bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Rheological Properties of Concentrated Suspensions. II. Stationary Flow Properties and the Influence of Additives and of Particle Size
Authors: Takano Masaharu , Kambe Hirotaro 
Published: July 2006

Abstract
The stationary flow properties of concentrated suspensions of barium sulfate in linseed oil and of those in polyisobutylenes have been measured at very low rates of shear with capillary viscometers and a Brookfield viscometer.
The dependence of the plastic viscosity and the yield value on the concentration, the particle sizes, and the polarizabilities of the medium and of the additive have been measured and explained by using a network model and by assuming van der Waals-London attraction between particles.
In suspensions of barium sulfate in linseed oil, the plastic viscosity and the yield value do not change on the addition of water below 2 wt. % based on pigments, and their dependence on the concentration of particles is monotonous. However, these values increase when the particles are covered with sodium stearate above a critical concentration.
In suspensions of barium sulfate in polyisobutylene, the plastic viscosity and the yield value appreciably increase above the critical concentration determined by the particle sizes, and these values decrease when the particles are covered with sodium stearate.
In both cases, a higher plastic viscosity and yield value are observed for suspensions of smaller particles in the same medium.
In suspensions of barium sulfate in polyisobutylene, antithixotropic behavior is observed at very low rates of shear. When the particles were covered by sodium stearate, the abnormal behavior disappears and normally thixotropic behavior is observed.
For plastic systems, the mean free energy of activation for breaking links between particles has been evaluated at 30∼kT. If we assume van der Waals-London attraction between particles, the distance between the surfaces of solid particles is within the range of 10∼55 Å, depending on the particle sizes and the presence of an additive.
Other parameters, the mean number of links to be broken for separating particles, the mean stiffness of links and other data have been approximately evaluated by assuming van der Waals-London attraction between particles.
Synthesis of Cyclic Peptide. I. Preparation of Cyclo-di-β-alanyl from 1,4-Cyclohexanedione
Authors: Watanabe Hiroshi , Kuwata Shigeru , Koyama Sugao 
Published: July 2006

Abstract
1) By the direct Beckmann rearrangement of 1,4-cyclohexanedione dioxime by polyphosphoric acid, trifluoroacetic acid, perchloric acid or sulfuric acid at about 100°C, no expected cyclo-di-β-alanyl but p-phenylenediamine was obtained.
2) By indirect Beckmann rearrangement using di-p-tosylate of 1,4-cyclohexanedione dioxime as an intermediate, the rearrangement occurs certainly though the isolation of the cyclic dipeptide was not successful.
3) By the Schmidt reaction of 1,4-cyclohexanedione, the expected rearrangement proceeded smoothly and from the reaction products cyclo-di-β-alanyl was easily isolated.
The Mechanism of Ethylenimine Formation by the Action of Grignard Reagents on Ketoximes
Authors: Eguchi Shoji , Ishii Yoshio 
Published: July 2006

Abstract
The reactions of aryl alkyl ketoximes with aliphatic Grignard reagents have been carried out under various conditions.
Gas chromatographic analyses of the reaction products showed the formation of an ethylenimine ring in which an α-carbon of the alkyl group in oximes constitutes a member of the ethylenimine ring. The reaction of acetophenon oxime with ethylmagnesium bromide containging lithium aluminum hydride produced 2-phenyl-2-ethylethylenimine, together with styrenimine.
A reaction process similar to that of the Neber rearrangement has then been proposed on the basis of the above findings.
Univalent-Bivalent Ion-exchange Equilibria on Some Permselective Membranes
Authors: Mandersloot W G B 
Published: July 2006

Abstract
The relative affinity coefficient Kji is shown to be dependent on the ratio of external and internal total concentrations, the ratio of the external activity coefficients and of the internal activity coefficients, a pressure-volume term and an electrical term. Kji is therefore dependent on the “ loading ” of the resin \barXj.
Several cation exchange resins exhibit a very strong affinity for calcium at high calcium loading and this affinity increases sharply with \barXCa; this effect is attributed to heterogeneity in the crosslinking of the resin and it is a strong indication that here the pressure-volume term plays a decisive rdle.
The pressure-volume term appears to be of relative importance also in the Cl/SO4 equilibrium on anion exchange resins, particularly when these are highly crosslinked. Heterogeneity in the crosslinking probably causes the sharp increase in affinity for Cl at high SO4 loading and low (0.01 n) external concentration.
Conductivity measurements on the resins in single and mixed forms is useful to get an indication of the binding forces between counterions and fixed ions and these measurements can also reveal interactions which may have a bearing on ion exchange equilibrium.
The Electronic Structures and Electronic Spectra of Benzylidene Methyl Amine N-Oxide and Its Related Compounds
Authors: Kubota Tanekazu , Yamakawa Masumi 
Published: July 2006

Abstract
The ultraviolet absorption spectra of benzylidene methyl amine, its protonaddition compound and benzylidene methyl amine N-oxide have been examined under various conditions. SMO calculations on those compounds have been carried out, and various physicochemical properties have been discussed.
On the basis of these calculations, the spectra of the above compounds have reasonably been assigned by using the spectroscopic exchange integrals βs(1A1) and βs(1B1), which were evaluated from the spectra and the MO, including C. I., of styrene.
The Spectrophotometric Determination of Titanium with Xylenol Orange
Authors: Otomo Makoto 
Published: July 2006

Abstract
A new method for the spectrophotometric determination of titanium has been described. This method is based on the formation of the colored complex between titanium and xylenol orange in a slightly acidic solution. The effects of pH and the reagent concentration on the color development of the complex have been thoroughly investigated, and experimental conditions which make possible the determination of titanium at microgram levels have been devised. The compositions of the two 1 to 1 complexes have been determined from the data of spectrophotometric measurements. The apparant formation constants of these complexes have also been calculated.
Hydroxyl Radicals in the γ-Radiolysis of Aqueous Benzene Solutions
Authors: Tsuda Minoru 
Published: July 2006

Abstract
Some experiments have been made in order to prove the hypothesis that the hydroxyl radical plays an important role in the oxidation of organic compounds by γ-radiolysis in aqueous solutions. Nitrous oxide and hydrogen peroxide have been found to be capable of converting radiation-induced hydrogen atoms (or their stoichiometrically-equivalent species) into hydroxyl radicals. In theγ-radiolysis of aqueous benzene solutions in the presence of nitrous oxide or hydrogen peroxide, the yield of the oxidation products from benzene has been found to equal, as had been expected, the sum of the yields of hydrogen atoms and hydroxyl radicals from water.
The Tracer Study of the Reactions of Diphenyl Sulfone and Diphenyl Sulfoxide with Sulfur
Authors: Oae Shigeru , Kawamura Shunichi 
Published: July 2006

Abstract
Diphenyl sulfoxide-35S was reduced to the sulfide-35S nearly quantitatively by heating with sulfur at 280°C, while diphenyl sulfone did not react with sulfur at the same temperature. At around 300°C, diphenyl sulfone-35S started to react with sulfur and gave diphenyl sulride that lost nearly 75% of the original activity of 35S of the sulfone used. The main reaction of the sulfone was found not to be reduction, but substitution involving induced C-S cleavage and replacement with sulfur chain.
The Cationic Copolymerization of Styrene and p-Brornostyrene in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Matsuda Minoru , Iino Masashi 
Published: July 2006

Abstract
1) The cationic copolymerization of styrene and p-bromostyrene in liquid sulfur dioxide using boron trifluoride etherate as a catalyst has been carried out; the monomer reactivity ratios (MRR) have been found to be r1=0.8 and r2=0.4. The MRR value was independent of the temperature and of the quantity of the catalyst in the copolymerization.
2) The effect of added solvents in liquid sulfur dioxide has also been examined. However, the MRR’s have been little affected by the added solvents, the rates of the copolymerization have largely been depressed, and the rates were not dependent on the dielectric constants of the added solvents, the rate in pure liquid sulfur dioxide being the fastest.
3) The same cationic copolymerization has been conducted in benzene, carbon tetrachloride, nitrobenzene and ethylene dichloride.
The MRR’s were almost equal in all (r1=1.8 and r2=0.3).
Sterically-hindered Organosilicon Compounds Containing Cyclohexyl Groups. III. Notes on Petrov and Chernysheva’s Tetracyclohexylsilane and Tricyclohexyl-n-butylsilane
Authors: Takakusa Michio 
Published: July 2006

Abstract
Discrepancies among reported melting ponints for tetracyclohexylsilane and tricyclohexylbutylsilane were discussed. Tricyclohexylcyclohexoxysilane was obtained in 2∼5% yield in addition to tricyclohexylchlorosilane from the reaction of cyclohexyllithium with silicon tetrachloride. Petrov’s compound melting at 198°C is most likely to be tricyclohexylcyclohexoxysilane and not a stereoisomeric tetracyclohexylsilane. Tricyclohexylbutoxysilane, m. p. 133°C, was prepared by treating sodium butoxide with tricyclohexylchlorosilane, and it was pointed out that Petrov’s “tricyclohexylbutylsilane” is probably tricyclohexylbutoxysilane.
Electrochemical Fluorination of 2,2,3,3-Tetrafluoro-1-propanol
Authors: Nagase Shunji , Baba Hajime , Kojima Rimpei 
Published: July 2006

Abstract
Perfluoropropionic acid, accompanied by a small amount of trifluoroacetic acid, was obtained in a good yield by the electrochemical fluorination of 2,2,3,3-tetrafluoro-1-propanol. The yield or current efficiency increased with an increase in the anodic current density and cell temperature. Although the yield decreased at lower temperatures, the reaction became milder, giving a smaller amout of trifluoroacetic acid in the product. The composition of the perfluorocarboxylic acids obtained by this fluorination reaction is very similar to that of those obtained by the fluorination of propanol, propyl propionate, diethyl ketone, and dipropyl ether. Only a trace of perfluorocarboxylic acid was formed by the electrochemical fluorination of 3H-tetrafluoropropionic acid.
Spectrophotometric Studies of the Complexes of o-Sulfobenzeneazochromotropic Acid Formed with Thorium
Authors: Miyata Haruo 
Published: July 2006

Abstract
o-Sulfobenzeneazochromotropic acid was prepared in the form of reddish brown needles of monosodium salt, and the value of the first dissociation constant, pKa1, was estimated spectrophotometrically to be 9.76 (25°C, μ=0.1).
The reagent reacts with thorium in the molar ratio 1:1, displacing one hydrogen atom, and the approximate value of the apparent stability constant of the complex, logK′, was estimated to be 3.2∼4.2 at pH values from 2.5 to 3.5, while the concentration of thorium was about (4∼8)×10−5.
The Nuclear Magnetic Resonance Spectra of Olefinic Protons and the Substituent Effects. I. Systems of ω-Substituted trans-Styrenes and 1-Substituted trans-Propenes
Authors: Kasiwagi Hazime , Niwa Jun 
Published: July 2006

Abstract
High resolution proton magnetic resonance spectra of ω-substituted trans-styrenes and 1-substituted trans-properies have been observed and discussed from the viewpoint of substituent effects. The chemical shifts of protons located at the cis-position to substituents depend roughly upon Hammett’s σP constants and presumably correlate better with the combination of potential inductive and resonance parameters, namely 0.40σI+0.70σR, proposed by Taft.
These results suggest that the chemical shifts of olefinic cis-proton may be computed from the viewpoint of the polar nature of the substituents, though the diamagnetic anisotropy and the long-range shielding effect of the substituents must be carefully considered side by side.
When the chemical shifts of protons situated at corresponding positions of structure in several systems are compared, a fairly good correlation is observed among them. This fact implies that the modes of the transmittance of substituent effects is similar in these systems.
The nature of the substituent effects on the chemical shifts of geminal protons is, however, very complicated and might be out of consonance with both the electronegativity and the available substituent parameters.
Studies of the Absorption Spectra of Azo Dyes and their Metal-complexes. II. The Absorption Spectra of Phenolazoacetoacetamide and its Derivatives
Authors: Yagi Yoshiharu 
Published: July 2006

Abstract
Phenolazoacetoacetamides take the hydrazone form. The phenolic hydroxyl group forms an intramolecular hydrogen bond with a hydrazone nitrogen atom in the solid state and in non-polar solvents.
The electronic absorption spectra of these compounds exhibit four groups of characteristic bands: The A bands arise from a transition involving electron migration along the whole conjugate system of the respective compound; the C bands originate in a conjugative electronic transition between a phenolic nucleus and a hydrazone group, and the D bands, in a conjugative electronic transition between a carboxylic acid anilide group and a hydrazone group.
From the investigation of the series of spectra in phenolazoacetoacetbenzylamides, the B bands have been assigned to the conjugation band; they arise from a conjugative electronic transition within a partial chromophore consisting of an acetyl carbonyl and a hydrazone group.
Studies of the Absorption Spectra of Azo Dyes and their Metalcomplexes. III. The Electronic Absorption Spectra of Metalcomplexes Derived from Phenolazoacetoacetanilides
Authors: Yagi Yoshiharu 
Published: July 2006

Abstract
1) The electronic absorption spectra of metallized phenolazoacetoacetanilides exhibit four characteristic groups of bands—A, B, C and D. These groups of bands originate in the band of the respective ligand-dye.
2) The metal-complexes have the structure shown in formula VI.
3) The bathochromic shifts of the A ligand-bands with complex-formation are ascribed to two causes: (i) the polarity of the M–O (M, tervalent metal; O, phenolic oxygen) bond, and (ii) the perturbation of the π-electron system by the dπ-pπ interaction. The shifts of the C ligand bands with the complex-formation are closely related to the polarity of the above-mentioned M–O bond. The cobalt (III)-complex has the covalent M–O bond with which to form a stable chelate ring, whereas the chromium (III)-complex has the ionic M–O bond.
4) The absorption characteristics of the iron (III)- and the aluminum-complexes have been discussed.
Studies of Organic Peroxides. VII. The Decomposition of Symmetrically Substituted Benzoyl Peroxides by Iron (II)
Authors: Hasegawa Shigeo , Nishimura Norio , Mitsumoto Seiichi , Yokoyama Ken’ichi 
Published: July 2006

Abstract
An investigation of the reactions between sym-metrically-parasubstituted benzoyl peroxides and iron (II) has been made. From the apparent first order specific reaction rates, which were obtained from the data of the thermal analysis method, the energy and entropy of activation have been estimated. In this reaction series, the linear enthalpy-entropy relationship was observed. William’s concept of the coördination of iron(II) to the peroxide molecule was assumed, and the effects of substituents on both the enthalpy of activation and the entropy of activation were discussed. It was also found that the Hammett’s equation is approximately applicable, except for nitrosubstituted benzoyl peroxide.
Studies of the Electrolytic Conductance of a Dye Solution. I. Complex Formation in an Aqueous Solution of the Mixture of Chlorazol Sky Blue FF and Chrysophenine G
Authors: Shinzawa Kinko , Tanizaki Yoshié , Ando Noboru 
Published: July 2006

Abstract
The conductances of aqueous solutions of Chlorazol Sky Blue FF (Blue), Chrysophenine G (Yellow), Sodium Chloride and their binary mixtures at various constant ratios have been measures. The conductance observed with a mixture of Blue and yellow increased abnormally compared with that obtained by the sum of individual dye conductances; the difference between the observed and the sum values reached a maximum at about the same fraction of the equivalent concentration of component dyes. A similar relation of the conductance against the fraction of the conductance against the fraction of the equivalent concentration of components, obtained with mixture, in which component dye was substituted by sodium chloride. did not always show a coincidence between the observed value and the sum one. the difference, however was much smaller than that obtained with dye mixtures. Thus, the abnormal increase described above may be attributed to the formation of complexes of Blue and Yellow; a 1:1 complex and a 1:2 complex, consisting of Blue and yellow already known, were sufficiently reflected in the conductance curve, especially in the conductance curve, especially in a 1:2 complex.
Stability Order in Metal Chelate Compounds. I. 4-Carboxy -and 4-Sulfocatechol Complexes
Authors: Murakami Yukito , Nakamura Katsuyuki , Tokunaga Masasuke 
Published: July 2006

Abstract
The stability constants of 4-carboxy- and 4-sulfocatechol chelates with bivalent transition metals and alkaline earth metals have been evaluated in aqueous media at 30.0±0.1°C and 0.10 m of ionic strength. The stability orders, manganese&lt;cobalt∼nickel&lt;zinc&lt;copper for transition metal chelates and strontium&lt;calcium&lt;magnesium for alkaline earth metal chelates, have been found to hold in these catechol chelate systems. A unique stability sequence, nickel&lt;zinc, has been discussed in terms of the electron delocalization effect, in which metal d orbitals, lone pair orbitals of catechol oxygens and π orbitals of the benzene ring are involved. A reverse relationship for ligand basicity and chelate stability was observed for copper(II) and zinc(II) chelates, and the stability of metal chelates was found to increase in the sequence; catechol&lt;4-carboxycatechol&lt;catechol-4-sulfonate&lt;Tiron. Substituent groups were considered to play an important role in this case.
Spectrochemical Study of Microscopic Crystals. XXIII. The Structure and Light Absorption of Red Cupric Complexes with Succinimide
Authors: Yamada Shoichiro , Miki Seiko 
Published: July 2006

Abstract
The dichroism in the visible and ultraviolet region has been determined by the microscopic method with single crystals of K2Cu(sucim)4·6H2O, Cu(deen)2(ClO4)2 and Cu(sucim)2 (iso-C3H7NH2)2. From a comparison of these spectra with the spectra of most cupric complexes, it has been concluded that these compounds contain square-planar complexes of copper(II), with the fifth and sixth co-ordination sites left empty. It has been concluded, in a similar way, that the compounds with a formula of Cu(sucim)2(amine)2, the amine being methyl, ethyl, n-propyl, isopropyl, n-butyl and n-amyl amines as well as ammonia, consist of quadri-co-ordinate, square-planar complexes in the crystalline state.
The absorption spectra of bis(succinimidato)-bis(alkylamine)-copper(II) complexes in chloroform, benzene and methylene chloride, in which the compounds are colored dark-blue, have been determined. The enormously large band shift toward a lower frequency, on going from the crystal to the solution, seems to indicate that the configuration in these solvents is not the square-planar or trans-bis-(chloroform) configuration, but deviates from the square-plane.
The Photoisomerization of cis-Azobenzene in the Presence of Iodine
Authors: Yamashita Shigeru , Cosgrave Desmond P , Ono Hiroshi , Toyama Osamu 
Published: July 2006

Abstract
The conversion of cis-azobenzene in a n-hexane solution to its trans-isomer in the presence of iodine has been studied by light irradiation. The experiments with wavelengths of 313 and 436 mμ at −78°C have shown that the excitation of the molecular complex formed between cis-azobenzene and iodine, by its charge-transfer transition or by the blue-shifted absorption of complexed iodine, yields trans-azobenzene with a quantum yield independent of the composition of the solution. By comparing this finding with the results previously obtained for the cis-trans photoiso-merization of free azobenzene in n-hexane, a probable mechanism has been presented: CI2 + hν → CI2*, CI2* → C* + I2 and C* → T, where C and T denote cis and trans-eizoben-zene respectively.
The results obtained at 0°C by irradiation at wavelengths of 546 and 577 mμ, which are solely absorbed by free iodine in the solution, are similar to those previously obtained for stilbene; they may, therefore, be explained in a similar way, i. e., by the photochemical dissociation of free iodine, followed by the iodine atom-catalyzed isomerization of cis-azobenzene.
Preparation of Radioactive Antimony-120 of a High Specific Activity by the Irradiation of Tin with Protons
Authors: Saito Kazuo , Suzuki Nobuo , Seto Kunio , Ikegami Hidetsugu 
Published: July 2006

Abstract
1) By irradiation of a tin target (antimony content, less than 8×10−4%) with 15 MeV. protons (120 μ amp. hr.), about 1 mc. of 120Sb was produced, with a specific activity more than 30 μc. per μg of antimony.
2) The radioactive antimony was either separated by extraction with amylacetate from more than 6 n hydrochloric acid containing tin(IV) or by cation exchange in a 0.4% tartaric acid solution of pH 0.6 to 1.6 containing tin-(II).
3) 120Sb is electrolytically deposited on an evaporated film of silver or copper from a 1 to 3n hydrochloric acid solution containing 1% hydroxylamine hydrochloride with a yield of 70% within 3 hr.
4) Care should be taken to avoid hydro-lytic aging of antimony in diluted hydrochloric acid, which vitiates the extraction, the ion exchange, and the electrolysis.
Thermal and Radiation Oxidations of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. II. The Effect of Iron Sulfate and Chloride on Phenol Yield
Authors: Hotta Hiroshi , Terakawa Akira , Shimada Kazuo , Suzuki Nobutake 
Published: July 2006

Abstract
In the ferric sulfate solution, benzene can be oxidized to phenol with a good yield above 170°C, when not irradiated, but at lower temperatures, when irradiated. In the ferrous sulfate solution, the yield of phenol is independent of irradiation, and somewhat larger than in the irradiated ferric sulfate solution. Such a high yield of phenol is due to the complexing of hydroxycyclohexadienyl peroxy radical, produced with OH radical and oxygen dissolved, with ferrous ions.
Synthetic Resins Catalyzing the Racemization of Amino Acids. I. The Preparation of the Resins
Authors: Toi Koji , Izumi Yoshiharu , Akabori Shiro 
Published: July 2006

Abstract
1) Four resinous catalysts (Resins A–D) for the racemization of amino acids were prepared. They had structures partially similar to that of salicylaldehyde or pyridoxal. Resins A and B were prepared by the chemical modification of o-cresol-phenol-formalin resin and salicylic acid-phenol-formalin resin respectively. Resins C and D were obtained by attaching chemically pyridoxal and salicylaldehyde residues respectively to a styrenedivinylbenzene lattice.
2) These resins catalyzed the racemization of amino acids in the presence of cupric ions at 100°C.