bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hydrogen Peroxide Oxidation. V. Selenium Dioxide Catalyzed Oxidative Rearrangement Reaction of Desoxybenzoin
Authors: Sonoda Noboru , Tsutsumi Shigeru 
Published: July 2006

Abstract
1) Selenium dioxide catalyzed oxidation of desoxybenzoin with hydrogen peroxide in tertiary butyl alcohol gave diphenyl acetic acid which was produced by the rearrangement of phenyl group to the methylene carbon atom.
2) Baeyer-Villiger reaction was also occurred competitively in this reaction system, and benzyl benzoate was isolated as ester from the neutral products. Such an observation shows that the active oxidizing species may be some kind of peroxyacid. This fact is consistent with our previous assumption that peroxy-selenious acid is the most probable catalytic form.
3) It is assumed in the reaction path of the formation of the rearranged carboxylic acid that the initial state of the attack of the peroxyselenious acid to the ketone may be analogous to that of selenious acid. From this point of view, a possible reaction path was proposed.
Organic Semiconductors with High Conductivity. III. Perylene-Iodine Complex
Authors: Uchida Tokiko , Akamatu Hideo 
Published: July 2006

Abstract
Concerning the solid complex of perylene-iodine system, it has been clarified that two sorts of molecular addition compounds are formed. One has the composition of Perylene· 1.5 I2 (or 2 Perylene· 3 I2) and the other is Perylene· 3 I2. Both complexes are semiconductive with low resistivity; the resistivity at the room temperature is 9∼10 ohm.cm. and the energy gap is 0.06 eV. Concerning those values, both complexes possess almost the same values. Not only the elecrical properties and the magnetic properties, but also, both complexes possess similar crystal structures. To explain those facts, the structural units for those complexes have been proposed. These consist of the conjugation between perylene molecules and iodine molecules with the charge tranfer type of interaction.
Polarographic Determination of the Formation Constant of Sulfatonickel(II) Complex
Authors: Tanaka Nobuyuki , Ogino Hiroshi 
Published: July 2006

Abstract
A method for the determination of the formation constants of less stable metal complexes has been developed. The method is based on the polarographic measurement of the sum of the equilibrium concentrations of hydrated metal ions and the complexes coordinating with acetate and/or co-existing ions in the presence of an appropriate auxiliary complex-forming substance. Essential advantages of the method are those of the method that was previously reported and applied to the formation constants of acetatonickel(II) complex.
The procedure developed is applied to the study of the nickel (II) complexes present in the acetate buffer solution containing nitrilo-triacetate as an auxiliary complex-forming substance and sulfate as co-existing ions. The results obtained reveal that, under the experimental condition, the monoacetatonickel(II) ions NiOAc+ and the monosulfatonickel(II) NiSO4 are present in the solution but not the acetatosulfatoniccolate(II) Ni(OAc)(SO4)−. The formation constants of monosulfato complex, KNiSO4, at ionic strength 0.2 are calculated to be 14.3±0.4 at 15°C, 11.6±0.9 at 25°C and 14.6±0.7 at 35°C.
Photoreduction of Methylene Blue by Visible Light in the Aqueous Solution Containing Certain Kinds of Inorganic Salts. II. Photobleached Product
Authors: Obata Hiroshi 
Published: July 2006

Abstract
In order to identify the photobleached substances which are produced when the aqueous solution of methylene blue is irradiated with visible light, the following three kinds of experiments were carried out.
1) Comparison of the absorption spectra of the photobleached product with those of leucomethylene blue, benzoylleucomethylene blue and acetylleucomethylene blue.
2) Comparison of the oxidative and reductive behavior of the photobleached product with that of leucomethylene blue.
3) Comparison of the pH dependence of the absorption spectrum of the photobleached product and that of leucomethylene blue.
It was concluded that the photobleached product is the leuco form dye and its oxidized form is most certainly a partially demethylated methylene blue, perhaps methylene azur A.
Infrared Spectra of Cyclohexanoxime and Cyclohexanoxime-d
Authors: Kimura Masao , Kuroda Yoko , Yamamoto Osamu , Kubo Masaji 
Published: July 2006

Abstract
The infrared absorption bands due to the functional group of cyclohexanoxime and cyclohexanoxime-d were reasonably assigned by taking into account the concentration dependence of these bands in solutions. Cyclohexanoxime having no conjugate system showed a spectral feature different in many respects from that of diacetyl monoxime or isonitrosoacetone already studied. The type of hydrogen bonding is −OH…N=C&lt; both in solutions and in the solid state. Consequently, the stretching frequency of bonded OH groups of cyclohexanoxime is different from those of diacetyl monoxime and isonitosoacetone. The doubling of absorption bands was observed for both the OH in-plane bending vibration and the NO stretching vibration of free molecules. This suggests the presence of rotational isomers. The wave numbers of the C=N stretching vibration is higher, while that of the NO stretching vibration is lower than those of the corresponding vibrations of diacetyl monoxime and isonitrosoacetone. This indicates that the double bond character of the C=N bond in cyclohexanoxime is greater than that in oximes having a conjugate system.
Dye-sensitized Photopolymerization of Vinyl Compounds. Polymerization of Acrylonitrile by Stannous Chloride and Acriflavine. I
Authors: Watanabe Ai , Koizumi Masao 
Published: July 2006

Abstract
When the aerated solution of acrylonitrile, acriflavine and stannous chloride in the mixture of water and dimethylformamide is irradiated by the visible light, the polymerization of acrylonitrile immediately takes place. The presence of water and oxygen was found to be unnecessary for the reaction to occur. The dependence of rate on the concentration of each species and on the light intensity (I0) can be summarized as follows.
Acriflavine &lt;ca. 1×10−5m, 1st order;
&gt;ca. 3.5×10−5m, const.
Stannous chloride &lt;ca. 3.5×10−3m, 1st order;
&gt;ca. 1.2×10−2m, const.
Acrylonitrile, 2nd order
I 0, 1/2th order
It was further found that the average degree of polymerization is proportional to the monomer concentration. The scheme involving the photoreduction of dye by stannous chloride and its recovery by the existent oxygen cannot explain the present result. It was proposed as a new mechanism that a transient metallic ion of tin with an odd valency is formed and this, interacting with acrylonitrile, initiates the polymerization.
Phase Relationship in System 3CaO·P2O5–MgO–SiO2
Authors: Sata Toshiyuki 
Published: July 2006

Abstract
The phase relationship in the system 3CaO·P2O5–MgO–SiO2 was investigated by a cooling experiment in the usual manner. The system 3CaO·P2O5–MgO, a side of this triangle, is a simple binary one, its eutectic being located at the composition of 4∼7% by weight of magnesia and 1570±20°C. The system 3CaO·P2O5–2MgO·SiO2 is not binary over the temperature of about 1350°C, below which it is considered as binary. Above 1350°C, nagelschmidtite is formed over the whole composition range and crystallized primarily from liquid at a high 3CaO·P2O5 portion. The minimum liquidus temperature is 1394°C, which is located at the composition of 70% C3P and 30% M2S. The system 3CaO·P2O5–MgO–2MgO·SiO2 was considered to be complex owing to the presence of nagelschmidtite, but the eutectic among their three components is located at the composition of 70% 3CaO·P2O5, 21% MgO, and 9% SiO2, and 1362±5°C.
From the results described above and from those of the author’s previous reports, the preliminary phase diagram of the system 3CaO·P2O5–MgO–SiO2 was constructed. In this diagram the problem that nagelschmidtite is formed in the composition range which is rich in 3CaO·P2O5 was not mentioned in detail. In addition to this, it was found by X-ray examination that β-tricalcium phosphate may be apparently stabilized at a higher temperature than β-α transition point, and has the appearance of dissolving magnesia component.
Kinetic Studies on Solvolysis. VII. On the Kinetic Resolution at the First Stage of the SNl-type Solvolysis of α-Phenethyl Chloride in Optically Active Carboxylic Acid Solvents
Authors: Okamoto Kunio , Takeuchi Ken-ichi , Shingu Haruo 
Published: July 2006

Abstract
1) In SN2 displacement reactions of (±)-α-phenethyl chloride with triethylammonium (+)-α-methyl camphorate and with triethylammonium (−)-pinonate in dioxane, α-phenethyl chloride of 0.08% of optical purity (l-configuration) and of 0.15% of optical purity (l-configuration) were recovered at the stage of about 5% conversion, respectively.
2) In SN1-type solvolysis of (±)-α-phenethyl chloride with anilinium (+)-α-methyl camphorate and (−)-pinonate in acetonitrile, the recovered α-phenethyl chlorides showed no perceptible optical activity on the half way for each of the reactions. From this, the possibility of the induced resolution caused at the first stage by kinetic resolution at the second stage of the SN1-type solvolysis was eliminated.
3) In SN1-type solvolysis of (±)-α-phenethyl chloride in (+)-α-methyl hydrogen camphorate and in (−)-pinonate, about half of the chloride was converted to the ester at the similar reaction conditions (temperature and time) to the SN2 displacement reactions carried out in dioxane. The recovered chloride in the reaction in hydrogen camphorate showed optical purity of 0.54∼0.58% (l-configuration). In pinonic acids with various optical activities the recovered chlorides possessed optical purity of 0.13∼0.27% (d-configuration).
4) In comparing the configurations and optical purities in SN1- and SN2-conditions, it is concluded that optically active solvent molecules, like (+)-α-methyl hydrogen camphorate and (−)-pinonic acid, can cause kinetic resolution in the first ionization stage of the SN1 type solvolysis and therefore they obviously play a rôle as a kind of reactant molecule which controls the steric course of the solvation reaction in the first stage of this solvolysis.
5) In the SN1-type solvolysis of optically active α-phenethyl chloride in presence of triethylamine in (+)-α-methyl hydrogen camphorate, optically active β-(α-phenethyl)-α-methyl camphorate gave optically active α-phenethyl alcohol of 37% inversion, 63% racemization of configuration. From this it was concluded that SN2-like spatial orientation predominates at the second stage of this solvolysis.
6) For each of the resolution results of α-phenethyl chloride under SN1- and SN2-conditions, the relationship between the configuration of the resolved alcohol and the resolution controlling stage was predicted on the basis of the observed inversion at the second stage of the solvolysis. The configurations observed for the α-phenethyl alcohols were found to be consistent with the predictions.
Abnormal Acceleration of the Rate of Bulk Polymerization of Styrene
Authors: Nishimura Norio 
Published: July 2006

Abstract
The bulk polymerization of styrene initiated by 2,2′-azobisisobutyronitrile was carried out up to high conversion at 60°C. The comparison of the experimental conversions∼time data with calculated ones showed that there was a considerable deviation between them. The rate of the polymerization became explosively great toward the last.
Assuming the combination termination, the cumulative degree of polymerization was calculated and the values were compared with those obtained experimentally. The deviation at high conversion might be owing to the decrease in the catalyst efficiency as suggested by Robertson. However, the assumption that the polymer molecules have been produced only by combination is very doubtful.
The study of the molecular weight distribution suggested that the abnormal increase in the rate and the degree of polymerization seemed to be owing to the burying of the growing polymer radicals in themselves in the highly viscous solution.
Interactions of Surface Active Agents with Congo Red
Authors: Hayashi Makoto 
Published: July 2006

Abstract
The spectral changes of Congo Red solution with the addition of Tween 80 and cetyl pyridinium chloride were measured at various pH.
The wavelength of the absorption peak of the interaction product between Congo Red and Tween 80 is 510 mμ in the acidic medium as well as those in the neutral and the basic ones, from which it is considered that they produce a molecular compound of a definite constitution irrespective of the medium pH. However, since the amount of Tween 80 required to show the same effect in spectra increases with lowering pH, it is considered that only a base form of Congo Red is probably active and binds with Tween 80 at the amino groups.
The solutions of Congo Red containing sufficient cetyl pyridinium chloride have an absorption peak at 460 mμ. The product is completely precipitated as the ratio of Congo Red to cetyl pyridinium chloride is 1/2 and dispersed in both sides of this ratio, which depends little on the medium pH. This is considered to show that cetyl pyridinium chloride binds with Congo Red at the sulfonate groups, the product becomes most hydrophobic as two sulfonates in a molecule are blocked and hydrophilic with an excess of the detergent.
Studies on Polymerization and Depolymerization of ε-Caprolactam Polymer. IX. Reformation Reaction of ε-Caprolactam from Poly-ε-capramide
Authors: Ogata Naoya 
Published: July 2006

Abstract
The reformation reaction of ε-caprolactam from poly-ε-capramide having modified end-groups has been studied. It was found that no ε-caprolactam was reformed at 230°C from the polymer of which all of the end-groups were –COONa or –NHAc groups, while ε-caprolactam was reformed slowly at 257°C. The rate of the reformation of ε-caprolactam from the polymer having –COONa or –NHAc end-groups is about 1/10 of that from the polymer having normal end-groups at 257°C and it is independent of the polymerization degree of the polymer.
The polymerization and the depolymerization reactions of ε-caprolactam polymer occur predominantly on the end-groups and the interchange reaction between two adjacent amide groups in the polymer chain occurs slowly.
Studies on Organophosphorus Compounds. III. On Phosphite Copper Cyanide Complex Compounds
Authors: Nishizawa Yoshihiko 
Published: July 2006

Abstract
Trialky phosphite reacts with copper cyanide to give phosphite or bis-phosphite copper cyanides according to the mole ratio of phosphite to copper cyanide.
It is made clear from their molecular weights that these products form polymer in various organic solvents. Moreover, these products have strong fungicidal action but this will be reported in another paper.
Mass Spectra at Low Ionizing Voltage and Bond Dissociation Energies of Molecular Ions from Hydrocarbons
Authors: Omura Itiro 
Published: July 2006

Abstract
Relative yields of parent and principal fragment ions from four paraffins and olefins by electron impact are measured for the first time. The characteristic features of the ion yields can be classified into four types related with the ionizing voltages. The decomposition processes for some fragment ions can be explained under some assumptions, and those for forbidden ions C2H5+ from isobutane and cis-2-butene under the assumption of hydrogen rerrangement.
Natural Fur an Derivatives. V. The Number of Double Bonds in Obacunone
Authors: Tokoroyama Takashi , Kamikawa Tadao , Kubota Takashi 
Published: July 2006

Abstract
Obacunone has only three double bonds in total, two in its furan ring and one in its α,β-unsaturated lactone group and, therefore, it possesses a bicarbocyclic ring.
Studies on the Composition and Properties of Less Familiar Metal Cyano Complexes. II. Composition of Copper Octacyano Molybdate and the Existence of the Redox System Cu++Mo(CN)83−\ightleftarrows Cu2++Mo(CN)84−
Authors: Malik Wahid U , Ali S Iftikhar 
Published: July 2006

Abstract
The reaction between copper sulfate and potassium molybdocyanide was studied using conductometric, potentiometric and amperometric methods. The stoichiometric ratio of 2 : 1 for Cu2+ to Mo(CN)84− correspond to the formation of Cu2Mo(CN)8. The interaction of cuprous chloride and potassium molybdicyanide resulted in the formation of K2CuIIMoIV(CN)8. Evidence for the existence of a redox potential in the system Cu++ Mo(CN)83−\ightleftarrows Cu2++Mo(CN)84− could be obtained for the latter reaction on the basis of potentiometric titrations.
Molecular Rotations of Terpenes in Relation to their Structures. I. The Internal Conformation of Isopropyl Group in Menthol-like Substance
Authors: Yamana Shukichi 
Published: July 2006

Abstract
From the standpoint of the fact that a menthol-like substance is a kind of hydroxycyclohexane, the molecular rotations of menthol-like substances are calculated by using the PM-method. A comparison of the calculated values with the corresponding observed values seems to make it possibe to presume the type of the internal conformation of (iso-C3H7)4α.
Photochemical Processes due to n-π* and π-π* Transitions of 3-Picoline N-Oxide in the Vapor Phase
Authors: Hata Norisuke 
Published: July 2006

Abstract
Gaseous photolysis of 3-picoline N-oxide was attempted by irradiation with the 3261Å (Cd 3P1) or 2537Å (Hg 3P1 resonance line corresponding to an n-π* or a π-π* absorption region, respectively, of this substance. In either case, the photolytic products were mainly 3-picoline, and we observed a remarkable temperature-dependence for the quantum yield of 3-picoline in the case of 3261Å irradiation but not in the case of 2537Å irradiation. This observation suggests that an activation energy would be required for the production of 3-picoline at 3261Å only. The activation energy estimated from the relation between the quantum yield of produced 3-picoline and the temperature at 3261Å irradiation was about 11.5 kcal. mol−1, which is almost about the same value as that of pyridine N-oxide. The reactions succeeding to an n-π* or a π-π* transition of 3-picoline N-oxide were considered to be similar to the case of pyridine N-oxide.
Studies on the Surface Structure of Porous Materials
Authors: Tsuruizumi Akie 
Published: July 2006

Abstract
1. The adsorption characteristics of ths sugar carbon prepared by carbonization or activation and silica gel were studied in detail by the adsorption of water, benzene and fatty acid vapors, and mercury porosimetry.
The pore distribution of the active carbon was tri-disperse. The effects of the partial filling of the pores were examined. The missing link in the distribution curve between the micro-pore and transitional pore in the previous reports was replenished.
2. The narrow-neck or ink-bottle structure of the pores of sugar carbon complicated the adsorption characteristics. The pores of the silica gel were cylindrical with a uniform section.
3. In order to specify the physical selective adsorption, the new term “ sieving coefficient” was defined from the relation between the pore radii and cross sections of the adsorbates.
Non-empirical Study of the π-Electronic Structure of Vinyl Chloride Molecule by Valence Bond Method
Authors: Takekiyo Shozaburo 
Published: July 2006

Abstract
π-electronic energy levels, probabilities of the resonance structures, π-electron densities, and the bond orders of the vinyl chloride molecule have been calculated non-empirically by the standard valence bond method, based on a complete set of the π-type resonance structures. Slater 2pπ- and 3pπ-orbitals have been assumed for the carbon and chlorine atoms and all the multiple exchange integrals have been considered. The calculated transition energy between the ground state and the first excited state is 11.41 eV., the ionic character is 31.54%, and the positive charge on the chlorine atom is 0.0849 (experimental value is 0.06.).
Thermodynamical Studies on Binary Systems Consisting of Polar and Non-polar Liquids. IV. Estimation of the Electrostatic Part of the Excess Enthalpy from the Observed Values aud Comparison with the Calculated Values
Authors: Amaya Kazuo 
Published: July 2006

Abstract
The electrostatic part of the van Laar coefficients were derived from the observed value of heats of mixing and some regularity was found between these values and the dielectric constant of polar components if non-polar components are non-aromatic (group I). However, no regularity exists between them if non-polar components are aromatic (group II). These values were also compared with the calculated values. For group I, qualitative agreements were obtained and this confirms the fact that the variation of α with concentration is due to dipolar interaction of the polar components. The agreement is poor for systems containing a polar component with large dipole moments or for one containing a non-polar component with quadrupole moment. For group II, no qualitative agreement was obtained.
Infrared and Raman Spectra of Dialkoxymethanes in Various Phases and the Assignment of Spectra of Methoxyethoxymethane
Authors: Nukada Kenkichi 
Published: July 2006

Abstract
The rotational isomerism of dialkoxymethanes (CH3OCH2OCH3, CH3OCH2OC2H5, C2H5OCH2OC2H5 and (CH3)2CHOCH2OCH·(CH3)2) is discussed from the spectroscopical point of view. The experimental results are as follows.
1) The appearance of infrared spectra is appreciably different among the vapor, liquid and solid phases. Of these, the solid spectrum gives the most complicated figure.
2) No solvent effect is obtained in acetonitrile solution.
3) No change is observed in the vapor infrared spectrum between room temperature and 100°C.
It is concluded from these results and data of dipole moment that dimethoxymethane exists as one configuration in the liquid and vapor phases, the terminal methyl groups of which are rotating about 120° anticlockwise sense from the central OCO plane.
The configuration of other dialkoxymethanes are assumed to be of one form by the analogy of experimental results.
Finally, the assignment of vibrational spectra of methoxyethoxymethane is presented.
Studies on Tritium Labeled Compounds. II. Preparation of Tritium Labeled Stearic Acid
Authors: Sato Yoshishige , Meshi Teruhiko , Takahashi Tadao 
Published: July 2006

Abstract
Chemical reduction method, exchange method, electric discharge method and recoil tritium labeling method were applied for preparing tritium labeled stearic acid. As the result of the recoil tritium labeling, the irradiated stearic acid was found to contain high destruction products which are mainly composed of esters of fatty acid.
Statistical Thermodynamics of Solutions of Optically Active Substances. I. Excess Free Energy of Binary Solution of d- and l-Isomers
Authors: Amaya Kazuo 
Published: July 2006

Abstract
A statistical mechanical theory of solutions consisting of d- and l-optical isomers is developed based on a new model of optically active molecules, and the excess free energy of the system is also derived and the order of magnitude of this quantity is examined.