bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Self-diffusion of Chloride Ions in Nickel Dichoride Crystallites and an Isotopic Exchange Reaction between Chlorine Gas and the Crystallites
Authors: Sensui Yoshihiro 
Published: July 2006

Abstract
The self-diffusion of chloride ions in the bulk of nickel dichloride crystallites was studied in the temperature range of 180–340°C in a carefully-evacuated vacuum system; the isotopic exchange reaction between gaseous chlorine and the crystallites was also studied. The activation energy for the migration of chloride ions was determined to be 1.01 eV (=23.3 kcal/mol). The exchange reaction proceeded with activation energies of 3.6 and 9 kcal/mol for the active and the less-active part of the surface first layer, 13 and 16 kcal/mol for the active and the less-active one of the second layer, and 21 kcal/mol for the third layer. (These activation energies converge to the value of the self-diffusion in the bulk.) The Θ-rule nearly holds good in the present case.
Oxygen Vacancies in the Perovskite-type Ferrites. II. Mössbauer Effect in the SrFeO2.5 -LaFeO3 Solid-solution System
Authors: Yamamura Hiroshi , Kiriyama Ryôiti 
Published: July 2006

Abstract
The Mössbauer effect was studied for the solid-solution Sr1−xLaFeO2.5+x⁄2 system, prepared by firing in a vacuum. The intensity of the characteristic six absorption lines of the tetrahedral-iron site in the brownmilleritetype phase (0.0≤x≤0.02) was weakened with an increase in the La content because of an increasing incorporation of oxygen, while the Mössbauer parameters remained constant. SrFeO2.5 with a brownmillerite-type structure, completely changed into a cubic perovskite-type structure at the composition with x=0.30; however, the original absorption peaks for the tetrahedral-iron site still exist even if the intensity is considerably decreased. Moreover, new peaks came out, with Mössbauer parameters different from those for the octahedral- or the tetrahedraliron sites. On the basis of the values of their Mössbauer parameters, the origin of the new peak can be assigned to the presence of a five-coordinated iron site surrounded by a trigonal bipyramidal polyhedron of oxygen rather than a square pyramidal one. The three kinds of iron site lead to a single octahedral one when most of Sr is replaced with La (x≥0.50). The oxygen-deficient, perovskite-type phase with a cubic symmetry may be stabilized by the presence of the mixed-coordination scheme of Fe3+, i.e., the octahedral, trigonal bipyramidal, and tetrahedral sites.
Ultrasonic Study of Solute-Solvent Interaction in Aqueous Solutions of Tetraalkylammonium Salts
Authors: Hirata Fumio , Arakawa Kiyoshi 
Published: July 2006

Abstract
Ultrasonic velocity of aqueous solutions of tetraalkylammonium chlorides was measured over wide ranges of concentration and temperature in order to study the nature of solute-solvent interactions. Adiabatic compressibility was obtained from the data of sound velocity and density. The results were discussed in terms of the influence of solutes upon the structure of liquid water. It has been shown that Me4N+ is a structure breaker, while n-Bu4N+ forms a structure or “icebergs” around the cations evidently, and that the ability of iceberg formation begins at n-Pr4N+. It was concluded that the icebergs have a more rigid structure than the ice-like structure in bulk water.
Hydrogenation by Cyanocobaltate. II. Mechanisms of the Hydrogenations of 1,3-Butadiene and Isoprene Catalyzed by Pentacyanocobaltate(II) in Aqueous Solution
Authors: Funabiki Takuzo , Matsumoto Mitsuo , Tarama Kimio 
Published: July 2006

Abstract
Hydrogenations of 1,3-Butadiene and isoprene catalyzed by pentacyanocobaltate(II) have been studied by the measurements of infrared and nuclear magnetic resonance spectra on the reaction solutions and by following the time-courses of the reactions. Infrared spectroscopy has revealed: (1) The aging reaction is promoted by CN- ion and it hardly occurs at a low CN/Co ratio. (2) In the hydrogenation of butadiene the formation of a σ-but-2-enyl complex at a high CN/Co ratio is very rapid, but that of a syn-π-(1-methylallyl) complex at a low CN/Co ratio is generally slow. The rate of the formation of these complexes is affected by the relative concentration of butadiene to Co(CN)5H3−. (3) In the hydrogenation of isoprene a σ-3-methylbut-2-enyl complex is formed regardless of the CN/Co ratio. Nuclear magnetic resonance spectroscopy has confirmed the structures of these complexes and it also showed that the σ-but-2-enyl complex consists of simliar amounts of the cis- and trans-isomers. The reactions are explained by the mechanisms, in which intermediate complexes in the formation of alk-1-enes and alk-2-enes are the cis- and trans σ-but-2-enyl and the syn-π- (1-methylallyl) complexes in the case of butadiene, and the σ-2- and -3-methylbut-2-enyl and the π-(1,2-dimethylallyl) complexes in the case of isoprene. It is described that the reactivity and the selectivity in the hydrogenation of conjugated dienes are strongly controlled by the steric factor in the transition state.
The Reaction between Hydrocarbon and Hydrogen Sulfide in Silent Electrical Discharge. I. The Reaction of Ethylene or Propylene with Hydrogen Sulfide
Authors: Nishimura Yoshiharu , Kawamoto Kazuaki 
Published: July 2006

Abstract
In order to examine the possibility of the direct introduction of the sulf hydryl radical into ethylene or propylene and that of the telomerization by means of a silent discharge, the mixture of ethylene or propylene and hydrogen sulfide was discharged in an ozonizer. (1) With ethylene and hydrogen sulfide, the main products were ethyl mercaptan, n-butyl mercaptan, and ethylene dithioglycol. Besides these compounds, the reaction products were confirmed to be diethyl sulfide, s-butyl, n-hexyl, n-propyl, and isopropyl mercaptans, and gaseous products. (2) With propylene and hydrogen sulfide, on the other hand, n-propyl mercaptan, di-n-propyl sulfide, isopropyl mercaptan, and 1,2-propyIene dithioglycol were obtained as the main products. Besides these compounds, there were diisopropyl sulfide, ethyl and n-butyl mercaptans, 4-methyl-1-pentene, 2,3-dimethylbutane, 1,5-hexadiene, 2-methylpentane, 1-hexene, n-hexane, and gaseous products. The maximum yield of the liquid products was obtained when ethylene or propylene and hydrogen sulfide were mixed in approximately the ratio of 1:1. Judging from the relative concentration of each compound in the reaction products, it may be said that vinyl, ethyl, and sulfhydryl radicals in the reaction system of ethylene and hydrogen sulfide, and 2-methylvinyl, isopropenyl, propyl, allyl, isopropyl, and sulfhydryl radicals in the reaction system of propylene and hydrogen sulfide, are the main intermediates.
Thermal Decomposition of Ammonium Salts of Transition Metal Oxyacids. III. Thermogravimetric Analysis of Ammonium Chromate
Authors: Park Il-Hyun 
Published: July 2006

Abstract
Thermal decomposition of ammonium chromate (AC) and ammonium dichromate (ADC) has been studied by means of TG, DTA, and DTG. It showed four steps in thermal decomposition of AC and three steps in that of ADC. Decomposition product in each step of the thermal decomposition was examined by X-ray diffraction method. From the results of both thermogravimetric analysis and X-ray study, it was concluded that the first decomposition product of AC was ADC, the second was CrO3 and the final product was Cr2O3. The third product gave the X-ray patterns of the mixture of Cr2O3 and CrO3, and the mole ratio of O/Cr in the temperature range for the existence of the product (300–390°C) was 2.1–2.0. The kinetics in the second decomposition step for AC and in the first decomposition step for ADC were studied, giving the values of the energy of activation of 24.2 and 22.4 kcal/mol, respectively.
Thermal Decompsition of Ammonium Salts of Transition Metal Oxyacids. IV. Determination of Constituents of Gases Evolved in Decomposition of Ammonium Chromate
Authors: Park Il-Hyun 
Published: July 2006

Abstract
Constituents of gases evolved in thermal decomposition of ammonium chromate and ammonium dichromate have been studied by an omegatron mass spectrometer. From the data of gas analysis, the following conclusions have been obtained. The decomposition of the first step started with proton transfer mechanism and the ratio of NH3 to H2O was not 2 : 1 at the beginning. The second step corresponded to the formation of N2, N2O, and H2O through oxidation of NH3 by the chromate anion. The decomposition in the third step was accompanied by the evolution of oxygen molecules. The production of CrO3 was confirmed by comparing the dissociation pressure of CrO3 produced in AC decomposition with that of pure CrO3. The decomposition in the last step corresponded to the process from CrO2 to Cr2O3, with the evolution of O2, CO2, and CO.
Reactions of Diazoketones in the Presence of Metal Chelate. IV. Formation and Reaction of Carbonyl Ylides
Authors: Ueda Kozaburo , Ibata Toshikazu , Takebayashi Matsuji 
Published: July 2006

Abstract
The copper chelate-catalyzed decomposition of o-methoxycarbonyl-α-diazoacetophenone was carried out in benzene. The reaction gave a dimer of a carbonyl ylide intermediate. The intermediate was trapped with dipolarophiles such as trans-dibenzoylethylene, ethyl fumarate, isoprene and dimethyl acetylenedicarboxylate, yielding 1,3-dipolar adducts in a stereospecific and stereoselective manner. Similar results were obtained in the catalytic decomposition of o-(n-butoxycarbonyl)-α-diazoacetophenone. The configuration of adducts and the mechanism of the reaction are discussed.
Anodic Reaction of 2-Furoic Acids. II. Electrolysis of Methyl 5-Acetyl-2-furoate and Its Homologous in Protic Solvents
Authors: Torii Sigeru , Tanaka Hideo , Okamoto Tsutomu 
Published: July 2006

Abstract
Anodic oxidation of methyl 5-acetyl-2-furoate 4 in methanol leads to ring-opened diesters 8 and 9, and lactone 10 in addition to methyl 5-acetyl-2,5-dimethoxy-2,5-dihydro-2-furoates 7. Formation of 8, 9, and 10 can be rationalized as arising from 7. On the other hand, oxidation of methyl 5-methoxy- and 5-bromo-2-furoates, 5 and 6, also give 9 and 10. The reactions involve initial production of cationic intermediates 13 and 15, which are readily solvolized to give 8, 9, and 10. A mechanism of the formation of the intermediates 13 from 5, 6, and 7 is discussed.
Reaction of α-Halosulfoxides with Amines
Authors: Numata Tatsuo , Oae Shigeru 
Published: July 2006

Abstract
When optically active bromomethyl p-toly sulfoxide was treated with sodium methylmercaptide or sodium ethoxide, optically active α-substituted methyl p-toly sulfoxides were obtained in good yields. By contrast, reaction with secondary amines produced achiral p-toluenesulfenamides, methylenediamines, and amine hydrobromides in nearly quantitative yields. The reaction with an amine is presumed to proceed through the initial nucleophilic substitution at α-carbon of the sulfoxide to form aminomethyl p-toly sulfoxide, followed by rearrangement to the corresponding sulfenate, and subsequent attack of the amine at the sulfur atom of the sulfenate to form the final product. Meanwhile, a facile interconversion of alkoxymethyl p-toly sulfoxide and corresponding sulfenate was also observed.
The Photochemistry of 4,5-Disubstituted 1,3-Dioxolen-2-ones
Authors: Hiyama Tamejiro , Fujita Shinsaku , Nozaki Hitosi 
Published: July 2006

Abstract
The benzene-sensitized photoreaction of 4,5-dipropyl- (IIa) and 4,5-tetramethylene-1,3-dioxolen-2-one (lIb) in isopropyl alcohol gives two reduction products, cis- (V) and trans-4,5-disubstituted 1,3-dioxolan-2-one (VI). The irradiation of octa- (IId) and decamethylene-bridged vinylene carbonate (IIe) results in transannular hydrogen atom transfer from a methylene group to the olefinic bond and a subsequent recombination affording three tricyclic products, IX, X, and XIX. An examination of the stereochemistry of the products has indicated the participation of a diradical intermediate.
The Phenolysis of Tetrahydrolinalyl and 2-Octyl Systems. The Rates, Steric Courses, and Product Distributions
Authors: Okamoto Kunio , Kinoshita Tomomi 
Published: July 2006

Abstract
As tertiary and secondary systems with optical activity, tetrahydrolinalyl (methylethylisohexylcarbinyl) chloride or p-nitrobenzoate and 2-octyl p-toluenesulfonate have been selected, and their titrimetric and polarimetric rate constants (kt and kp) for SN1 phenolyses have been measured in the presence of triethylamine (or sodium phenoxide) in 50 wt% phenol–benzene. At higher amine (or phenoxide) concentrations, the kt and kp coincide with each other for tetrahydrolinalyl chloride (at 25.0°C) or p-nitrobenzoate (at 100.0°C), and also for 2-octyl tosylate (at 75.0°C), exhibiting the typical features of the nN1 solvolysis rate constant. In the absence of the amine (or sodium phenoxide), the kt diminishes to show a gap between the kp and the kt, indicating the occurrence of an ion-pair return in the phenolysis for both systems. Under the same reaction conditions as those of the rate measurement, tetrahydrolinalyl chloride and p-nitrobenzoate yield the phenyl ether, with a predominant racemization accompanied by some net inversion of the configuration, whereas 2-octyl tosylate gives 2-octyl phenyl ether, o-, and p-2-octylphenols, with a net inversion of the configuration accompanied by a slight racemization. These steric results indicate that phenol can be considered as a typical solvolytic solvent. The product distributions have been assessed for the reactions of 2-octyl chloride (200°C) and of tetrahydrolinalyl chloride (25.0°C) with the molecule of phenol under the SN1 phenolysis conditions, by extrapolating the product composition curves to a zero concentration of the phenoxide. For both systems, the phenol molecule is predominantly O-alkylated (74 and 99% respectively), accompanied by minor amounts of C-alkylation. In contrast to the phenol reaction, the phenoxide ion undergoes more C-alkylation (42 and 50% respectively).
Friedel-Crafts Aralkylation. II. The AlCl3·CH3NO2-catalyzed Phenethylation of Benzene and Toluene with 2-Arylethyl Chlorides in a Nitromethane Solution
Authors: Ichii Makoto 
Published: July 2006

Abstract
The rates of AlCl3·CH3NO2-catalyzed phenethylations of benzene (50°C) or toluene (25°C) with 2-arylethyl (ring-substituted phenethyl) chlorides were measured in homogeneous nitromethane solutions. The reactions are first-order in the aromatic component, first-order in the phenethyl chloride, and second-order in aluminum chloride. Substituent effects in the phenethyl chlorides give linear relationships with Hammett’s σ constants. A displacement mechanism involving a nucleophilic attack by the aromatic substrate on the phenethyl chloride-catalyst system is proposed for the reactions. Competitive phenethylations of benzene and toluene were also carried out at 50°C. Both the isomer distribution and the relative reactivity of toluene to benzene are affected by the ring-substituents, the effects of which are correlated closer with the substrate selectivity. These results suggest that the transition state in the rate-determining step for the phenethylations is in nature an (oriented) π complex rather than a σ complex.
The Reaction of Elemental Sulfur with Organic Compounds. IV. The Reactions of N-Arenesulfonylsulfilimine and Sulfoximine with Sulfur and Diaryl Disulfide
Authors: Oae Shigeru , Tsuchida Yoshiyuki , Tsujihara Kenji , Furukawa Naomichi 
Published: July 2006

Abstract
The reactions of elemental sulfur and diaryl disulfide with the compounds bearing a semipolar S→N linkage were investigated. Elemental sulfur was found to react with N-arenesulfonylsulfilimine and sulfoximine affording the corresponding sulfide and the sulfoxide respectively. Diaryl disulfide also was found to undergo similar reactions with these compounds. In the reaction of diaryl disulfide with N-arenesulfonylsulfilimine, N,N-bis-(arylthio)arenesulfonamide was obtained as a main product besides the corresponding sulfide. The mechanisms of these reactions are discussed.
Optical Resolution of Aspartic Acid by Using Copper Complexes of Optically Active Amino Acids
Authors: Harada Kaoru , Tso Wung-wai 
Published: July 2006

Abstract
Optical resolution of Dl-aspartic acid by using copper complexes of l-alanine, d-alanine, l-glutamic acid, d-glutamic acid, and l-proline in aqueous solution is described. In this investigation the effects of (1) the concentration of reactants and (2) the ratio of the optically active amino acid to racemic aspartic acid in the reaction mixture were studied.
Model Reactions for the Biosynthesis of Thyroxine. XIX. The Formation of a Thyroxine Precursor by Photooxidation of 4-Hydroxy-3,5-diiodophenylpyruvic Acid in Organic Solvents
Authors: Omura Kanji , Nishinaga Akira , Matsuura Teruo 
Published: July 2006

Abstract
Photooxidation of 4-hydroxy-3,5-diiodophenylpyruvic acid (I) in methanol was found to yield a hydroperoxide (IV). This hydroperoxide reacted anaerobically with 3,5-diiodotyrosine (II) to form thyroxine (III). A photo-product, presumably IV, apparently accelerated the oxidation of I. Methanol, among several organic solvents, was found to be the best solvent for the photooxidation. Similar oxidations with 4-hydroxy-3-iodo-5-methoxyphenylpyruvic acid (V) and 4-hydroxyphenylpyruvic acid (VI) showed that the rate of oxidation decreased in the order I&gt;V&gt;VI. A product of the photooxidation of I, probably the hydroperoxide IV, also acts as an accelerator in the photooxidation of the desiodo analog VI of I.
Studies of Acyl and Thioacyl Isocyanates. IX. The Cycloaddition Reactions of Benzoyl and Thiobenzoyl Isocyanates with Anils
Authors: Tsuge Otohiko , Kanemasa Shuji 
Published: July 2006

Abstract
Thiobenzoyl isocyanates react with benzylidenanilines, benzylidenalkylamines and dianils to yield the corresponding mono- and bis (4+2) cycloadducts. Benzoyl isocyanates do not react with benzylidenanilines, but they are easily added to benzylidenebenzylamine to give the (4+2) cycloadducts in good yields. Cycloaddition of these isocyanates to anils is dependent upon the basicity of the nitrogen atom of C=N bond. Neither benzoyl isocyanates nor thiobenzoyl isocyanates are added to the C=C bond of cinnamylidenanilines, but they react with the C=N bond to afford the (4+2) cycloadducts.
The Synthesis and Stereochemistry of 2,3-Ferrocenocyclopentenone
Authors: Shirafuji Tamio , Odaira Akio , Yamamoto Yasusi , Nozaki Hitosi 
Published: July 2006

Abstract
An optical isomer of 2,3-ferrocenocyclopentenone (X) has been synthesized from methyl (1S) (−)-2-hydroxy-methylferrocenecarboxylate via a six-step synthesis. The absolute configuration of (−)-X has been confirmed by a comparison of its CD and ORD curves with those of the corresponding ferrocene homologs previously recorded. The mass spectrum of X is also discussed.
Electrocatalytic Chemistry of the Transition Metal Complexes. II. Dehydrogenation of Cyclohexene Catalyzed by the Electroreduced Cobalt Complex of α,β,γ,δ-Tetraphenylporphine
Authors: Kageyama Hironori , Hidai Masanobu , Uchida Yasuzo 
Published: July 2006

Abstract
The metal complexes of α,β,γ,δ-tetraphenylporphine (M(TPP), M=Co(II), Ni(II), FeCl(III), Pd(II), Pt(II), Cu(II), MnCl(III), and V(IV)O) were electrolyzed at −2.0 V vs. Ag wire in the presence of cyclohexene under nitrogen atmosphere. The cobalt complex only had the catalytic activity of dehydrogenating cyclohexene to 1,3- and 1,4-cyclohexadiene and benzene. With the use of dimethylformamide, dioxane, and hexamethylphosphoric triamide as solvent, cyclohexadienes were produced, and with that of benzonitrile, and dimethyl sulfoxide, benzene was produced and cyclohexadienes were scarcely produced at all. In all cases, the current efficiency of the products was much higher than 100%, indicating that the dehydrogenation reaction is catalytic. The composition of the products also varied with the reaction temperature. When ethanol was added to the reaction solution, the amount of cyclohexadienes increased with benzonitrile used as solvent. The ESR spectrum observed at g=2.003 under electrolysis at the second wave potential is due to the anion radical of cobalt(I) tetraphenylporphine. From polarographic data and other experiments, the species is considered to be an intermediate for dehydrogenation of cyclohexene. The active sites for dehydrogenation are considered to be both the central metal atom and the conjugated ring.
Photolyses of Diaryl α-Disulfones
Authors: Kobayashi Michio , Tanaka Koji , Minato Hiroshi 
Published: July 2006

Abstract
Di-p-tolyl disulfone and diphenyl disulfone were decomposed in various arenes by irradiation of UV light. The products found were arenesulfonic acids, arenesulfonic anhydrides, thiolsulfonates, diaryl sulfones, biaryls, and sulfur dioxide. All the findings indicate that photolyses of α-disulfones yield a pair of arenesulfonyl radicals.
Diazotization of Tetrafluoroanthranilic Acid and Several Reactions of Related Compounds
Authors: Hayashi Sei-ichi , Ishikawa Nobuo 
Published: July 2006

Abstract
Diazotization of tetrafluoroanthranilic acid with nitrosylsulfuric acid in acetic acid gave a ring-hydroxylated, stable diazonium salt 4, which was isolated in high yield. Several reactions on this diazo compound were carried out. Replacement of the diazonium group with hydrogen, chlorine, or bromine was accomplished with the usual reagents. The reaction of diazo compound with diazomethane afforded a benzoxadiazine compound 13. Other related polyfluoroaromatic compounds were prepared.
The Crystal Structure of Cupric Complex with Succinimide I. Cesium Tetrakis(succinimidato)copper(II) Dihydrate
Authors: Tsukihara Tomitake , Katsube Yukiteru , Fujimori Kumiko , Ito Toshiaki 
Published: July 2006

Abstract
The crystal structure of cesium tetrakis(succinimidato) copper(II) dihydrate, Cs2(Cu(sucim)4)·2H2O, has been determined by means of X-ray analysis. The crystals are violet rhombic plates. Dimensions of the triclinic unit cell are a=9.19, b=15.32, c=8.39 Å, α=88.7°, β=92.0°, γ=93.8°, and z=2. The space group is C\bar1. The structure has been determined by the Patterson synthesis, a series of Fourier syntheses and the least-squares method. The coordination around the copper atom is a square planar. Two independent cesium ions have a quite different environment. Complex anions, (Cu(sucim)4)2−, are linked with each other through the hydrogen bonds between water and carboxyl oxygen atoms.
ESR Studies of the Conformation and Restricted Rotation of 4-Phenyl-1,3-dioxane Anion
Authors: Iwaizumi Masamoto , Matsuzaki Takashi , Isobe Taro 
Published: July 2006

Abstract
The ESR of the 4-phenyl-1,3-dioxane anion shows a line-width alternation effect which can be attributed to the restricted rotation between the 1,3-dioxane and benzene rings. From the temperature dependence of the line-width alternation effect, the activation energy was determined to be 180±110 cal·mol−1. The preferential conformation between the two rings was estimated from the hyperfine splitting constant of the proton at the 4 position in the 1,3-dioxane ring, to be that where the two rings have some angle close to 90° rather than the structure where they are parallel. It was also found that an odd electron, which mainly occupies a vacant π orbital in the benzene ring, delocalizes appreciably into a part of the 1,3-dioxane ring.
Vibration Spectra and Molecular Structures of n-Butyl Chloride and n-Butyl Bromide in Relation to Parallel (1:3) Interactions
Authors: Fujiyama Tsunetake 
Published: July 2006

Abstract
The vibration spectra of liquid n-butyl chloride and n-butyl bromide are observed in the region of 1500–100 cm−1. From the analyses of spectra corresponding to the skeletal deformation vibrations, the molecular configurations are determined for both molecules. All the possible rotational isomers, the TT, GT, TG, GG, and GG′ forms, are observed for n-butyl chloride, while four isomers, the TT, GT, TG, and GG forms, are observed for n-butyl bromide. The results are compared with those of the electron-diffraction methods. It is shown that unfamiliar interactions must be considered for the parallel (1:3) interaction between methyl and chlorine substituents.