bluuebunny/crossref_metadata_2025_split huggingface dataset:
Studies of Aminosugars. XVIII. Syntheses of Amino Derivatives of Schardinger α-Dextrin and Raffinose
Authors: Umezawa Sumio , Tatsuta Kuniaki 
Published: July 2006

Abstract
In continuing our study of the relationship between structural and biochemical characteristics of aminoglycosides, amino-deoxy derivatives of polysaccharides have been synthesized. The six primary hydroxyl groups of Schardinger α-dextrin and the three primary hydroxyl groups of raffinose have successfully been replaced by amino groups respectively, to give hexa-(6-amino-6-deoxy)-cyclohexaglucan (α-1,4) (IV) and 1″,6,6″-triamino-1″,6,6″-trideoxyraffinose (X). Their structures were confirmed by their NMR and IR spectra and by the studies of their chemical reactions. It has been found that hexa-(6-amino-6-deoxy)-cyclohexaglucan (α-1,4) showed significant antitumor activity.
Studies of the ζ-Potential of Natural and Synthetic Fibers in Dye Solutions. XVIII. ζ-Potential and Surface Dyeability of Heat-Set Nylon 6 Fiber in an Acid Dye Solution
Authors: Suzawa Toshiro , Saito Tomoyuki 
Published: July 2006

Abstract
In order to ascertain the relation between the change in the fibrous fine structure and the dyeability of nylon 6 fiber caused by its heat-setting, the ζ-potential, the surface dye adsorption, and the total dye adsorption of the heat-set nylon 6 fiber in an acidic solution (pH 3.0) of acid dye—Orange II were determined. The crystallinity and the birefringence of the fiber increase in the order of the untreated, the wet-heat-treated, and the dry-heat-treated fiber. The isoelectric points of the untreated, the wet-heat-treated, and the dry-heat-treated fiber are pH 5.4, pH 4.6, and pH 2.8 respectively. With the increase in the dye concentration, the sign of the ζ-potential of the untreated and the wet-heat-treated fiber in a dye solution change from positive to negative because of the electrostatic bonds between the NH3+ of the fiber and the dye anion, RSO3−, while the ζ-potential of the dry-heat-treated fiber increases its negative value because of the van der Waals’ forces between the fiber and the dye. The surface dye adsorption, as calculated from the difference between the surface charge density, Δσ, of the system with dye and that without dye, increases in any case as the dye concentration increases. The total dye adsorption increases as the dye concentration increases and attained the plateau regions at higher dye concentrations. The surface dye adsorptions become smaller in the order of the untreated, the dry-heat-treated, and the wet-heat-treated fiber. The total dye adsorptions become smaller in the order of the wet-heat-treated, the untreated, and the dry-heat-treated fiber. The differences in behavior among the fibers may be attributed to the adsorption of the dye to the loosely-packed portions in the amorphous region of the wet-heat-treated fiber, in addition to the differences in crystallinity and birefringence among the fibers. Moreover, the surface areas covered by adsorbed dye molecules, which were calculated from the reciprocal of the slope of the surface dye adsorption vs. the total dye adsorption curve of each fiber, were 1.8, 4.0, and 0.6×106cm2/g fiber in the order of the untreated, the wet-heat-treated, and the dry-heattreated fiber.
Studies of Poly-2-vinylpyridine. V. Temperature Dependence of the Intrinsic Viscosity and Osmotic Pressure of an Ethanol Solution
Authors: Arichi Shizuo 
Published: July 2006

Abstract
The viscosity of a series of 10 fractions of poly-2-vinylpyridine and the osmotic pressure of a fraction of the same polymer in ethanol were measured at several temperature. The temperature coefficients of the intrinsic viscosities of all the fractions measured were found to be completely negative. The Mark-Houwink equations for molecular-weight-homogeneous samples were obtained in ethanol at 10, 25, 40, and 65°C. The Flory constant, K=[η]θ⁄M1⁄2, obtained by the method of Fixman was found to be 13.0×10−4 at 25°C; this value is considerably larger than those estimated from the intrinsic viscosity data of this polymer in non-acidic solvents. The K value lowered to an ordinary level when it contained 2.7 n of dry ammonia in ethanol at 25°C. The values of the thermodynamic interaction parameters for dilution, ψ1 and θ, were obtained from the viscosity data; the former was negative, but nearly zero (−0.02), while the latter was unusually large (397°C). The excess molar entropy of dilution obtained from the measurements of the temperature dependence of the osmotic pressure was found to be negative, but almost zero, which was in accordance with the value of ψ1 described above; the excess molar heat of dilution obtained in the same way was found to be completely negative. Thus, the exhothermic interaction and negative excess entropy for dilution in this system were studied somewhat quantitatively.
Determination of the Self-diffusion Coefficient of Nickel Atoms in Nickel Sulfide
Authors: Fueki Kazuo , Oguri Yasuo , Mukaibo Takashi 
Published: July 2006

Abstract
The self-diffusion coefficient of ions or atoms in such crystals as halides, oxides and sulfides can be determined from the rate of the diffusion-controlled solid-state reaction as well as by the tracer method. In the present study, the self-diffusion coefficient of nickel atoms in nickel sulfide was determined from the rates of the sulfidation and desulfidation of nickel sulfide in H2S-H2gas mixtures. The results agreed well with the data obtained by the previous investigators employing the tracer technique.
Extraction-Photometric Determination of Osmium with Thenoyltrifluoroacetone
Authors: Rangnekar Asha V , Khopkar S M 
Published: July 2006

Abstract
The study of the liquid-liquid extraction of some platinum group elements (A. V. Rangnekar and S. M. Khopkar, Bull. Chem. Soc. Japan, 38, 1696 (1965); 39, 2169 (1966)), with fluorinated β-diketones showed that, osmium reduced to trivalent state with hydroxylamine hydrochloride forms a red chelate with 2-thenoyltrifluoroacetone, TTA. The chelate is readily extracted in benzene giving strong absorbance at around 440 mμ.
The Coprecipitation and Spectrophotometric Determination of Iron as 8-Hydroxyquinolinate
Authors: Shigematsu Tsunenobu , Matsui Masakazu , Munakata Megumu , Sumida Takayuki 
Published: July 2006

Abstract
The coprecipitation and spectrophotometric method, which is likened to the solvent extraction and spectrophotometric method, was applied to the following system for the first time; ferric ion was coprecipitated as 8-hydroxyquinolinate with an organic coprecipitant, and was determined spectrophotometrically after the precipitate was dissolved with an organic solvent. The effect of the ligand concentration on the pH vs. absorbance curve in the present method was apparently similar to that for solvent extraction. A nearly constant absorbance was obtained above pH 4 at a ligand concentration of 4×10−3 m. Over 100 mg of o-phenylphenol, an almost quantitative coprceipitation was obtained, though the absorbance decreased gradually as the coprecipitant was increased. The effect of diverse ions was also examined. Titanium(IV), vanadium(V) and molybdenum(VI) interfered considerably, while others have little effect on the absorbance. The method was applied to the determination of trace amounts of iron in natural waters and reagent grade sodium chloride.
Synthesis of Pyridoxine. II. The Preparation of Pyrrole Derivatives
Authors: Murakami Masuo , Takahashi Kozo , Matsumoto Jun , Tamazawa Kazuharu , Murase Kiyoshi , Iwamoto Hidenori , Iwanami Masaru 
Published: July 2006

Abstract
A new method for the synthesis of 2-acetyl-3, 4-diethoxycarbonylpyrrole and its derivatives by the Diels-Alder reaction is described, and the reaction mechanism of their formation is discussed.
Thermal Transformation of Alkali Salts of Aromatic Carboxylic Acids. V. Reaction of Potassium and Sodium Salts of Naphthoic Acids
Authors: Dozen Yasuhiko 
Published: July 2006

Abstract
The cadmium fluoride-catalyzed thermal transformation of potassium and sodium salts of naphtoic acids has been investigated. At the initial reaction stage both potassium and sodium α-naphthoate gave naphthalene and naphthalene-1, 2- and 1, 3-dicarboxylates, which were converted to naphthalene-2, 3- and 2, 6-dicarboxylates. The products composition, however, differed between potassium and sodium salts. Potassium β-naphthoate gave naphthalene and naphthalene 1, 2- and 2, 3-dicarboxylates, which were then further converted to naphthalene-2, 6-dicarboxylate. On the other hand, sodium β-naphthoate gave naphthalene and naphthalene-1, 2- and 2, 3-dicarboxylates. In the presence of potassium cyanate, potassium α- and β-naphthoates gave a high yield of naphthalene-2, 6-dicarboxylate. The mechanism of the reaction was discussed.
Organic Catalysts. IV. The Role of the Iron as an Oxidation Catalyst in Copper-Iron-Polyphthalocyanine
Authors: Inoue Hiroo , Kida Yasuji , Imoto Eiji 
Published: July 2006

Abstract
The role of the iron in copper-iron-polyphthalocyanine in the catalytic action in the oxidation of acetaldehyde ethylene acetal and cyclohexene was investigated on the basis of the inhibition of the reaction by the treatment of copper-iron-polyphthalocyanine with iron-binding agents and oxidizing agents. The catalytic action of copper-iron-polyphthalocyanine decreased or disappeared upon the addition of 2-phenylimidazole and pyridine to the reaction system, and upon the treatment with bromine or concentrated hydrochloric acid in the presence of air. However, the reduction of the oxidized copper-iron-polyphthalocyanine with ascorbic acid or sodium thiosulfate recovered the catalytic activity. Furthermore, the catalytic activities of iron-metal-polyphthalocyanines (metal; V, Cr, Mn, Co, Ni, Cu and Zn) and copper-metal-polyphthalocyanines (metal; V, Cr, Co, Ni and Zn) in the oxidation of acetaldehyde ethylene acetal were investigated. The former groups showed the catalytic actions, but no catalytic actions were observed in the latter groups. The catalytic activities of iron-metal-polyphthalocyanines increased with a decrease in the activation energy of the electrical conductivity of the polymer. From these results, it was presumed that the Fe(II) ions located in the conjugated system act as active sites for the activation of oxygen and for the decomposition of peroxide.
Organic Catalysts. V. Specific Catalytic Properties of Copper-Iron-Polyphthalocyanine in the Oxidation of Aldehydes
Authors: Inoue Hiroo , Kida Yasuji , Imoto Eiji 
Published: July 2006

Abstract
Copper-iron-polyphthalocyanine showed a specific catalysis for the oxidations of the substituted benzaldehydes and the saturated aldehydes with oxygen. The catalytic activity of copper-iron-polyphthalocyanine was solvent-dependent: tetrahydrofuran, ethanol, acetonitrile, ethyl acetate and anisole inhibited the oxidation of benzaldehyde by copper-iron-polyphthalocyanine and oxygen, while benzene and acetone resulted in catalytic oxidation. Benzaldehyde and the saturated aliphatic aldehydes in benzene were oxidized catalytically with copper-iron-polyphthalocyanine and oxygen to afford the corresponding peroxy acids and acids in quantitative yields. Furthermore, oxygen was absorbed with no induction period; the rate of oxygen absorption was in the range of 8–13 ml/min. On the other hand, the unsaturated aliphatic aldehydes, cinnamaldehyde and acrolein, were oxidized with a very slow rate of oxygen absorption in spite of the existence of copper-iron-polyphthalocyanine in the reaction system. p-Methylbenzaldehyde and p-chlorobenzaldehyde were oxidized by copper-iron-polyphthalocyanine and oxygen in Induction periods of about 8 and 15 min respectively, thus affording the corresponding peroxy acids and acids. However, no oxidations of p-nitrobenzaldehyde, p-hydroxycarbonylbenzaldehyde, p- and m-hydroxybenzaldehyde, p- and m-methoxybenzaldehyde and p-dimethylaminobenzaldehyde with copper-iron-polyphthalocyanine and oxygen were observed.
A Study on Mixed Vanadium Catalysts for the Ammoxidation of Xylene
Authors: Ito Masatomo , Tanaka Hazime , Matsumoto Akira 
Published: July 2006

Abstract
The phase composition and the physicochemical properties of an antimony-vanadium catalyst and a chromium-vanadium catalyst for the ammoxidation of xylene were studied by X-ray diffraction method, differential thermal analysis, infrared absorption analysis and ESR measurement. An antimony-vanadium catalyst consisted essentially of SbVO4 which contained no double covalent bond V=O, while a chromium-vanadium catalyst consisted essentially of a chemical compound which was different from CrVO4. SbVO4 and CrVO4 were hard to be reduced with ammonia at 400°C, while a chemical compound in the chromium-vanadium system was reducible. The activity and the selectivity of reaction were affected by the nature and the distribution of metal ions and oxygen ion on surface.
A Measure of the Electron-donating Power and Electron-accepting Power of Liquid Organic Compounds
Authors: Kagiya Tsutomu , Sumida Yūzō , Inoue Tokuji 
Published: July 2006

Abstract
A quantitative study has been made of the measurement of the electron-donating nature and the electron-accepting nature of various liquid organic compounds. The position of the O–D or C=O absorption band of a liquid compound which contained a small quantity of methanol-d or of acetophenone was measured by means of an infrared spectrophotometer. The relative magnitude of the electron-donating nature or of the electron-accepting nature of the compound was compared by a measurement of the perturbation which it produced on the O–D vibrational band of methanol-d or on the C=O vibrational band of acetophenone. The electron-donating power or the electron-accepting power of a compound is defined as the relative difference (counted as wave numbers) of the O–D or the C=O absorption band observed in the compound from that in benzene. From the results, it was found that, in a homologous series, the electron-donating power decreased with an increase in the ionization potential in the gaseous phase, or with an increase in the pKb value in the liquid phase, and that it increased linearly with the co-ordination power to diethyl zinc. It was also found that the electron-accepting power increased with an increase in the electron affinity in the gaseous phase and decreased with an increase in the pKa value in the liquid phase. Moreover, the various liquid organic compounds, classified into four typical groups, were considered on the basis of their electron-donating and electron-accepting power.
A Definition of Selectivity of Nucleophilic Solvation in a Binary Solution
Authors: Kagiya Tsutomu , Sumida Yūzō , Inoue Tokuji 
Published: July 2006

Abstract
This is the third paper of a series in which the behavior of nucleophilic solvation is investigated by a measurement of the position and the area of the O–D vibrational band of methanol-d. In a binary solution which consisted of two components remarkably different in electron-donating power, the relation between the mol fraction (n1) of the S1 component and the area fraction (n1) of S1 was not a straight line, but a concave or convex curve. This fact suggests that a component co-ordinates selectively to a deuterium atom in a methanol-d molecule. The following definition of the selectivity of nucleophilic solvation to methanol-d as a cation model of the S2 component to the S1 component is proposed:
(Remark: Graphics omitted.)
The selectivity of the S2 solvent to the S1 solvent was considered in detail in connection with the equilibrium constant of the nucleophilic solvation to methanol-d of the solvent; the selectivity was also found to be defined as the ratio of the equilibrium constants of the solvents used. Since there was a correlation between the equilibrium constants and the electron-donating powers, it was concluded that the selectivity of an S2 solvent to a standard solvent, S1 could be quantitatively estimated by measuring only the position of the O–D vibrational band of methanol-d in each solvent.
Electron Spin Resonance Study on Ultraviolet Light Irradiated Benzene Adsorbed on Silica Gel and Alumina
Authors: Tanei Tadayoshi 
Published: July 2006

Abstract
Benzene adsorbed on silica gel was irradiated at 77°K with ultraviolet light. Three kinds of samples, with different degree of adsorption, were examined. ESR spectra were strongly dependent on the amount of benzene adsorbed and three different spectra were observed; (1) six-line spectrum with a splitting value of 6 gauss, assigned to phenyl radical, (2) seven-line spectrum with a splitting value of 4.5 gauss, assigned to benzene cation radical, and (3) apparent nine-line spectrum with 2.4 gauss splitting due to benzene dimer cation radical. Upon raising temperature, benzene cation radical was found to transform into benzene dimer cation radical. In UV-irradiated benzene-alumina system, cyclohexadienyl radicals were observed in addition to the ion radicals. It is suggested that the above reaction may be occurred by two photon absorption process involving the excitation of triplet benzene.
Synthesis of Chelating Agents. V. 1,2,3-Triaminopropanehexaacetic Acid and Its Acid Dissociation Scheme
Authors: Miyazaki Mitsumasa , Moriguchi Yoshiki , Ueno Keihei 
Published: July 2006

Abstract
1,2,3-Triaminopropane-N,N,N′,N′,N″,N″-hexaacetic acid (TAPHA) was synthesized by the carboxymethylation of 1,2,3-triaminopropane. The acid dissociation scheme of the ligand was studied by means of potentiometric titration, infrared absorption spectroscopy and proton nuclear magnetic resonance spectroscopy. It is found that TAPHA exists as a zwitter ion in aqueous solution, in which protons attach to each nitrogen atom of 1- and 3-carbon, and that the dissociations of first four and the last two steps correspond to the dissociations of carboxylic protons and ammonium protons, respectively. The stepwise proton dissociation constants of the ligand is determined as pK1≈2, pK2=2.43, pK3=3.52, pK4=4.30, pK5=8.26 and pK6=9.88 (μ=0.1, 25°C).
The Mössbauer Spectra of Various Natural Minerals
Authors: Takashima Yoshimasa , Ohashi Shigeru 
Published: July 2006

Abstract
The Mössbauer spectra have been measured for sixteen samples of natural minerals, including siderite, vivianite, garnets, olivines, pyroxenes, and other silicate minerals, The spectra were analyzed for the isomer shifts and quadrupole splittings, and the information thus obtained was correlated with the oxidation states of irons and the crystal structure of minerals. The relative abundances of the various sites present in a given mineral were also estimated by measuring the relative intensities of the absorption peaks in the resolved spectrum of the mineral. All the basic Mössbauer spectral patterns observed for the natural minerals are presented in graphic form.
Kinetic Study of the Gas-phase Oxidation of Propylene in a Propylene-excess Atmosphere under Pressure
Authors: Masai Mitsuo , Echigoya Etsuro , Morikawa Kiyoshi 
Published: July 2006

Abstract
Reaction-rate equations are derived for oxygen, acetaldehyde, propylene oxide, carbon monoxide, and ethylene on the basis of a plausible reaction scheme. These rate equations are shown to fit the experimental results obtained using a flow-type reactor. It seems most reasonable to conclude that the above reaction mechanism is correct. The type of flow of the reactant gas through the reactor used in this work can be practically regarded as a plug flow from the measurements of the resisdence time distribution using the pulse-tracer method.
The Chemiluminescence of Indole Derivatives. III. On the Mechanism of the Chemiluminescence of 2,3-Dimethylindole and 5-Substituted- 2,3-dimethylindoles in the Dimethyl Sulfoxide - Alkali System
Authors: Sugiyama Noboru , Akutagawa Masamoto , Yamamoto Hiroshi 
Published: July 2006

Abstract
A bright green light is observed on the treatment of a solution of 2,3-dimethylindole (I) and its hydroperoxide (II) in dimethyl sulfoxide (DMSO) with alkali (potassium t-butoxide or granular potassium hydroxide) under streams of oxygen and hydrogen respectively. The change in their ultraviolet and fluorescent spectra with the time and the chemiluminescent spectra is measured. The compound II is concluded to be the reaction intermediate of I; it decomposes to yield an excited singlet state of an o-acetamidoacetophenone anion (III*), a light emitting species in this reaction. The investigation, then extended to four 5-substituted-2,3-dimethylindoles, revealed that three of them displayed chemiluminescence through the same mechanism as in the case of I.
The Mechanism of the Alkaline Fusion of Halodiphenyl Sulfone and Halobenzenesulfinic Acids
Authors: Furukawa Naomichi , Oae Shigeru 
Published: July 2006

Abstract
The alkaline fusion of 2-chlorophenyl phenyl sulfone afforded phenol, benzene and chlorobenzene. The initial step of the reaction appears to be the aromatic SN2-type replacement of chlorine to form 2-hydroxyphenyl phenyl sulfone upon which the hydroxide ion further attacks both phenyl carbon-1 and the sulfur atom of the sulfone group to form the final products. The 14C tracer experiment indicates that the preference of the nucleophilic-attacking site of the hydroxide ion appears to vary with the reaction temperature. A similar alkaline fusion of 2-bromo-4-tolyl phenyl sulfone gave not only benzene, bromotoluene, and phenol, but also o- and m-cresol, indicating that the reaction proceeds through a somewhat different path. Meanwhile, the alkaline fusion of 2-chlorobenzenesulfinic acid appears to proceed through the o-sulfinic benzyne formation; thus 2-bromo-4-tolylsulfinic acid gave equal amounts of o- and m-cresols.
Studies on Isothiazoles. IV. A New Synthetic Route to 4-Cyanoisothiazoles
Authors: Naito Takayuki , Nakagawa Susumu , Okumura Jun , Takahashi Kiyoshi , Masuko Kenji , Narita Yukio 
Published: July 2006

Abstract
4-Cyanoisothiazoles have been prepared by a novel procedure which comprises the reacreaction of β-cyano enamines with thionyl chloride or sulfur monochloride. The reaction proceeds favorably in nonpolar solvents or in the absence of solvent. However, the cyclization did not occur in dimethylformamide and instead an amidine derivative was isolated. The preparations of the corresponding isothiazole-4-carboxylic acids are also described briefly.
Solvent Effect under High Pressure. II
Authors: Kondo Yasuhiko , Uchida Miyoji , Tokura Niichiro 
Published: July 2006

Abstract
The activation volume of the reaction of triethylamine with ethyl iodide has been measured in four solvents. A linear relationship has been observed between the values of ΔV0\eweq for the Menschutkin reaction in various solvents and the products of the compressibility and the molar volume of the pure solvent, as has been suggested in a previous paper. From the slope of the plots of (−ΔV0\eweq) vs. KV°, the product of the solvation number and the average pressure within the solvation shell of an activated complex has been calculated to be 2.6×103 (kg·cm−2) according to a model proposed by the authors. An abnormal acceleration due to pressure has been observed for the reaction of triethylamine with ethyl iodide in p-xylene and dioxane at 30°C. This acceleration effects has been attributed to the partial freezing of the solvent under high pressure.
The Crystal Structure of (−)D-Tris(trimethylenediamine)cobalt(III) Bromide Monohydrate
Authors: Nomura Teruo , Marumo Fumiyuki , Saito Yoshihiko 
Published: July 2006

Abstract
The structure of (−)D-[Co(tn)3]Br3·H2O (tn: H2N–CH2-CH2-CH2-NH2) has been solved by the heavy atom method and refined to R=0.11 by least-squares analysis based on 1845 threedimensional data. The substance crystallizes in the monoclinic space group P21 with unit cell dimensions: a=16.274, b=9.863, c=9.489 Å, β=126.4° and Z=2. The complex ion in the structure has approximately a three-fold axis of rotation. The three six-membered Co-tn rings are nearly identical and take chair form. The chelate ring is rather flattened out, owing to the strong H-H repulsion. The absolute configuration of (−)D-[Co(tn)3]3+ has been found to be the same as that of (+)D-[Co(en)3]3+.