bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Photochemical Reduction of Hydrazobenzene
Authors: Hashimoto Shizunobu , Sunamoto Junzo , Nishitani Syunpei 
Published: July 2006

Abstract
Hydrazobenzene was irradiated with an ultraviolet light in n-hexane under a nitrogen atmosphere. The products were azobenzene, aniline, and a trace of semidines. The yield of azobenzene was usually larger than that calculated on the basis of the disproportionation of hydrazobenzene, while the yield of aniline was less. The reactions were followed by the determination of the disappearance of hydrazobenzene and that of the formation of azobenzene. On the basis of the available data, in the photochemical reaction of hydrazobenzene it was assumed that the formation of azobenzene was not due to the disproportionation, but to the oxidation of hydrazobenzene, and that no fission of the N–N bond of hydrazobenzene occurred to give azobenzene.
Kinetic Studies of the Oxidation of Benzils with Peroxyacetic Acid in Acetic Acid
Authors: Furuya Yoshiaki , Urasaki Iwao 
Published: July 2006

Abstract
The oxidation of benzils with peroxyacetic acid in the presence of sulfuric acid in acetic acid has been studied kinetically. The rate of the consumption of peroxyacetic acid has been found to be the sum of the four terms shown in the following equation:
-d[AcO_2H]/dt={k_d+k_t[H_2SO_4]}[AcO_2H]+{k_2+k_2’[H_2SO_4]}[Bz_2][AcO_2H]
It is considered that the first and second terms correspond to the decomposition of peroxyacetic acid itself and to the acid-catalyzed reversible transformation of peroxyacetic acid to acetyl peroxide, while the third and fourth terms represent, respectively, the non- and the acidcatalyzed oxidations of benzils with peroxyacetic acid. In both non- and acid-catalyzed oxidations, a probable mechanism passing through benzoic anhydride is postulated.
Syntheses and Reactions of Nitrogen- and Sulfur-Analogs of 2-Piperazinone
Authors: Masuzawa Kuniyoshi , Masaki Mitsuo , Ohta Masaki 
Published: July 2006

Abstract
2-Piperazinone oxime, 2-piperazinoneimine, and 2-piperazinethione were synthesized. The reaction mixture of ethylenediamine and glycolonitrile was treated with an excess amount of hydroxylamine in methanol to give 2-piperazinone oxime in a 53% yield. 2-Piperazinone oxime was easily reduced to 2-piperazinoneimine, which was then treated with hydrogen sulfide to yield 2-piperazinethione. Some reactions of these compounds are described.
Synthesis and Reactions of Functional Polymers. XXXIV. Low Polymerization of Ethylene Oxide with Sodium N,N-Dimethyldithiocarbamate in Dipolar Aprotic Solvents
Authors: Nakai Takeshi , Okawara Makoto 
Published: July 2006

Abstract
The low polymerization of ethylene oxide with sodium dimethyldithiocarbamate in a homogeneous system was studied. This reaction was verified as proceeding through a step-by-step addition mechanism, due to the enhanced nucleophilicity of the dithiocarbamate anion in dipolar aprotic solvents. The solvent effects and the catalyses of various dithiocarbamate salts were also examined. Epichlorohydrin was reacted with this salt in dimethylformamide to afford a polymer with a dithiocarbamate moiety through both ring-opening and substitution processes.
Solubility of Chlorine in Hydrochloric Acid
Authors: Hine Fumio , Inuta Shusei 
Published: July 2006

Abstract
The solubility of chlorine in a concentrated HCl solution at various conditions of concentration, partial pressure, and temperature was determined. The concentration of chlorine in a solution as the sum of Cl2 and Cl3− was found to be proportional to the partial pressure of chlorine in the gas phase, and its slope was a function of the HCl concentration and the temperature Empirical equations representing these relations and the solubility of chlorine were obtained. It was confirmed that the results agreed with the experimental data in the 2–10 n HCl concentration range at partial pressures of chlorine lower than 1 atm and at 30–90°C. Such physico-chemical properties as the Gibbs free-energy change were considered by using the data of solubility, and the behavior of the system consisting of Cl−, Cl2, and Cl3− was discussed.
Initiation Step of Methane Pyrolysis
Authors: Yano Takayuki , Kuratani Kenji 
Published: July 2006

Abstract
Equimolar mixtures of CH4 and CD4 were pyrolyzed at 1560°K by a reflected shock wave. From the isotope distribution of H2, HD and D2 which are components of the product in early stage, the initiation step of methane pyrolysis is concluded to be the splitting to a methyl radical and a hydrogen atom.
Effects of Heating Temperature and Irradiation on the Catalytic Activities of Active Carbons for Phosgene Synthesis
Authors: Sato Shoichi , Yoneda Yukio 
Published: July 2006

Abstract
The kinetic factors for phosgene synthesis over thermal and irradiated sucrose carbons were examined in particular regard to their dependences on the heating temperature and irradiation. Gamma-irradiation on carbons prepared at 900 or 1000°C produced new active sites with EA of 11–12 kcal/mol. An explanation is suggested of the effects of heating temperature and irradiation on the catalysts; the catalytic activity is most reasonably related to the degree of growth of the network structure of carbons. In the case of carbons prepared by heating at 900 or 1000°C and having the structure grown to the largest extent, a high dose of gamma-rays presumedly destroys most efficiently the thermally generated active sites and forms sites with a high activation energy. Free radicals and peripheral atoms which also comprise characteristics of amorphous carbons seem to behave independently of catalytic activities and are supposed to have no direct relation to the activities.
Spectrophotometric Determination of Formation Constants of Iron(III) Complexes with Chloride Ion in Dimethyl Sulfoxide
Authors: Wada Goro 
Published: July 2006

Abstract
The formation constants of FeCl2+ and FeCl2+ have been measured in dimethyl sulfoxide (DMSO) containing Fe(ClO4)3, NaCl, HClO4 and NaClO4. Some spectrophotometric methods giving the formation constants and molar extinction coefficients of the complexes were developed and gave, on the average, logK1=3.62 and logK2=2.10, at 0.02 m HClO4 and an ionic strength of 0.10 m at 25°C. It is rather surprising that these values are only slightly larger than those in N-methylacetamide, which is expected, however, to give much smaller values than DMSO, due to its extraordinarily large dielectric constant. The species formed between Fe(III) and Cl− ion is reasonably supposed to be a true complex bonded directly with each other and not an ion-pair association product. At higher concentrations of Fe(III), formation of polynuclear complexes can occur.
Crystalline Complexes of Allylamine and Propylamine with Copper(I) Chloride and Bromide
Authors: Ogura Tetsuya , Hamachi Takeshi , Kawaguchi Shinichi 
Published: July 2006

Abstract
Crystalline 1 : 1 and 1 : 3 complexes of allylamine and propylamine with copper(I) chloride and bromide were synthesized in vacuo. Equilibrium vapor pressures of these complexes were measured at several temperatures and the enthalpy of ligation of each amine molecule was determined. Both the thermochemical and infrared absorption data indicate that in the 1 : 1 complexes of allylamine the ligand molecule serves as a bidentate, but in the 1 : 3 complexes the second and third ligand molecules link to the metal only through the amino nitrogen atom.
Reaction Rates in Binary Mixed Solvents. IV
Authors: Kondo Yasuhiko , Honjo Yoshitoshi , Tokura Niichiro 
Published: July 2006

Abstract
Three cases of combinations of the solvation free-energy differences in two solvents, with respect to a reactant and an activated complex, have been proposed. The theoretical expressions for the rate constant and for the activation energy in binary mixed solvents have been derived for each model. From the theoretical calculations based on these models, it has been demonstrated that the behavior of a system in which the reaction rates are mainly dependent on the difference in the solvation energies of an activated complex can be distinguished from behavior of a system where the reaction rates are controlled by the difference in the solvation energies of a reactant. The reaction rates of the Menschutkin reaction in binary mixed solvents containing liquid sulfur dioxide as one component of the mixed solvent have been analyzed on the basis of these models.
The Extraction of Uranium(VI) from Sulphuric Acid Solutions by Di-n-octylamine
Authors: Sato Taichi 
Published: July 2006

Abstract
The partition of uranium(VI) between sulphuric acid solutions and solutions of di-n-octyl-amine (DOA) in benzene has been investigated at different concentrations of sulphuric acid, solvent and aqueous uranium, and at different temperatures. The acidity and the water content of the organic phase, and the effect of the organic solvent on the extraction have also been examined. An infrared spectral study has been made of the organic solutions. The mechanism of the extraction of uranium from sulphuric acid solutions by DOA is discussed on the basis of the results obtained, and a composition is proposed for the complex formed in this extraction system.
Polarographic Behavior of Tris(2,2′-bipyridine)chromium(III) and Tris(ethylenediamine)chromium(III) in Acetonitrile Solutions
Authors: Sato Yuichi , Tanaka Nobuyuki 
Published: July 2006

Abstract
Polarographic behavior of tris(2,2′-bipyridine)chromium(III) perchlorate and tris(ethylenediamine)chromium(III) perchlorate in acetonitrile solutions has been investigated by the measurement of d.c., a.c. and Kalousek polarograms. The bipyridine complex gives a six-step reduction wave when tetraethylammonium perchlorate is used as supporting electrolyte. The limiting currents of the first four steps are all diffusion-controlled, and each of them is of a one-electron reduction process. It has been proposed that at the fourth step univalent tris(2,2′-bipyridine)-chromate anions, [Cr(bipy)3]−, are formed at the electrode surface in acetonitrile. The limiting current of the one-electron reduction wave of tris(ethylenediamine)chromium(III) is increased upon the addition of 2,2′-bipyridine. It was explained as a reduction of an electroactive species, Cr(II)-bipyridine complex, which was formed by the reaction between Cr(II) produced by the reduction of tris(ethylenediamine)chromium(III) complex and 2,2′-bipyridine at the electrode surface.
Catalysis in Peptide Synthesis with Active Esters. I. Bifunctional Catalysis in the Aminolysis of Benzyloxycarbonyl-l-phenylalanine p-Nitrophenyl Ester in Dioxane
Authors: Nakamizo Nobuhiro 
Published: July 2006

Abstract
The aminolysis reaction of benzyloxycarbonyl-l-phenylalanine p-nitrophenyl ester (I) with glycine t-butyl ester (II) was kinetically investigated in anhydrous dioxane. The spontaneous reaction was confirmed to follow the equation:
d[p-nitrophenol]⁄dt=kobs[I]=(k0+kamine[II])[I][II]
The catalytic actions of various additives were studied at a 2×10−3m concentration of I and II, where the amine-catalyzed term could be neglected. Of the many additives, only carboxylic acids and α-pyridone were effective as catalysts. The catalytic effect apparently decreased in the sequence: trimethylacetic acid&gt;acetic acid&gt;α-pyridone&gt;monochloroacetic acid. For these catalyses, a bifunctional, concerted mechanism was proposed which involves an 8-membered transition state.
The Surface Structure of Silica Gel Studied by Dielectric Dispersion
Authors: Kondo Seiichi , Muroya Masa-aki 
Published: July 2006

Abstract
The effect of water adsorption and heat treatment at various temperatures between 200 and 1100°C on the dielectric dispersions of silica gel was measured in the frequency range from 50 to 3×106 Hz and 9.81 GHz and in the temperature range from −196°C to 180°C. Two anomalous dispersions (Dispersion I and II) and one anomaly (Anomaly III) were found. The mechanisms of those anomalies were discussed in relation to some physical properties and silica crystal structures. Dispersion I, having activation energy ΔE equal to 11 to 14 kcal/mol, can be ascribed to the monomolecular layer of adsorbed water. Dispersion II, with activation energy of about 5 to 7 kcal/mol, can be attributed to proton diffusion through hydrogen-bond chain of surface silanol groups. Anomaly III, having activation energy of about 3 kcal/mol, may be assigned to dipolar rotation of free silanol.
The Micellar Properties of Disodium Monoalkyl Phosphates in Aqueous Solutions
Authors: Tahara Takashi , Satake Iwao , Matuura Ryohei 
Published: July 2006

Abstract
The disodium monoalkyl phosphate with n-dodecyl, n-tetradecyl and n-hexadecyl radical was synthesized, and pNa and light scattering studies were performed on the micellar properties of these surfactants in aqueous solutions. The critical micelle concentrations (CMC) of these salt solutions were confirmed to be considerably higher than those of ordinary 1–1 type ionic surfactants with the same alkyl chain length. The degree of dissociation of the micelle was, however, found to be not so different from that of corresponding sodium alkyl sulfate. The fact that these salts have comparatively large aggregation number reflects one of the characteristic features of alkyl phosphate anion which has two dissociable groups.
Coulometric Titration of a Microamount of Water after Conversion to Ammonia
Authors: Yoshimori Takayoshi , Ishiwari Syuiti 
Published: July 2006

Abstract
Sodium amide was used to convert a microamount of water into ammonia in a carrier gas. The ammonia was then titrated with coulometrically generated hypobromite ions. The reaction between water and sodium amide was completed stoichiometrically, and the reaction rate was considerably promoted by heating sodium amide at 80°C. The sample hydrogen was oxidized with copper(II) oxide at 800°C, and the water thus produced was determined by this method. 0.096–0.665 ml (8.6–59.8 μg) of hydrogen and 0.055–0.465 mg of water in barium chloride crystals were determined within errors of 3.6% and 3.0% respectively. The water adsorbed on the surfaces of the weights was also determined by this method at various humidities.
The Separation of Hexacyanoferrate(II) and Hexacyanoferrate(III) Ions by Reversed-phase Partition Chromatography
Authors: Akaza Ikuko , Kiba Toshiyasu , Taba Minoru 
Published: July 2006

Abstract
The separation of hexacyanoferrate(II) and (III) ions with a TBP-HCl extraction system has been carried out by reversed-phase partition column chromatography. TBP adsorbed on Kel-F powder was used as the stationary phase in the column. Elution was performed with hydrochloric acid of various concentrations and with water, both having been saturated with TBP. The actual separation of hexacyanoferrate(II) and (III) ions from each other was successfully achieved, even in a large volume of a sample solution, by carrying out the elution with 3n HCl. The dependencies of the distribution ratio on the acidity of the solution and on the concentration of TBP in the stationary phase were examined on the basis of the elution curves under various conditions. The liquid-liquid batch extraction was also carried out under the same conditions; it was found an identical relation of distribution between the two phases held in both column and batch extractions. The principal extracted species might be assumed to be a large ion-pair hydrated and solvated.
Graft Copolymerization onto Cellulose in Dimethyl Sulfoxide by Means of a Ceric Salt Containing Lauryl Sulfuric Ions
Authors: Kaeriyama Kyoji 
Published: July 2006

Abstract
Styrene was polymerized in dimethyl sulfoxide by alcohol-ceric salt containing lauryl sulfuric ions. The rate of polymerization increased with the amount of ethyl alcohol added. A deuterium isotope effect was observed when tetradeuteromethyl alcohol was used as an initiator. Accordingly, the generation of radicals by the elimination of the hydrogen atom from the alcohol molecule was concluded. When styrene was polymerized in the presence of cellulose, graft copolymer was obtained. The grafting efficiency amounted to about 70%.
Synthesis and Physical Properties of Long Chain Compounds. X. Studies on the X-Ray Diffraction Patterns of Normal Higher Primary Amines
Authors: Watanabe Akira , Ishizawa Akio , Kosaka Masao , Got\={o} Ry\={o}z\={o} 
Published: July 2006

Abstract
For the members of n-higher primary amines from C12 to C20 the crystal structure was studied by X-ray powder method. From the values of long spacings and the splitting of (110) reflections it was concluded that the structure is probably similar to that of fatty acids and that the hydrocarbon chains are tilted with respect to the plane formed by end groups. This structure seems to be stable over the temperature range between room temperature and melting points. The dependence of melting points on chain length was discussed.
Reaction of Acyl Oxime with Mercaptan
Authors: Sudo Rokuro , Kaneda Akira , Furuoya Nobuo 
Published: July 2006

Abstract
The acyl derivative of oxime, derived from a strong acid, is generally unstable. However, acyl oximes of the ethyl α-oximinoacetate derivative were prepared and were found to be more stable than ordinary acyl oxime. Acetyl, carbethoxy, benzoyl, and even tosyl ester were prepared, and their reactions with the mercaptide anion were investigated.
Reaction of Vetivazulene with Sulfur. 3,5,9-Trimethylazuleno-[1,2-b]thiophene
Authors: Hayashi Shûichi , Kurokawa Shinji , Matsuura Tamon 
Published: July 2006

Abstract
Vetivazulene was heated with sulfur to give a new sulfur-containing azulene, 3,5,9-trimethylazuleno[1,2-b]thiophene. On Vilsmeier formylation, the compound normally resulted in the formation of 4-formyl derivative, while the acetylation according to the Vilsmeier procedure proceeded abnormally to produce 4-dimethylamino-3,5,9-trimethylazuleno[1,2-b]thiophene.
Syntheses of Pterocarpans. II. The Synthesis of (±)-Pterocarpin
Authors: Fukui Kenji , Nakayama Mitsuru 
Published: July 2006

Abstract
The reduction of medicagol methyl ether with lithium aluminum hydride in tetrahydrofuran yielded a diol. The dehydration of the diol in boiling diethylene glycol gave an ether (anhydropisatin, O-methyl anhydrosophorol). Then, the above ether was hydrogenated with 10% Pd-C to (±)-pterocarpin.
A Cationic Polymerization of Formaldehyde in Liquid Carbon Dioxide. V. Reaction Mechanism
Authors: Yokota Hisao , Kondo Masatsune , Kagiya Tsutomu , Fukui Kenichi 
Published: July 2006

Abstract
The present work was carried out in order to elucidate the reaction mechanism in the polymerization of formaldehyde in liquid carbon dioxide. Methylene glycol methylether acetate with a structure similar to that of methylene glycol monocarboxylate, which was assumed to be an initiator, exhibited a catalytic activity. On the other hand, methyl acetate terminated the polymerization. Moreover, the resulting polymer, which was terminated by the addition of methyl-2H3-acetate, contained deuterium originating from the terminator used. On the basis of these experimental results, a reaction mechanism of the elementary processes is discussed.
Photoemission from Polycyclic Aromatic Crystals in the Vacuum Ultraviolet Region. III. Aromatic Crystals and Charge-transfer Complexes
Authors: Hirooka Tomohiko , Kochi Masakatsu , Aihara Jun-ichi , Inokuchi Hiroo , Harada Yoshiya 
Published: July 2006

Abstract
The photoemission from various types of charge-transfer complexes, quinolinium-tetra-cyanoquinodimethane Q(TCNQ2 (I), dibenzophenothiazine (DBP)-dicyanodichloro-p-benzoquinone (DDQ)[(DBP)(DDQ)(II) and (DBP)2(DDQ)(III)], trinitrobenzene (TNB)-coronene (IV), and TNB-perylene (V),and also large polycyclic aromatic hydrocarbons, violanthrene A (VI), violanthrene B (VII), coronene (VIII), pyranthrene (IX), and pyranthrone (X), was observed in the vacuum ultraviolet region. The experimental equation Y ∝(E–E*)3, where Y is the quantum yield of photoemission; E, the incident photon energy, and E*, the threshold energy, was used to determine the ionization potential. The E*-values, as estimated from the experimental equation, were I=4.85 eV, II 4.99, III 4.75, IV 5.62, V 5.52, VI 5.06, VII 5.13, VIII 5.58, IX 5.04, and X=5.71 eV. A band structure scheme for these organic semiconductors was introduced to analyse the emission mechanism.
Infrared Spectra of Biuret-hydrate and Its Deuterated Compound
Authors: Uno Toyozo , Machida Katsunosuke , Saito Yutaka 
Published: July 2006

Abstract
The infrared spectra between 4000 and 33 cm−1 of biuret-hydrate and between 4000 and 250 cm−1 of its deuterated compound have been recorded. The vibrational assignments have been made by referring to the infrared spectra of the related compounds and the isotopic frequency shift. Normal coordinate analysis of the in-plane vibrations of biuret and biuret-d5 as twelve-body problem has been carried out by using the molecular model of the planar trans-cis conformation. A simple Urey-Bradley force field has been employed and the force constants have been refined by the least squares method. The calculation of potential energy distributions has shown that the NH in-plane deformation and the CN stretching vibrations couple appreciably with each other and give the imide II and III bands at 1515 and 1365 cm−1, respectively, just as in the case of diacetamide.
Scandium Content of Igneous Rocks and Some Oceanic Sediments
Authors: Shimizu Tsuneo 
Published: July 2006

Abstract
Based on the analyses of 105 individual samples and 5 composites, totaling 158 rock samples, the following averages of scandium for various types of Japanese igneous rocks have been obtained (in ppm): granites 5.6, granodiorites 7.4, liparites 6.1, quartz diorites and diorites 11.4, dacites 14.1, andesites 21.8, gabbros 26.9, basalts 27.2 and ultramafic rocks 9.5. Scandium is determined by a combined ion-exchange-spectrophotometric method. Using Poldervaart’s suggested ratio of rock types, an abundance figure of 17 ppm Sc for the crust is suggested. The results on the abundance values for scandium in various types of igneous rocks confirm generally the figures given by Norman and Haskin in 1968. Analyses are also performed on Pacific oceanic sediments, giving as averages 18.7 ppm Sc for 4 red clays, 12.1 ppm Sc for 2 volcanic muds and 13.1 ppm Sc for 2 globigerina oozes. Brief discussion on the geochemistry of scandium is given.
The Alkaline Ethanolyses of Chlorophenyldiphenylsulfonium Halides, Chlorophenyl Phenyl Sulfones and Chloronitrobenzene in Aqueous Ethanol
Authors: Oae Shigeru , Khim Yong He 
Published: July 2006

Abstract
o-, m-, and p-Chlorophenyldiphenylsulfonium halides were prepared and subjected to the alkaline ethanolysis in order to compare the activating effects of o-, m-, and p-diphenylsulfonio groups with those of o-, m-, and p-phenylsulfonyl and nitro-groups. The diarylsulfonio group at either ortho or para position was found to facilitate the nucleophilic substitution of aryl chloride powerfully. While the effect of diarylsulfonio group was not only substantially larger than that of phenylsulfonyl group, but also exceeding even that of nitro group. Meanwhile, with ethoxide ion in ethanol the alkaline decomposition reaction, presumed to be initiated by the attack of ethoxide on the sulfur atom of chlorophenyldiphenylsulfonium halide, occurred competitively along with the SN reaction, but the rate of the SN reaction of p-chlorophenyldiphenylsulfonium perchlorate was found to be about 9 times larger than that of the decomposition reaction. Substitution of a methyl group at ortho to diphenylsulfonio, phenylsulfonyl and -sulfinyl groups did change very little the rates of the ethanolyses of the corresponding p-substituted chlorobenzenes, suggesting that essentially there is no or little steric inhibition for the 3d-orbital resonance with either sulfonio, sulfinyl, or sulfonyl group in the SN reaction of these compounds.