
The Direct Spectrophotometric Determination of Iron with Dibenzoylmethane in the Organic Phase
Authors: Umezaki Yoshimi
Published: July 2006

A method has been described for the direct spectrophotometric determination of up to 40 μg. of iron (III) with DBM in the organic phase.

An orange complex, which is formed with the addition of DBM and pyridine to the MIBK extract of iron, has a maximum absorbance at 410 mμ. The effect of the diluent on the color reaction has been studied; methanol has been selected as the best diluent of those tried. The color reaction conforms to Beer’s law and has a sensitivity of 0.0046 μg. Fe/cm2 for −logT=0.001. The effects of diverse ions on the determination of iron have been studied; it has been found that this method is simple and is sensitive and selective to iron.
The Condensation of Acetonitrile with Formaldehyde
Authors: Ogata Yoshiro , Izawa Yasuji , Osumi Yasuo
Published: July 2006

The condensation of acetonitrile with formaldehyde using sodium naphthalene as a base catalyst has been studied. The results showed that formaldehyde reacted with acetonitrile through the aldol-type condensation to form ethylene cyanohydrin (1.0∼7.7%). 2,4,6-Trimethyltriazine was detected as one of the by-products.
The Rheological Properties of Concentrated Suspensions. III. Dynamic Properties and Their Correlations with Stationary Flow Properties
Authors: Takano Masaharu
Published: July 2006

The dynamic properties and stationary flow properties of suspensions of barium sulfate in polyisobutylene and in linseed oil have been measured by the use of an electrically-recording rotational rheometer.

The concentration dependence, the influence of mixing conditions, the effects of the addition of water and of sodium stearate on the dynamic viscosity and the dynamic modulus, and the correlation of the dynamic properties with stationary flow properties have been examined experimentally.

In suspensions of barium sulfate in linseed oil, the dynamic viscosity and dynamic modulus increase monotonously with an increasing concentration, and no critical concentration is observed up to the highest concentration. The apparent relaxation time shows a slight increase with an increase in the concentration of particles.

In suspensions of barium sulfate in polyisobutylene, the dynamic viscosity and dynamic modulus increase abruptly above a critical concentration. The apparent relaxation time also increases remarkably above the critical concentration. The mean free energy of the activation for breaking links between particles and the mean number of links to be broken for the separation of two neighboring particles have been evaluated as 33∼34 kT and 1.49 respectively.

The influence of additives on dynamic properties resembles that on stationary flow properties and can be explained qualitatively by assuming a van der Waals-London attraction between particles. However, in a viscoelastic medium, contractive forces arising from the elastic property of the medium seems to be altered by the addition of additives.

For pseudo-plastic systems, the dynamic viscosity coincides with the apparent viscosity at lower frequencies. However, for plastic systems, the apparent viscosity may be higher or lower than the dynamic viscosity at lower frequencies, depending on the sensitivity of the network structures formed by particles and on the time necessary for the restoration of broken structures. The dynamic modulus at lower frequencies increases with an increase in the yield value, while the former increases proportionally to the latter at higher concentrations also.

The non-linearity of dynamic properties has been observed as a feature of their amplitude dependence. The change in the dynamic modulus is more remarkable than that in the dynamic viscosity.

The experimental results described above at least qualitatively agree with the theoretical predictions based on a network model.
The Photometric Determination of Titanium with Acetylacetone
Authors: Fujiwara Shizuo , Nagashima Kozo , Codell Maurice
Published: July 2006

A new method has been proposed for the determination of small amounts of titanium in various substances. Acetylacetone forms an intensely-colored red complex in an acid solution with titanium(III), but this complex had not previously been used for the photometric estimation of titanium, probably because of the great instability of its color. A process has now been proposed for stabilizing the color. Up to 30 mg. of niobium and 30 mg. of iron do not interfere. Interference is encountered from chromium and vanadium, and in their presence, or in the presence of more than 30 g. of iron, a mercury cathode separation must be made. The method has been applied to quantities of titanium as small as 0.2 mg. in 50 ml. of solution.
The Synthesis and 1,4-Addition Type Ring-opening Polymerization of N-Substituted Cyclic Iminocarbonates
Authors: Fujisawa Tamotsu , Tamura Yorikazu , Mukaiyama Teruaki
Published: July 2006

As one of a series of studies of 1,4-addition type ring-opening polymerizations, the synthesis and ring-opening polymerization of N-substituted cyclic iminocarbonates have been studied.

N-Alkyl and N-aryl cyclic iminocarbonates have been prepared by the reaction of sodium ethylene glycorate with the corresponding imidophosgenes. N-Halogeno cyclic iminocarbonates have been prepared from glycols, potassium cyanide and halogenes.

The ring-opening polymerization of the N-substituted cyclic iminocarbonates, which are considered to be cyclic enol derivatives of urethanes, in the presence of cationic catalysts gives the corresponding poly(ethylene N-substituted carbamates).
The Preparation of Poly(ethylene N,N′-Disubstituted Ureas) by the 1,4-Addition Type Ring-opening Polymerization of 2-Imino-1,3-oxazolidines
Authors: Nohira Hiroyuki , Nishikawa Yoshihiro , Mukaiyama Teruaki
Published: July 2006

Various 2-imino-1,3-oxazolidines have been prepared from β-chloroethylureas or from ethanolamines and cyanogen bromide.

N,N′-Disubstituted 2-imino-1,3-oxazolidines give poly(ethylene N,N′-disubstituted ureas) by 1,4-addition type ring-opening polymerization in the presence of a cationic catalyst such as boron trifluoride etherate. On the other hand, 2-unsubstituted imino-1,3-oxazolidines polymerize with difficulty and give polymers with low melting temperatures.
Radiolysis of Solid Glycine
Authors: Meshitsuka Gisuke , Shindo Kotaro , Minegishi Atsuko , Suguro Hiroshi , Shinozaki Yoshiharu
Published: July 2006

Solid glycine has been radiolyzed by 60Co γ-rays in vacuo at room temperature, and all the products except H2 have been measured after dissolving the irradiated samples in water. The hydrogen has been collected and measured directly from the irradiated solid samples. All products except H2 increase linearly with the dose, while H2 shows a plateau from a relatively low dose. The yields of products are as follows: G(H2)∼0.2, G(NH3)=4.8, G(CH3NH2)=0.2, G(CHOCO2H)=2.5, G(CH3CO2H)=2.3, G(CO2)∼0.2, and G(HCHO)∼0.03. The mechanisms of the primary process and the reactions to give final products have been proposed with reference to the results of the ESR studies.
The Bromination of Aromatic Compounds with a Mixture of Peroxyacetic Acid and Bromine in Acetic Acid
Authors: Ogata Yoshiro , Furuya Yoshiaki , Okano Kenji
Published: July 2006

Bromobenzene is obtained in a 56% yield when an acetic acid solution of peroxyacetic acid is slowly added to an acetic acid solution of bromine, benzene and a catalytic amount of sulfuric acid. The rate of the consumption of peroxyacetic acid has been expressed as v=k2 [CH3CO3H] [Br2], where k2 is independent of the concentration of benzene and of the acidity of solution. However, the rate of the formation of bromobenzene is accelerated by sulfuric acid and a more effective use of the attacking species is possible. A mechanism has been suggested which involves the ratedetermining formation of bromine monoxide or acetyl hypobromite, followed by its rapid attack on benzene. The rate is slower with benzene substituted with electron-attracting groups. Some evidence for the formation of acetyl hypobromite has been obtained by ultraviolet spectrophotometry.
Syntheses and Ultraviolet Spectra of Aromatic Azo Compounds. III. Methoxyazobenzene Derivatives
Authors: Nomura Yujiro , Anzai Hiroyuki , Tarao Ryokichi , Shiomi Kengo
Published: July 2006

1) Nine tolylazoanisoles, six dimethoxyazobenzenes, and six bromophenylazoanisoles have been synthesized by the reactions of Grignard reagents with zinc chloride double salts of diazonium compounds; thirteen of them are new compounds.

2) The ultraviolet and visible absorption spectra of the methoxyazobenzene derivatives have been measured, and some regularities of the absorption maxima have been observed in them.
Syntheses and Ultraviolet Spectra of Aromatic Azo Compounds. IV. Naphthylazobenzene Derivatives
Authors: Nomura Yujiro , Anzai Hiroyuki
Published: July 2006

1) α- and β-Naphthylazobenzene and their twenty-four derivatives with a substituent on a benzene ring have been synthesized by the reactions of Grignard reagents with zinc chloride double salts of diazonium salts. Twenty-one of them are new compounds.

2) Six naphthylazobenzoic acids have been prepared by the hydrolysis of the corresponding ethyl esters; five of them are new compounds.

3) The ultraviolet and visible absorption spectra of these naphthylazobenzene derivatives have been measured.
The Inhibitive Behavior of the Fluoride Ion and the Destruction of Its Protective Film in the Corrosion of Magnesium in Neutral Solutions
Authors: Wada Goro , Maekawa Seihei
Published: July 2006

Fluoride ions exhibit an anomalous inhibitive ability against the corrosion of magnesium ; this may be attributed to the formation of a fine film of insoluble magnesium fluoride. This film conducts the cathodic current fairly well, but it conducts the anodic current not at all, as far as it is not destroyed. The cathode reaction through the magnesium fluoride film has a low apparent activation energy because of its electronic conduction, while, when magnesium is anodically polarized, the film is no longer electron-conductive and still permits to a lesser extent the diffusion of any other charged particles; consequently, this is a kind of rectifier in a solution containing potassium fluoride alone.

If a solution contains chloride ions in addition to fluoride ions, the matter is quite different and fluoride ions rather promote the corrosion, like other halide ions. When magnesium, the surface of which has previously been covered with magnesium fluoride is anodically polarized in a solution containing only chloride ions or containing fluoride ions as well as chloride ions, the film soon begins to be destroyed at the initial stage, the bare area of high conductivity appears, and then the surface is gradually again covered with the bulky products, magnesium hydroxide, at the later stage. The destruction of the magnesium fluoride film may occur through a mechanical process regardless of the presence of fluoride ions.
Formation Constants of Chromium (III)-Oxalato Complexes
Authors: Nagata Kyoichi , Umayahara Akira , Tsuchiya Ryokichi
Published: July 2006

The formation constants of chromium(III) complexes with the oxalate ion, which is the simplest bidentate ligand coordinating by two oxygen atoms, have been determined by the pH method.

It has been shown that the formation constants of oxalato chromium(III) complexes are larger than those of the corresponding titanium-(III) complexes, but smaller than those of the corresponding manganese(III), iron(III) and cobalt(III) complexes in the first transition series.

The formation constants of oxalato chromium(III) complexes have been found to be remarkably smaller than those of the ethylenediamine chromium(III) complexes. This result suggests that two nitrogen atoms form a more stable complex with chromium than do the two oxygen atoms serving as donors in the bidentate chelate.
Electrometric Studies on the Reaction between Silver and Alkali Metavanadate
Authors: Saxena R S , Sharma O P
Published: July 2006

The reaction between Ag+ and VO3− ions has been investigated by means of electro-metric techniques involving amperometric, potentiometric and glass electrode titrations between silver nitrate and Na2O·V2O5 in 40% alcoholic media. The end point obtained from the sharp breaks and inflections in the titration curves, occurs at a stage where the molecular ratio of Ag+ and VO3− ions is 1:1 and corresponds to the formation and precipitation of silver metavanadate, Ag2O·V2O5, in the pH range 6.25–7.0. Amperometric titrations yield very accurate results and offer a simple and rapid method of determining vanadium (V) as silver metavanadate.
Phosphorylation by the Use of Diethylphosphorosuccinimidate
Authors: Mukaiyama Teruaki , Obata Teisuke , Mitsunobu Oyo
Published: July 2006

Phosphorylation of alcohols, phenol, and dialkyl hydrogen phosphates by means of diethylphosphorosuccinimidate has been described. Phorphorylation of alcohols with diethylphosphorosuccinimidate could only be carried out in the presence of certain acid catalysts; while more acidic compounds such as phenol and dialkyl hydrogen phosphates were readily phosphorylated to give the corresponding phosphate and sym.- or unsym.-pyrophosphate in quantitative yields even in the absence of catalysts.
The Distribution of Gas Molecules at the Diffraction Center in the Electron Diffraction Experiment
Authors: Morino Yonezo , Murata Yoshitada
Published: July 2006

A method has been proposed for estimating the distribution of gas molecules at the diffraction center in order to evaluate the correction for finite sample size in gas electron diffraction. The distribution measured in this way has been interpreted by a simple model regarding the motion of the gas molecules in the vicinity of the nozzle. A slight asymmetry of the nozzle construction produces in the atomic distances a deviation which cannot be disregarded if an accurate measurement is desired.
The Dimerization of Benzoic Acid in Carbon Tetrachloride and Chloroform
Authors: I’haya Yasumasa , Shibuya Tai-ichi
Published: July 2006

The dimerization equilibrium of benzoic acid has been studied by high resolution infrared spectroscopy over a wide range of acid concentrations. The concentrations of the monomer and the dimer fractions have been determined from the integrated intensities of the respective carbonyl-stretching vibration bands. The calculated equilibrium constant is 2300 l.mol−1for carbon tetrachloride and 400 1. mol−1 for chloroform, both values being considered more reliable than that determined by peak intensity measurements. A weak association of chloroform with benzoic acid has been suggested as occurring through hydrogen bonding to the monomer carbonyl.
Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. V. Synthesis of the Peptide Fragments, His-Phe-Arg-Try, His-Phe-Arg-Try-Gly and Glu-His-Phe-Arg-Try-Gly
Authors: Inouye Ken
Published: July 2006

1) Synthesis of the peptides l-histidyl-l-phenylalanyl-l-arginyl-l-tryptophan, l-histidyl-l-phenylalanyl-l- arginyl -l-tryptophyl-glycine and l-glutamyl-l-histidyl-l-phenylalanyl-l-arginyl-l-tryptophyl-glycine, which corresponded to the amino acid sequences of positions 6–9, 6–10 and 5–10, respectively, of the corticotropin and α-MSH molecules, has been described.

2) The synthetic procedure for γ-t-butyl-l-glutamyl-l-histidyl-l-phenylalanlyl-l-arginyl-l-tryptophyl-glycine, a key intermediate to the higher peptides eliciting the adrenocorticotropic activity, has been improved.

3) An active ester Nα, NIm-dicarbobenzoxy-l-histidine p-nitrophenyl ester has been found to be of value for the synthesis of histidyl peptides.

4) An effective use of partition chromatography on a Sephadex column for purification of peptides has been cited.
Szilard-Chalmers Reaction of Trioxalatochromium Ion on Ion Exchange Resin—Static Irradiation and Its Kinetic Analysis
Authors: Sensui Yoshihiro , Matsuura Tatsuo
Published: July 2006

Trioxalatochromium ion, on Dowex 1X18 immersed in a solution of pH 2.0–3.85, was irradiated batch-wise in the thermal column of a reactor for various irradiation times. With decreasing pH, the 51Cr yield of the most enriched species (hexaquo- and monoxalatotetraquo-chromium ion) increased, but the enrichment factor decreased. With increasing irradiation time, while the changes in the 51Cr yield of each chemical form are small at pH 2.0, the recombination reaction becomes noticeable at pH 3.15 and 3.85. These results were analyzed kinetically, and the rate constants of the aquation and the complex formation under irradiation condition as well as the initial fractions of distribution of 51Cr and the total chromium among each chemical species were determined for the respective pH values.
Structure of Three-coordinated Copper(II) Complexes. Salicylalsalicylaminecopper(II) and Related Compounds
Authors: Inagaki Yoko , Ohashi Osamu , Kishita Michihiko , Kubo Masaji
Published: July 2006

On the basis of infrared spectroscopy and X-ray powder patterns, it is shown that 5-chlorosalicylalsalicylamine and its copper(II) salt are different from salicylal-5-chlorosalicylamine and its copper(II) salt, respectively, in the crystalline state. The nuclear magnetic resonance studies on salicylalsalicylamine and related compounds in solutions show that the double bond in the –CH=N–CH2- portion of these molecules is localized, i. e., the prototropic rearrangement of hydrogen atoms does not take place. Therefore, salicylalsalicylamine-copper(II) presents an example of a new type of three-coordinated copper (II) complexes showing a subnormal magnetic moment in spite of having ligands of a three-dimensional structure. This provides an additional evidence in favor of a presumption made by the present writers on the structure of three-coordinated copper(II) complexes showing a normal magnetic moment.
Electron Paramagnetic Resonance Study of γ-Ray Irradiated Phosphate Glasses
Authors: Nakai Yasuo
Published: July 2006

The EPR spectrum, consisting of a two-line structure and two other distinct types of weak resonances, obtained from irradiated phosphate glasses suggests that these paramagnetic centers are connected with the peculiar structure of phosphate glasses.

The two-line structure arises from an axiallysymmetric hyperfine interaction of a hole with a 31P nucleus. Two distinct types have been demonstrated: one is a trapped hole produced in the glass network, and the other is the trapped electron in the alkaline or alkaline earth ion. In phosphate glasses modified with such ions as calcium, barium or lithium that can coordinate with the tetrahedral oxygen atom in “End” groups (-PO3), the weak resonances seem to appear easily.
The Addition Reaction of Dinitrogen Trioxide with Cinnamyl Acetate
Authors: Kurihara Yoshie , Yamagishi Kazuo
Published: July 2006

This study of the reaction between dinitrogen trioxide and cinnamyl acetate has indicated that the 3-acetoxy-2-nitro-1-phenyl-1-propylnitrite (IIb) is formed, in addition to 3-acetoxy-1 - nitroso- 2 -nitro - 1 - phenylpropane (IIa), in yield depending on the experimental conditions. Those products have been transformed in good yields into 1, 3-dimethoxy-2-nitro-1-phenylpropane, from which dl-erythro-2-amino-1-(p-nitrophenyl)-l, 3-propanediol has been synthesized.
Chemical Effects Associated with β-Decay Process. I. The Chemical Behavior of a Decayed Product, 144Pr, in the EDTA Complex System
Authors: Shiokawa Takanobu , Kudo Hiroshi , Omori Takashi
Published: July 2006

The chemical behavior of 144Pr formed by the β−-decay of the 144Ce(III)-EDTA complex has been investigated. The chemical behavior of 144Pr is remarkably different from that of 144Ce. The results suggest that an increase in the nuclear charge of 144Pr plays the most important role in determining the yield of 144Pr ions and leads to the extensive disruption of the complex molecule by intramolecular electron - transfer. The liberated 144Pr ion reforms the complex according to its kinetic law. The recoil as a result of β−-decay seems not to be the cause of the formation of the free 144Pr ions.
Studies in the Two Phase System: Sodium Formate-Pyridine. VII. Extraction of Mercury
Authors: Deshmukh G S , Rao A L J
Published: July 2006

The distribution of mercuric mercury in the two phase system sodium formate-pyridine is studied. Almost quantitative extraction of mercury into pyridine is obtained from sodium formate (4 m) at a pH range of 7–7.5 with 5 ml. of pyridine and the extracted mercury is determined volumetrically using diphenylcarbazone as an internal indicator.
The Reaction of the Copper(II) Chelate of Ethyl Acetoacetate with Bromine and the Reactions of the Copper(II) Chelates of Acetylacetone and Ethyl Acetoacetate with Dry Hydrogen Bromide
Authors: Ogura Tetsuya , Kojima Yoshitane , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

When the copper(II) chelate of ethyl acetoacetate reacts with bromine in dry dichloromethane, the chelate is broken, forming the α-bromoester and copper(I) or copper(II) bromide depending on the reactants’ mole ratio. However, in the reaction between bromine and the chelate at a mole ratio of 1 : 1 in dichloromethane saturated with water, copper-(I) bromide is not produced primarily; instead copper(II) hydroxide is formed, as is copper-(II) bromide.

In the reactions of the copper(II) chelate of acetylacetone or ethyl acetoacetate with dry hydrogen bromide at the mole ratio of 1 : 1 or 1 : 1.5, more than 98% of the total copper precipitated as copper(I) bromide. Even when 2 mol. of hydrogen bromide was employed against 1 mol. of the chelate, more than 90% of the original copper changed to copper(I) bromide, in contrast with the results obtained in a similar reaction with bromine.

The entire reaction pattern has been suggested employing a presumed intermediate binuclear complex containing a bromine double brigde.
Cobalt(II) Complexes of Schiff Bases Derived from Salicylaldehyde and Aromatic Amines
Authors: Nishikawa Hiroaki , Yamada Shoichiro
Published: July 2006

Bis(N-aryl-salicylideneiminato)cobalt(II) complexes, including several new compounds, have been prepared and their configurations examined. These cobalt(II) compounds have been concluded, from their electronic spectra, to have a tetrahedral configuration around the cobalt(II) ion. All these compounds in pyridine have been concluded to take an octahedral configuration with the exception of the N-o,o′-disubstituted cobalt(II) compounds.
The Determination of Micro Amounts of Polythionates. I. A Photometric Method for the Determination of Pentathionate by Means of Its Cyanolysis
Authors: Koh Tomozo
Published: July 2006

The photometric method for the determination of a small amount of pentathionate has been developed; it is based on the formation of thiocyanate equivalent to the pentathionate, and on the determination of thiocyanate with an excess of ferric iron.

The buffer solution is first added to the standard pentathionate solution so that the pH values of the mixture solution after the addition of the cyanide solution may be over an optimum range; othewise the pentathionate undergoes alkaline decomposition because of the higher pH value which results from the addition of the cyanide.

The conditions under which the reaction of pentathionate with cyanide is rapid and goes well to completion have been established by varying the cyanide amount, the pH, the reaction time, and the temperature.
The Oxidation-Reduction Potential of the System of Mn(II)EDTA-Mn(III)EDTA Complexes and the Stability Constant of Mn(III)EDTA Complex
Authors: Tanaka Nobuyuki , Shirakashi Takashi , Ogino Hiroshi
Published: July 2006

The standard oxidation-reduction potential of the system of Mn(II)EDTA-Mn(III)EDTA complexes has been determined to be E°MnY=0.579V. vs. SCE from the potentiometric measurement with the rotated platinum electrode. From this value the logarithmic stability constant of the Mn(III)EDTA complex (logKMn(III)Y) has been calculated to be 24.9 at 25.0°C and μ=0.2.
t-Amyloxycarbonyl as a New Protecting Group in Peptide Synthesis. I. The Synthesis and Properties of N-t-Amyloxycarbonylamino Acids and Related Compounds
Authors: Sakakibara Shumpei , Shin Masaru , Fujino Masahiko , Shimonishi Yasutsugu , Inoue Sumiko , Inukai Noriyoshi
Published: July 2006

It has been shown that the t-amyloxycarbonyl group (AOC group) can be introduced quite readily into amino acid esters by using t-amyl chloroformate as a reagent, and that the AOC group can be cleaved as smoothly as the t-butoxycarbonyl group (BOC group) under acidic conditions. Since this reagent is much easier to prepare than any other reagents used for the introduction of the BOC group, the new procedure is considered to be of great use in the practical synthesis of complicated peptides. 3-Methyl-3-pentoxycarbonylamino acids were also prepared by following the same procedure as was used in the case of AOC-amino acids.
Transition Metal Complex Catalysts for the Oligomerization of Butadiene. II. The Reaction of Catalyst Components
Authors: Tamai Katsumi , Saito Taro , Uchida Yasuzo , Misono Akira
Published: July 2006

In order to obtain some knowledge on the behavior of catalysts in the oligomerization of butadiene, the reaction between cobalt(III) acetylacetonate or iron(III) acetylacetonate and trietylaluminum has been investigated by means of magnetic susceptibility measurements, infrared spectra, gasometry, and electron spin resonance spectra.

When triethylaluminum was added to an excess of cobalt(III) acetylacetonate, the infrared spectra and gasometry suggested that the latter was reduced via stable cobalt(II) acetylacetonate to zero valent cobalt and that, at the same time, the former was transformed into aluminum(III) acetylacetonate. The extraordinarily large magnetic moment (μeff=12) and the absence of the signal of the electron spin resonance spectra suggested the formation of metallic cobalt. The metallic cobalt was active enough to be readily oxidized by the addition of methanol. The addition of butadiene to this solution decreased the magnetic moment to 7.8. This shows some coordination of butadiene to reduced cobalt.

When cobalt(III) acetylacetonate was reduced in the presence of an excess of triethylaluminum (Al/Co>4), the zero valent cobalt was stablilized as a result of the formation of a certain diamagnetic complex with triethylaluminum. However, the addition of cobalt(III) acetylacetonate to this reaction mixture decomposed the above complex, and the very large magnetic moment indicated the formation of metallic cobalt.

Iron(III) acetylacetonate was, like cobalt(III) acetylacetonate, reduced to zero valent iron via stable iron(II) acetylacetonate. In the presence of an excess of triethylaluminum, however, zero valent iron did not form a stable complex with triethylaluminum, and from the ferromagnetism metallic iron was observed toresult.
The Cation Exchange Adsorption of Calcium and Strontium from an Ammonium Formate or Ammonium Acetate Solution in Mixtures of Organic Solvents and Water
Authors: Tsubota Hiroyuki
Published: July 2006

Ion exchange equilibria of calcium- and strontium-ammonium exchange systems have been studied in methanol-water, acetone-water and dioxane-water mixtures in which acetate or formate ions co-exist as a complexing anion. The selectivity coefficients of calcium against ammonium and those of strontium against ammonium decrease, while the separation factor between strontium and calcium increases, with an increase in the organic solvent concentration. Therefore, by the column operation, calcium can easily be eluted from the column, and strontium can be well separated from calcium when a suitable elutriant with a high separation factor between strontium and calcium and with a low selectivity coefficient of calcium against ammonium is selected. A 1 : 1 mixture of a 2 m ammonium formate aqueous solution and acetone or a 1 : 1 mixture of a 2 m ammonium acetate aqueous solution and methanol is recommended. When strontium in a large amount of calcium is to be analyzed, the latter elutriant is the most suitable.
The Synthesis of Four Isomeric Diiodo-m-xylenes. Their Isomerization in Sulfuric and Polyphosphoric Acids
Authors: Suzuki Hitomi , Maruyama Kazuhiro , Goto Ryozo
Published: July 2006

Four isomeric diiodo-m-xylenes have been synthesized and their isomerization in concentrated acids investigated in order to elucidate the mechanism of the new rearrangement observed in the Jacobsen reaction of 2-iodo-m-xylene. 2,4- and 4,5-Diiodo-m-xylene, in the presence of cold sulfuric or hot polyphosphoric acid, isomerize to 4,6- and 2,5-diiodo-m-xylene respectively. All four isomers readily undergo disproportionation with hot sulfuric acid to give mixtures of tri- and tetraiodo-m-xylenes. No disproportionation has been observed in the reaction with polyphosphoric acid. The important role played by a sulfo group in this reaction has been discussed.
An Attempt to Determine Fluorescein’s S–T Transition Probability and a Preliminary Investigation of the Behavior of Its Semiquinone in an Alkaline Solution
Authors: Momose Yoshihiro , Uchida Kengo , Koizumi Masao
Published: July 2006

An attempt to obtain a reliable value of \varphiS-T for fluorescein in an alkaline solution has been unsuccessful since the values for EDTA and ATU were quite different. It has been found that a large quantity of semiquinone is produced when EDTA is used as a reducing agent. In the case of ATU, the quantity of semiquinone produced is very small. Semiquinone in an alkaline solution reverts to the oxidized dye by the second-order thermal reaction and, quite astonishingly, mostly by the reaction 2DH → 2D+H2. The photochemical behavior of leuco-fluorescein has been investigated to some extent in the presence of and in the absence of a reducing agent.
Semi-empirical Self-consistent Field Molecular Orbital Calculation of the Electronic Structure of the Base Components of Nucleic Acids
Authors: Nagata Chikayoshi , Imamura Akira , Tagashira Yusaku , Kodama Masahiko
Published: July 2006

SCF MO calculations have been carried out for adenine, guanine, thymine, cytosine, uracil, 9-methyladenine and 1-methylthymine. In evaluating the two-center repulsion integral, the Pariser-Parr and Mataga-Nishimoto approximations have both been used, and the results compared with each other and with the experimental data on the optical properties. In the calculation of thymine, 9-methyladenine, and 1-methylthymine, the hyperconjugation of the methyl group has been taken into account. The calculated wavelength and the oscillator strength of the singlet-singlet transition for the above-mentioned molecules explain the experimental values well except for thymine and 1-methylthymine. The theoretically determined directions of the polarization of the transition moments have been compared with the experimental results for adenine, 9-methyladenine and 1-methylthymine. With regard to the direction of the polarization of the transition moments of the first and the second absorptions of adenine and 9-methyladenine, the results are questionable. From the theoretical point of view, it is difficult to determine which assignment is correct, however, in view of the wavelength and the oscillator strength, the first absorption may reasonably be assigned to the long-axis polarized band. The calculated and the experimentally-determined direction of polarization for 1-methylthymine agree well with each other. The energies of the highest and lowest vacant orbitals and the π-electron densities for the molecules treated in the present paper have been calculated and compared with the result obtained by the Hückel MO method.
Studies of the Aqueous Solution of a Surface Active Substance by Means of an Ultrasonic Interferometer. I. Determinations of the Critical Concentration and Compressibility of Micelles of Several Alkyl Sulfates
Authors: Shigehara Koji
Published: July 2006

The sound velocity and the density of aqueous solutions of sodium hydrogen (SHS), methyl (SMS), octyl (SOS), dodecyl (SDS) and tetradecyl (STS) sulfates have been measured by using, respectively, a differential ultrasonic interferometer and a float balance, and the compressibility (β) has then been calculated from these results. Each of these three quantities, when plotted against the concentration (C), has shown a nearly straight line for SHS and SMS, while it consists of two nearly straight lines, with a break point between them at CMC, in the cases of SOS, SDS and STS. The values of dβ/dC below and above CMC, when plotted against the number of carbon atoms in the alkyl chain of the solute molecule, again showed two straight lines which intersected with each other at the zero number of carbon atoms. This value of dβdC is equal to that of SHS at a moderate concentration. These results have been explained by taking account of the dissolved state of these solutes. The compressibility of the micelle (βm), the molar volume of the CH2 radical in the micellar state (Vm), and the ionic hydration number of solute have been calculated; the values of βm and Vm show evidence for the view that the hydrocarbon interior of the ionic micelle is liquid-like rather than solid-like.
Studies on the Liquid-Liquid Partition Systems. II. The Determination of Water Activity by the Solvent Extraction Technique
Authors: Hasegawa Yuko , Sekine Tatsuya
Published: July 2006

An attempt has been made to apply the solvent extraction technique to the determination of the water activity in various electrolyte solutions.

Benzene was agitated with a sample solution until the distribution equilibrium was attained, the water content in the benzene was then measured by Karl Fischer titration. The water activity was calculated on the basis of the water content.

The results agree with the data obtained by the vapor pressure method. On the basis of these, a solvent extraction procedure has been recommended as an easy and rapid method to determine the water activity in various electrolyte solutions.
Studies of Thio Acids. IV. Dipole Moments of Methyl Thiostearate, Thiostearic Acid and Thioacetic Acid
Authors: Hirabayashi Yoshio
Published: July 2006

The dipole moments of methyl thiostearate, thiostearic acid, and thioacetic acid have been measured in n-hexane, benzene, and dioxane solutions at 30°C. The values obtained are: methyl thiostearate, 1.30 D (n-hexane), 1.37 D (benzene), 1.37 D (dioxane); thiostearic acid, 2.06 D (n-hexane), 2.14 D (benzene), 2.21 D (dioxane); thioacetic acid, 2.12 D (n-hexane), 2.16 D (benzene), 2.36 D (dioxane). On the basis of the above results, a planar configuration similar to the cis configuration of carboxylic ester is considered to be the most probable structure of methyl thiostearate; three probable alternative configurations have been suggested for the structure of thio acid.
The Heat Capacity and the Entropy of Transition of Würster’s Blue Perchlorate
Authors: Chihara Hideaki , Nakamura Minoru , Seki Syûzô
Published: July 2006

The heat capacity of Würster’s Blue perchlorate (N,N,N′,N′-tetramethyl-p-phenylene-diamine perchlorate) has been measured between 66 and 200°K. A phase transition occurs at 189.9°K with its tail extending down to about 160°K. The transition is probably of the first order. The heat and the entropy of the transition are 408.6±4.5 cal./mol. and 2.19±0.02 cal./deg.mol. respectively. The magnetic susceptibility of the specimen at room temperature indicates that the paramagnetic spin density is 100±3%. The experimental results have been compared with current theories, and it has been inferred that some unknown structural changes are involved in the phase transition.
Some Reactions of Mercuridiacetaldehyde
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Fuji Saburo
Published: July 2006

Mercuridiacetaldehyde is soluble in polar solvents and rather instable in the state of solution, yielding an insoluble and infusible substance. The decomposition reaction has been proved to include the formation of mercuri(I)-acetaldehyde Hg2(CH2CHO)2 by the cleavage of one of the Hg–C bonds. On the other hand, mercuridiacetaldehyde reacted with aldehyde reagents as usual aldehydes. The change in the infrared spectra on these reactions has been interpreted in terms of σ-π conjugation, as has been suggested previously by Nesmeyanov.

Nef’s compound, which is considered to be a mercuric salt of vinyl alcohol, has been found to be almost identical with the mercuri-(I)-acetaldehyde.
Kinetic Studies of Solvolysis. X. Transition from a van’t Hoff to an Arrhenius Intermediate Caused by Steric Hindrance at the Product-Formation Step of SN1 Reactions
Authors: Okamoto Kunio , Matsui Yoshihisa , Shingu Haruo
Published: July 2006

1. The SN1 reactions of benzhydryl halides and hindered nucleophiles, i. e., potassium 2,6-di-t-butyl-4-methylphenoxide (I), tri-n-butylammonium 2,6-di-t-butyl-4-methylphenoxide (III), tri-n-butylamine and tri-n-butylammonium phenoxide (II), proceed through an Arrhenius intermediate and obey good second-order kinetics in acetonitrile at 110–140°C, whereas in the same solvent the reaction with potassium phenoxide is a typical SN1 reaction with a van’t Hoff intermediate at 70–120°C. This transition of the characteristics of the intermediates from a van’t Hoff to an Arrhenius type has been explained as being due to steric hindrance at the product-formation step of the SN1 reactions.

2. The reactions of benzhydryl halides and some hindered nucleophiles, i. e., tri-n-butylamine, I and III, afford not products anticipated for the nucleophilic substitution in acetonitrile, but rather products derived from benzhydyl radicals, i. e., sym-tetraphenylethane, diphenylmethane and 1-(3′,5′-di-t-butyl-4′-hydroxyphenyl)-2,2-diphenylethane, whereas potassium phenoxide and II give rise to substitution products typical of the nucleophilic reactions, i. e., benzhydryl phenyl ether and p-benzhydrylphenol. A one-electron transfer mechanism between these hindered nucleophiles, such as tri-n-butylamine, I and III, and the SN1 intermediate has been suggested for the formation of benzhydryl radicals.
The Trifluoroacetate Method of Peptide Synthesis. I. The Synthesis and Use of Trifluoroacetate Reagents
Authors: Sakakibara Shumpei , Inukai Noriyoshi
Published: July 2006

The trifluoroacetates of various phenol, thiophenol and N-hydroxyimide derivatives, which are known as hydroxylic partners of various active carboxylic acid ester, have been synthesized, and it has been found that they are good reagents for the preparation of the respective active esters of acylamino acids by the ester-exchange reaction in pyridine. The new method is especially effective in the preparation of p-nitrophenyl, 2,4,5-trichlorophenyl and N-hydroxysuccinimide esters of acylamino acids, which are well known to be useful intermediates for peptide synthesis. The direct syntheses of peptides using these reagents, without the isolation of the intermediates, have been studied, and the new procedure has been found to be wise elongation of peptides.
The Effect of Temperature on Electrodialytic Demineralization
Authors: Weiner Susan A
Published: July 2006

The process of electrodialysis, as a means of demineralizing brackish water, is briefly described. Polarization, a limiting factor in the practical application of the process, is a function of several variables, one of which is temperature. In this study the temperature dependence of limiting current density and power consumption was examined. Experiments conducted at elevated temperatures (35.5°C and 40°C) showed that the limiting current densities are increased and the power consumption is decreased. At low temperatures (5°C) marked decrease in limiting current density was observed. Comparison of power consumption data at 40°C and 5°C show that significant differences occur with feeds more concentrated than 2000 p.p.m.
The Spectrophotometric Determination of Chromium with 2-Hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-naphthalein (Sodium Salt)
Authors: Uesugi Katsuya , Katsube Yukiteru
Published: July 2006

A spectrophotometric method for the determination of traces of chromium (III) with 2-hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-naphthalein has been described. Beer’s law is obeyed up to 1.2 p. p.m. of chromium. The spectrophotometric sensitivity is 0.0013 μg. Cr/cm2 based on an absorbance of 0.001 unit at 630 mμ. The accuracy and precision are satisfactory. The interference of foreign ions can be avoided by 8-hydroxyquinoline chloroform extraction or by acetylacetone chloroform extraction.
The Dehydrogenation of All-cis-5,11,14-Eicosatrienoic Acid to Arachidonic Acid
Authors: Takagi Toru
Published: July 2006

Ethyl 5,11,14-eicosatrienoate has been fed to fat-deficient rats. The gas chromatographic analysis of the fatty acids in the liver lipids and the alkali isomerization and oxidation scission of the eicosatetraenoate separated from the fatty acid has given evidence for the transformation of all-cis-5,11,14-eicosatrienoate to arachidonate.
Photoreduction of Methylene Blue and Thionine in Ethanol
Authors: Usui Yoshiharu
Published: July 2006

The photochemical behavior of methylene blue and thionine in ethanol is quite different from that of eosine in the same solvent. They are compared from several viewpoints below.

From the preliminary flash experiment and the kinetic results by steady illumination, it has been concluded that interaction between the ground state and the excited state dye is essential for photoreduction.

It is most probable that the overall scheme for the photoreduction of thiazine dyes in alcohol is similar to that in the case of the same dyes in a phosphate buffer solution.
Studies on Geometric Isomerism by Nuclear Magnetic Resonance. II. Geometric Configurations of Alkylidenecyanoacetic Esters
Authors: Hayashi Toshio , Igarashi Minoru , Hayashi Shoichi , Midorikawa Hiroshi
Published: July 2006

The Knoevenagel reaction of a methyl alkyl ketone with cyanoacetic ester gives a stereoisomeric mixture of α-cyano-β-alkylcrotonic ester. The NMR technique has been applied to the study of the geometric configurations of the mixture. It has been found that the isomer with a β-methyl group cis to the alkoxycarbonyl group always occurs predominantly. The magnitude of the cis-trans composition of the mixture is parallel to the steric requirement of the β-substituted alkyl group.