bluuebunny/crossref_metadata_2025_split huggingface dataset:
Influence of Metal Ions and of Metal Chelates on the Hydrolysis of α-d-Glucose 1-Phosphate
Authors: Murakami Yukito , Tanaka Michio 
Published: July 2006

Abstract
The hydrolysis reaction of α-d-glucose 1-phosphate has been studied in the presence of several metal ions and metal chelates at 40.0 and 60.0°C, in the pH range of 1.69–2.71, and at an ionic strength of 0.10 m (KNO3). The reaction rate was followed by the colorimetric method using a combination of the amidol reagent and 8.3% molybdate solution. Among the metal ions employed in this work, dipositive ions, such as manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and uranyl ions, were observed to be nearly without effect on the rate of hydrolysis, while iron(III) and thorium(IV) ions demonstrated a negative catalytic effect. On the other hand, all the chelating agents employed tend to restore the reaction rate in reference to the corresponding metal-ion-effected reactions. With the 1:1 thorium(IV)-EDTA and the 1:1 iron(III)-EDTA chelate system, the rate was completely restored. Both iron(III)-kojate and thorium(IV)-Tiron chelate systems restored the reaction rate to a lesser extent. The roles of the chelating agents were discussed. The reaction mechanism in the presence of the catalyst species has been considered, and two possible mechanisms have been put forward for the present reactions.
Studies of the Photoreduction of Acridine in Ethanol by the Flash Technique
Authors: Kira Akira , Kato Shunji , Koizumi Masao 
Published: July 2006

Abstract
With the flash technique, the absorption spectra of the triplet state and of the semireduced form of acridine were observed, and the kinetics of the reactions involving these transient species was investigated. It was established that the photoreduction of acridine in the deaerated ethanol solution proceeds via two paths. One is a path via semireduced acridine; this path is strongly inhibited by the presence of oxygen, which efficiently oxidizes semireduced acridine. In the other path, the final product, acridan, is produced immediately after flashing, with no appreciable transient species being formed. The photoreduction by this path is not affected by the presence of oxygen. It may be presumed that this process is a molecular one between singlet acridine and alcohol. The reactive species in the former path also seems to be the singlet excited state instead of the lowest triplet state.
Aldehydes in Lake and Sea Waters
Authors: Kamata Eijiro 
Published: July 2006

Abstract
The vertical distribution of aldehydes in Lake Kizaki during summer stagnation is described. Aldehydes are found only in the hypolimnion, not in the upper aerobic water layers. The highest aldehyde content in three series of vertical samples is 0.11 mg./l. in terms of formaldehyde equivalents. It was shown by laboratory experiments that formaldehyde is rapidly decomposed in aerobic lake water, but very slowly in anaerobic lake water. In sea waters, aldehydes are not found in the surface water layer, and no systematic variation is noticed in the verticall distribution.
The Solvation of Ions in Liquid Sulfur Dioxide
Authors: Kondo Yasuhiko , Goto Tsutomu , Suo Isamu , Tokura Niichiro 
Published: July 2006

Abstract
The variation in the density and in the sound velocity with the concentration was measured in a liquid sulfur dioxide solution of electrolytes. The amounts of solvations and the volume changes which accompany the dissolving of the electrolytes were estimated. In liquid sulfur dioxide they were found to be considerably greater than those in water. The relations between the volume changes and the solvations were also discussed.
A New Mode of the Formation of the Meso-ionic Pyrido[2,1-b]-3,4-dihydro-4-oxothiazole: An Attempted Preparation of Pyrido[2,1-b]-3,5-dihydro-5-oxothiazole
Authors: Kato Hiroshi , Tanaka Kazuo , Ohta Masaki 
Published: July 2006

Abstract
The acylation of 2-mercaptopyridine gives S-acyl derivatives, which, on treatment with chloroacetic acid, give the title compound.
The Synthesis of Pyrido[2,1-b]-3,4-dihydro-4-iminothiazole Derivatives. A New Meso-ionic Heterocyclic System
Authors: Kato Hiroshi , Ohta Masaki 
Published: July 2006

Abstract
The action of acyl chlorides on 2-pyridylthioacetonitrile and related compounds gives the corresponding N-acylated pyrido[2,1-b]-3,4-dihydro-4-iminothiazoles and related compounds.
The Reaction of the Exo-cyclic Imino Group of “4-Thiazone Imine”
Authors: Ohta Masaki , Yoshida Kei , Sato Shigeru 
Published: July 2006

Abstract
In order to accumulate further information about the properties of meso-ionic compounds -with an exo-cyclic imino group, the reactivity of an exo-cyclic imino group of thiazone imine as compared with that of sydnone imine was investigated. Moreover, for the purpose of the pharmacological test, 2,3-disubstituted thiazone imine hydrochlorides and their N-acetyl derivatives were prepared.
Organic Sulfur Compounds. IV. The Reactions of Arylsulfonic Acids with Alkyl Chlorocarbonates
Authors: Yamamoto Asami , Kobayashi Michio 
Published: July 2006

Abstract
The reactions of p-toluenesulfonic acid salt with alkyl chlorocarbonates have been investigated and their mechanism discussed. The reactions were slow at low temperature, and the intermediates, sulfonic carbonic anhydrides, could be isolated. When heated, these mixed anhydrides decomposed to alkyl sulfonates and carbon dioxide. p-Toluenesulfonic acid-18O was prepared and its reaction with ethyl chlorocarbonate examined. All three oxygen atoms of the sulfonic acid were retained in the ethyl sulfonate formed. The reaction of isobutyl chlorocarbonate with silver p-toluenesulfonate gave a mixture of isobutyl- and s-butyl sulfonate. On the basis of these experiments, the mechanism involving the free alkyl cation has been proposed for the decomposition of the sulfonic-carbonic anhydrides.
Rearrangements of Tertiary Amine Oxide. XV. The Reaction of Heterocyclic N-Oxides with p-Nitrobenzenesulfinyl Chloride
Authors: Oae Shigeru , Ikura Katuyata 
Published: July 2006

Abstract
In the reaction of pyridine and α-picoline N-oxide with p-nitrobenzenesulfinyl chloride, the N–O bond of the intermediate salt appears to cleave homolytically, as in the case of N-oxide with p-nitrobenzenesulfenyl chloride, and the p-nitrosulfonyl radical which arises from the homolytic cleavage of the N–O bond is considered to be so stable that only the secondary reaction products from the sulfonyl radical, and no heteroring-substituted products, are obtained. It is the same in the case of unsubstituted benzenesulfinyl chloride.
The Simultaneous First- and Second-Order Esterifications of l-Menthol by Acyl Chlorides: Autocatalyses by Menthol in Acetonitrile and in Liquid Sulfur Dioxide
Authors: Akiyama Fuminori , Tokura Niichiro 
Published: July 2006

Abstract
The propionylation and p-methoxybenzoylation of l-menthol in various solvents have been studied. In chloroform, benzene, ethyl methyl ketone and carbon tetrachloride, the reaction follows the second-order rate law. However, in acetonitrile or in liquid sulfur dioxide, the rate follows the second-order rate law only at the initial stage of the reaction; thereafter it gradually deviates from the second-order type to the first-order one. Moreover, the first-order rate equations both in acetonitrile and liquid sulfur dioxide are dependent on the initial concentration of the alcohol; the over-all rates being expressed as:
Rate=k1°(AcCl)(ROH)0+k2(AcCl)(ROH)
where(ROH)0, (ROH), (AcCl), k1° and k2 are the concentrations of the alcohol at time zero and t, that of the acyl chloride at time t, the first-order rate constant and the second-order rate constant respectively.
The Studies of the Cage Effect of Solvents. VI. The Photolysis of Methylazoethane in n-Heptane
Authors: Fujita Shin’ichi , Kodama Sukeya , Toyama Osamu 
Published: July 2006

Abstract
Methylazoethane was photolyzed in n-heptane in order to study the effect of a solvent cage quantitatively; the results obtained were then compared with those for azomethane and azoethane previously studied. By using styrene as a scavenger for radicals, it was demonstrated that a large fraction (90% at −75°C and 58% at 100°C) of a pair of methyl and ethyl radicals formed by the decomposition of a molecule of methylazoethane combines to form propane or disproportionates to form methane and ethylene in an original solvent cage. The ratio of the rate constant for the disproportionation to that for the combination is small, and it decreases with a rise in the temperature, as was previously found for azoethane. The effect of the temperature on the yields of the products of cage reactions in the present work and in the previous work with azomethane and azoethane shows that the combination of ethyl radicals and the cross-combination of methyl and ethyl radicals in a solution require appreciable activation energies, even if that for the combination of methyl radicals is zero.
The Refined Calculation of the Band-gap Energy of Tetramethylammonium Pentaiodide
Authors: Kusabayashi Shigekazu , Mikawa Hiroshi , Konda Misako , Hayashi Masano 
Published: July 2006

Abstract
The band-gap energy has been calculated by a tight-binding approximation in a previous report. Although the value thus calculated coincided rather well with the experimental value, it might yet be possible that the band-gap energy will change appreciably when the interactions of all the energy levels are considered at one time. It was, therefore, calculated by the following method, which considers in principle all the level interactions. A repeating unit is composed of 30 atomic orbitals. Each atomic wave function makes three-dimensional Bloch functions. The crystal wave function is set up in the form of a linear combination of these 30 Bloch functions. The energy is then calculated by applying the variation principle and by using the Hückel approximation. The band-gap energy thus calculated is 1.20 eV. This value is near the experimental value, 1.36 eV.; it was also close to the previous result, 1.26 eV., thus confirming the previous calculations. The consideration of the band-widths and the density of the state may interpret the experimental results on the sign of the carrier. The results offer additional support for our previous conclusion regarding the conduction mechanism.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. X. Nitrates of α-Hydroxy-carboxylic Acids
Authors: Tsuzuki Yojiro , Tanabe Koko , Okamoto Kikuhiko , Fukubayashi Michiyo 
Published: July 2006

Abstract
The rotatory dispersion (RD) and ultraviolet absorption of some α-hydroxy-carboxylic acids and their nitrates have been measured and analyzed. A distinct relation has been found between the configuration and the sign of the Cotton effect; namely, nitrates of α-d-hydroxy-carboxylic acids (R-configuration) show positive Cotton effects, while those of α-l-hydroxy-carboxylie acids (S-configuration) show negative Cotton effects. Thus a rotatory contribution by the nitrates of the α-hydroxyl group has been suggested, though it is opposite in sign to the xanthates of the α-hydroxy-carboxylic acids.
A Thermodynamic Approach to Thixotropy
Authors: Sen\={o} Manabu 
Published: July 2006

Abstract
The thixotropic behavior is discussed on the basis of the thermodynamics of irreversible processes. The fundamental equations are given for the thixotropic fluids by accepting the concept that the internal structure of the system is destroyed by the applied forces, and the general phenomenological equations are written for all the processes occurring in this system. The process by which the thixotropic recovery takes place is non-stationary. A method of specifying this process is proposed by introducing the concept of a fictitious pressure tensor; the data on a rubber latex suspension given by Mooney is analyzed by this method.
The Application of the Molecular Orbital Theory to the Bond Scissiom of Aliphatic Amines
Authors: Hirota Kozo , Itoh Michiyasu 
Published: July 2006

Abstract
The relative scission-probabilities of C–C bonds of n-propyl, n-butyl and isobutyl amines being formed by electron impact (90 V.) were determined by the use of mass spectrometers of the usual type and of the high-resolution type. They were in good accordance with the theoretical values calculated by the LCBO-MO theory which had been proposed and found successful in explaining the mass spectra of n-paraffins and methyl alkyl ketones.
Organic Syntheses by Means of Noble Metal Compounds. XIV. The Carbonylation of Cyclooctadienes
Authors: Tsuji Jiro , Hosaka Shuntaro , Kiji Jitsuo , Susuki Tosaku 
Published: July 2006

Abstract
The 1,5-cyclooctadiene - palladium chloride complex and carbon monoxide react in ethanol to form ethyl 4-cyclooctenecarboxylate. The carbonylation of 1,5-cyclooctadiene catalyzed by palladium chloride has given ethyl 4-cyclooctenecarboxylate and cyclooctanedicarboxylate. It has been found that the monoester can be obtained selectively under certain conditions; the further carbonylation of the monoester gives the diester. Under the same reaction conditions, 1,3-cyclooctadiene gives ethyl 2-cyclooctenecarboxylate in a low yield. Metallic palladium has been found to be the true catalyst and the presence of hydrogen chloride has been found to be essential for the catalysis. It has also been found that the 1, 5-cyclooctadiene - palladium chloride complex can be formed from 1,5-cyclooctadiene, metallic palladium and hydrogen chloride by heating them in an autoclave under nitrogen. It seems likely that the catalytic carbonylation of 1,5-cyclooctadiene proceeds through the formation of the 1,5-cyclooctadiene - palladium chloride complex.
The Benzene-photosensitized Isomerization of Butene-2 and Pentene-2
Authors: Tanaka Masahiro , Kato Masaaki , Sato Shin 
Published: July 2006

Abstract
The benzene-photosensitized cis-trans isomerization of butene-2 has been reinvestigated, using 2537 Å as the light source. A comparative study with pentene-2 has also been carried out. In all experiments, pentene-2 behaved very similarly to butene-2. The quantum yield of the isomerization was estimated to be 0.27±0.03, irrespective of the olefin used. The following photostationary ratios of the cis to the trans isomer were obtained: 1.05±0.1 for butene-2, and 0.99±0.1 for pentene-2. The ratio of the initial rates of isomerization was, for both olefins, 1.15±0.15, in favor of the isomerization from the cis to the trans isomer. Both ratios are very close to unity; this finding is in agreement with our previous results (M. Tanaka, T. Terao and S. Sato, Bull. Chem. Soc. Japan, 38, 1645 (1965)).
On the Asymmetric Interaction of the Optical Antipodes with Amylose
Authors: Ohara Masaaki , Chen Chau-Yang , Kwan Takao 
Published: July 2006

Abstract
The asymmetric adsorption of d, l-mandelic acid and its homologues has been demonstrated on amylose by means of the column chromatographic and static techniques. The d-(−)-isomer of mandelic acid has been found to be adsorbed more weakly than the l-(+)-isomer; the separation factor of the two antipodes has been estimated to be 1.09 at 0°C. This value is greater than that on starch, suggesting that amylose may have a somewhat higher selectivity for the asymmetric adsorption of the optical antipodes than amylopectin. The anomalous interaction of d, l-atrolactic acid has been observed on the amylose much as in the case with starch reported previously.
Hydrothermal Synthesis of Fluor-Hydroxyl Muscovite
Authors: Noda Tokiti , Endo Yasuhiko , Ushio Masumi 
Published: July 2006

Abstract
Fluor-hydroxyl muscovite was synthesized from a mixture of gels and chemicals of the KAl3Si3O10Fx(OH)2−x composition, where x=0, 0.5, 1.0, 1.5 and 2.0, in the temperature range of 500–600°C under pressures ranging from 500 to 900 atm. The fluorine content of the synthetic muscovite increased with the increase in x, but the distribution coefficient of fluorine [(the fluorine content of the crystal)/(the fluorine concentration of the solution)] decreased with the increase in x, increased with the increase in the temperature of synthesis, and decreased with the increase in the pressure of synthesis. The synthetic fluor-hydroxyl muscovite crystallized mainly in 1M polymorph, and very little in 2M polymorph, at 500°C in 20 hr. The fraction of 2M muscovite increased with the increasing temperature of synthesis. The d005 and d060d lattice spacings of the mica were observed to decrease linearly with the increase in the fluorine content of the mica.
The Stability of Fused Rings in Metal Chelates. III. The Relative Stability of Copper(II) Complexes of Aldehyde- and Ketone-Schiff Bases
Authors: Nakao Yasuo , Sakurai Ken-ichi , Nakahara Akitsugu 
Published: July 2006

Abstract
The relationship between the structure of fused-ring systems and the relative stability of copper(II) Schiff base chelates has been discussed, on the basis of the properties of six copper(II) complexes, in connection with the transamination reaction. As the conclusion it has been suggested that the transamination reaction in fused-ring systems containing copper(II)-glyoxylate- or -pyruvate-Schiff bases may be expected only in such appropriately unstable systems as have two five-membered rings and that it is generally accompanied by a stabilization of the system. The preparation and properties of the two new copper(II) chelates, glyoxylidene-β-alaninatoaquo-copper(II) and pyruvidene-α-alaninatoaquocopper(II), have been described.
The Effect of Acetates on the Synthesis of Acetic Acid from Methanol and Carbon Monoxide in the Presence of Cobalt(II) Iodide as a Catalyst
Authors: Mizoroki Tsutomu , Nakayama Mikitake 
Published: July 2006

Abstract
In the synthesis of acetic acid from methanol and carbon monoxide in the presence of cobalt(II) iodide as a catalyst, the addition of an acetate has been shown to have a great influence upon the methanol conversion into total acetic acid. When the added amounts of potassium acetate are from one to two times as much as that of cobalt (II) ion, both methanol conversion and its reaction rate reach a maximum, and methanol is prevented from forming dimethyl ether. On the other hand, the reaction nearly stops when the amount of potassium acetate becomes more than four times as large. The variation in the absorption spectrum of cobalt (II) ion in course of the reaction shows that the increase in the added amount of an acetate is favorable for the formation of cobalt carbonyls and that most cobalt(II) ions are tetrahedral species of the [Co(AcO)4−n-In]2− type so long as the reaction is promoted with the catalyst. From these experimental results, the course of the reaction has been discussed.
The Reaction of Amino Alcohols with Acrylates
Authors: Ogata Naoya , Asahara Tomohiko 
Published: July 2006

Abstract
The addition reaction of amino alcohols with acrylates were studied. The addition takes place at the amino group of amino alcohol, producing N-(hydroxyalkyl)-β-alanine in a good yield. The reaction rate becomes slower as the ester group of acrylate becomes larger, and phenyl acrylate gives a polymer as soon as it is mixed with ethanolamine. The rates of the addition reaction with acrylate are in the following order: NH2CH2CH2OH&gt;CH3NHCH2CH2OH&gt;&gt;RNH2&gt;NH(CH2CH2OH)2.
Intramolecular Hydrogen Bonds. VII. Methyl Mandelates and Related Compounds
Authors: Mori Nobuo , Tanaka Yoshiteru , Tsuzuki Yojiro 
Published: July 2006

Abstract
The infrared OH spectra of an ArCH(OH)(CH2)nCOOMe series (n=0 and 1) in dilute carbon tetrachloride solutions have been measured at 25°C with a Perkin-Elmer 21 spectrometer. A comparison of the data with those of other related compounds shows that the OH group forms a hydrogen bond predominantly with the carbonyl-oxygen atom and also with the ether-oxygen atom and/or the π-electrons of the phenyl group, while, practically speaking, no free OH group is present. Further, the NMR chemical shifts of the methine- and the methyl-protons when n=0, as measured with a Varian A-60 spectrometer, have been correlated with the Hammett substituent constants; the shift of the methine-proton, when the ring-substituent is a halogen, does not fall on the correlation line, but falls on a separate line.
The Heats of Dilution of Atactic Polystyrene Solutions
Authors: Kagemoto Akihiro , Murakami Sachio , Fujishiro Ryoichi 
Published: July 2006

Abstract
The heats of dilution of atactic polystyrene (\barP=244)-various solvent systems have been measured by using a micro-twin-calorimeter at 25°C. Toluene, anisole, ethyl methyl ketone, dioxane and ethyl acetate were used as the solvents. For the analysis of the experimental data obtained by each dilution process, the simple Van Laar formula has been used, and the apparent enthalpy parameter between the polymer and the solvent has been derived. Since these interaction parameters seemed to depend on the concentration, we tried to analyze the experimental data with a modified Van Laar formula which contained interaction parameters depending on the concentration. The interaction parameters obtained by these analyses are considerably dependent on the concentration in good solvents, while those in poor solvents depend hardly at all on the concentration. This dependence of the interaction parameters on the concentration has been explained by using the dilute solution theory of polymer solutions proposed by Flory and Krigbaum (J. Chem. phys., 18, 1086 (1951)). The interaction parameters in the dilute region have been compared with those obtained by other methods, and the agreement between our values and those obtained by other methods has been found to be fairly good.
Ferrocene-containing Polymers. IX. Polycondensation of Ferrocene with Formaldehyde
Authors: Neuse Eberhard W , Quo Edward 
Published: July 2006

Abstract
The Lewis acid-catalyzed polycondensation of ferrocene with formaldehyde or its dimethyl-acetal gives rise to the formation of soluble, novolac-type polymers comprising ferrocenylene units interlinked by methylene bridges. In contrast to earlier work performed by other investigators in liquid hydrogen fluoride or sulfuric acid media, where only non-polymeric products were described, propagation is accomplished in the present case by condensing the reactants in a closed system in bulk at temperatures up to 170°C. The resulting polymers, with Mn values up to 4000 (unfractionated), are shown by elemental and spectroscopic analyses and viscometric data to be essentially identical with the previously reported polycondensation products of N, N-dimethyl-aminomethylferrocene with ferrocene. Infrared spectroscopy shows the intralinear substitution to be predominantly homoannular, which is expected as a result of the electronic effects exercised by the methylene substituent. Under appropriate conditions, additional methylene groups can be incorporated into the polymer, giving rise to double-bridged segments and inter-chain bridging. Strongly crosslinked polymers are obtained if excess aldehydic reactant is employed at temperatures in the 170–185°C range.
The Catalytic Dehyrochlorination of 1, 2-Dichloroethane on Active Carbon in the Presence of Some Hydrocarbons
Authors: Okamoto Kunio , Tanaka Noboru , Adachi Kiyoshi , Shingu Haruo 
Published: July 2006

Abstract
The catalytic pyrolysis of 1, 2-dichloroethane on active carbon, carried out at 300 and 400°C in the presence of toluene, benzene and n-hexane, resulted predominantly in ethylene instead of vinyl chloride, which is known in the literature as the major pyrolysis product of the titled compound; the pyrolysis rates were suppressed by these hydrocarbons. These results have been explained by assuming a radical-chain mechanism similar to that suggested for the “homogeneous” pyrolysis of this compound. The chain length derived from the proposed mechanism has been estimated to be 20 to 50.