bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cationic Arylation. II. Phenylation of Substituted Benzenes with Phenylazo-p-tolylsulfone in Acidic Solutions
Authors: Kobayashi Michio , Minato Hiroshi , Kobori Nobumasa 
Published: July 2006

Abstract
The acid-catalyzed decomposition of phenylazo-p-tolylsulfone was studied in PhX, PhX-CH3CN and PhX-DMSO (X=OCH3, C2H5, CH3, Cl, CO2CH3, NO2). The decomposition was of first order but was faster with greater concentration of trifluoroacetic acid. The orientation and the partial rate factors for the phenylation of substituted benzenes were quite different from those for the radical phenylation but quite similar to those for the phenylation with phenyl cation generated from PhN2+BF4−. Experiments with deuterated compounds indicated that the abstraction of proton from the phenylated complex was not rate-determining. A mechanism involving phenyl cation was proposed for the acid-catalyzed decomposition of azosulfone.
The Stereoselectivity of the Methylcarbenoid of Zinc in the Reaction with Styrene, Indene, and Naphthalene
Authors: Nishimura Jun , Furukawa Junji , Kawabata Nariyoshi 
Published: July 2006

Abstract
The stereoselectivity of the methylcarbenoid generated from diethylzinc and ethylidene iodide was investigated in the reactions with styrene, indene, and naphthalene. 1-Methyl-2-phenylcyclo-propanes (cis/trans=4.1) were obtained from styrene in a 13% yield. Indene gave exclusively the endo-isomer of 6-methyl-2,3-benzobicyclo[3.1.0]hex-2-ene in a 28% yield. From naphthalene, three isomers of 5,8-dimethyl-2,3-benzotricyclo[5.1.0.04,6]oct-2-ene were obtained favorably to the syn-form, as in the cases with styrene and indene, but two isomers of 7-methyl-2,3-benzobicyclo[4.1.0]-hepta-2,4-diene were formed favorably to the anti-form. This anti-selectivity was explained by the step-by-step addition mechanism which had previously been proposed for the ring-expansion reaction of alkylbenzene by the methylcarbenoid.
Thermal Decomposition of Lead Carbonate Tablets Prepared by Compressing Fine Particles
Authors: Komoda Ryozo , Nishi Yasuhide , Kano Matsutaro , Imoto Tatsuya 
Published: July 2006

Abstract
The thermal decomposition of lead carbonate tablets was kinetically studied in a nitrogen gas stream at temperatures of 240, 320, and 360°C. The tablets used in this work were prepared by compressing lead carbonate particles in a steel mold under pressures of 2–15 ton/cm2. The decomposition reaction for the tablet was represented in two ways. Rate expressions were developed from the unreacted-core shrinking model applied to the individual particles (for the first of the two decomposition processes) and to the whole tablet (for the second). The effect of the pressure applied in preparing the tablet on the decomposition rate was attributed to the deviation in the pressure profile for carbon dioxide in a tablet (for the first process) or to the variation in the effective diffusivity and bulk density of the tablet (for the second).
Isotopic Exchange between Hydrogen Sulfide and Deuterium on the Surface of Cuprous Sulfide
Authors: Fueki Kazuo , Inaba Hideaki , Mukaibo Takashi 
Published: July 2006

Abstract
The isotopic exchange between H2S and D2 has been followed in the temperature range 425–525°C on a cuprous sulfide specimen. At high sulfur activities of Cu2S, the predominant reaction is H2S+D2=H2+D2S, and at moderate sulfur activities the same reaction is predominant in the initial period. Analysis of kinetic data shows that the exchange reaction is first order. From the first-order rate constant, ki, the rate constant of sulfidation of Cu2S by “hydrogen sulfide”* and ki′, the rate constant of reduction of Cu2S by “hydrogen”* are determined. It is shown that ki is inversely proportional to the sulfur activity of Cu2S and that ki′ is independent of it. Dependence of ki and ki′ on sulfur activity is interpreted on the basis of a theory proposed by Kobayashi and Wagner. The formation of HD becomes remarkable as the sulfur activity of Cu2S decreases. This finding shows that the reaction, H2S+D2=HD+HDS, becomes appreciable with the decrease in sulfur activity.
The Crystal Structure of Bis-(2-hydroxyacetophenone)trimethylenediiminocopper(II)
Authors: Iida Kiyoto , Oonishi Isao , Nakahara Akitsugu , Komiyama Yoshimichi 
Published: July 2006

Abstract
The crystal structure of bis-(2-hydroxyacetophenone) trimethylenediiminocopper(II), [Cu-(hapt)], has been determined on the basis of the X-ray diffraction data. The crystals are monoclinic. The cell dimensions are: a=17.746, b=9.467, c=10.646 Å, and β=114.06°. The space group is Cc, with four formula units in the unit cell. The structure has been refined from threedimensional data by the least-squares method with anisotropic temperature factors to an R-value of 0.093. The copper atom is four-covalent, with the two planar 2-hydroxyacetophenone groups oriented so as to give a flattened tetrahedral co-ordination geometry. The six-membered coppertrimethylenediamine ring takes a “twisted boat” configuration. The Cu–O bonds are 1.88 and 1.89 Å in length, while the Cu–N bonds are 1.94 and 1.97 Å. The angle between the mean planes of the 2-hydroxyacetophenone moieties is 46.2°.
The Interaction of Polymer Ions with Counterions. II. Polymethacrylates
Authors: Tamaki Kunio , Horiuchi Teruo 
Published: July 2006

Abstract
The equivalent conductivities and the electrophoretic mobilities of sodium, tetramethyl-, tetraethyl-, and tetrabutyl- ammonium salts of polymethacrylic acid (PMA) in 0.05 m solutions of the simple salts of the corresponding cations are measured at 25°C, and the results obtained are interpreted in terms of the counterion binding. The calculated values of the apparent degree of ionization for sodium, tetramethyl-, and tetraethylammonium salts of PMA are found to be larger than those of the corresponding salts of polyacrylic acid (PAA), indicating that the methyl groups in PMA generally hinder the binding of counterions with polyions. With tetrabutylammonium salt of PMA, the apparent degree of ionization is nearly equal to that of the tetrabutylammonium salt of PAA. This fact suggests hydrophobic interaction between the methyl groups in PMA and tetrabutylammonium ions.
Association of a Reduced Riboflavin Derivative with Purities, Pyrimidines and Nicotinamide
Authors: Yu Byung Sul , Kyogoku Yoshimasa 
Published: July 2006

Abstract
Hydrogen bonding of a reduced riboflavin derivative in chloroform has been studied by infrared spectra measurements. The self-association of the reduced form of riboflavin tetraacetate is much stronger than that of the oxidized form. The reduced form can also form hydrogen bonded complexes with some aminopurines, aminopyrimidines, aminopyridines and nicotinamide derivatives. In the bonding with aminopyridines the contribution of a proton transfer must be predominant. At partial reduction states the formation of radicals, semiquinone forms, was detected with the aid of the electron spin resonance. The concentration of free radicals, however, is about 1 per cent of dissolved riboflavin tetraacetate. The infrared spectra at various stage of reduction can be interpreted by the sum of the two individual spectra of the fully reduced and oxidized forms.
The Crystal and Molecular Structure of Bis(acetylacetonato) manganese(II) Dihydrate
Authors: Onuma Shigeki , Shibata Shuzo 
Published: July 2006

Abstract
The crystal and molecular structure of bis (acetylacetonato)manganese(II) dihydrate, Mn-(C5H7O2)2·2H2O, has been determined from three-dimentional X-ray diffraction data. The compound has a center of symmetry. The octahedral arrangement of the ligand atoms about the central manganese atom is distorted; the Mn–O(1) and Mn–O(2) distances are 2.129 and 2.150 Å, Respectively, the Mn–O(H2O) distance is 2.267 Å. The metal atom lies 0.561 Å out of the least-squares plane of the chelate ring. The chelate is isostructural with the cobalt, nickel, and magnesium analogues.
An Electron Spin Resonance Study of 1,1′- and 2,2′-Biazulenyl Anion Radicals
Authors: Ikegami Yusaku , Seto Shuichi 
Published: July 2006

Abstract
The electron spin resonance (ESR) spectra of the anion radicals of 1,1′- and 2,2′-biazulenyls have been examined. The ESR spectrum of the latter shows that the unpaired spin is distributed equally between both azulene rings of the molecule. Theoretical calculation of the spin densities by the McLachlan procedure gave satisfactory agreement with the experimentally estimated densities. The ESR spectrum of the anion radical of 1,1′-biazulenyl, which could only be generated by an electrolytic technique, is explained by the fact that the spin exchange between the two halves of the molecule is slow. However, the ESR spectrum of the anion radical of the 3,3′-dicarbethoxy derivative of 1,1′-isomer showed rapid spin exchange through 1,1′-bond.
Oxidation of Substituted Glycollic Acids by Ce(IV) in Sulphuric Acid Solutions
Authors: Grover V K , Gupta Y K 
Published: July 2006

Abstract
A comparison of the rate constants, dissociation constants, tendency of complex formation and catalytic activity of Mn(II) in the oxidation of substituted glycollic acids (benzilic, Dl-atrolactic, 2-hydroxyisobutyric, p-chloromandelic, p-bromomandelic, mandelic and lactic acids) by Ce(IV) in sulphuric acid solutions has been made. Hydrolyzed species of Ce(IV) are reactive and the kinetics conform to the empirical rate law
-\fracd[Ce(IV)]dt=\frackK[Ce(IV)][Org. Acid][HSO_4^-]^2([H^+]+K[Org. Acid])
The reactivity and the chelating tendency of the acids seem to follow the substituent order, C6H5&gt; CH3&gt;H. The catalytic activity of Mn(II) appears to follow the same order as in the oxidation of these acids by Mn(III).
Polarographic Study of Metal Complexes. X. The Disulfitotetracyanocobaltate(III) Complex
Authors: Maki Nobufumi , Yamamoto Kouei 
Published: July 2006

Abstract
The sodium disulfitotetracyanocobaltate(III), Na5[CoIII(SO3)2(CN)4]·3H2O, was found to be irreversibly reduced in one step to the cobalt(I) state in a 0.5m Na2SO3 aqueous solution at the dropping mercury electrode(DME). As for the resulting cobaltate(I) complex, neither further reduction to the metal nor oxidation was observed in the potential range of 0–−2.0V (vs. SCE). Above 40°C, a partial reduction to the metal was observed to take place at about −1.9 V (vs. SCE). The reduction was interpreted as being of the “inert-inert” type, as shown below:
trans-[Co^III(SO_3)_2(CN)_4]^5- \overset2e→ trans-[Co^I(SO_3)_2(CN)_4]^7-.
Here, the disulfito complex was presumed to take a trans-configuration rather than that of a cis-form on the evidence of its polarographic behavior and the absorption spectrum. That is, the tetracyano complexes with a cis-configuration are considered to be reduced to the metal, whereas those with a trans-configuration are reduced to the cobalt(I) state, and not to the metal polarographically, at the DME.
Studies of the Ion-pairing of Hexylate and Picrate Ions with Alkali Metal Ions by Capillary Analysis
Authors: Sano Kazuaki , Sakuma Michio , Motomizu Syoji , Iwachido Tadashi , Tôei Kyoji 
Published: July 2006

Abstract
The hexyl (Dipicrylamine) anion, hexylate, and picrate form weak ion-pairs with alkali metal cations in an aqueous solution. The composition and the association constants of the ion-pairs are determined by capillary analysis based on the difference in the adsorbability of the anions and of the ion-pairs on a filter paper. A new constant temperature-humidity apparatus is devised, and by means of it the analysis is successfully carried out. The compositions of the cation and the anion in the ion-pairs formed are 1:1, in either case; the association constants of the ion-pairs for Li, Na, K, Rb, and Cs cations are about 102, and they tend gradually to decrease with the ionic radii.
A New Method of Preparing θ-Alumina and the Interpretation of Its X-Ray-powder Diffraction Pattern and Electron Diffraction Pattern
Authors: Yamaguchi Goro , Yasui Itaru , Chiu Wen-Chau 
Published: July 2006

Abstract
Highly crystallized θ-alumina was obtained by a two-step treatment, by hydrothermal and thermal treatment, of η-alumina. Its X-ray-powder diffraction pattern was interpreted based on the structure of θ-gallia, and least-squares refinements were carried out. The electron diffraction pattern of θ-alumina from boehmite was also interpreted, and the directional relations between the phases were established.
Ring-opening Reactions of Cyclic Ethers. VIII. Acid-catalyzed Ring-opening Reactions of Isobutylene Oxide in Alcohols
Authors: Sekiguchi Shizen , Matsui Kohji , Yasuraoka Yoshihiro 
Published: July 2006

Abstract
The rates of the ring-opening reaction of isobutylene oxide have been measured in methyl, ethyl, w-propyl and isopropyl alcohols in the range from 10 to 40°C under conditions where the molar ratio of an alcohol to the epoxide was kept at 10 and the range of the concentration of boron trifluoride etherate was ca. 1.0×10−3 to ca. 4.0×10−3 mol/l. The rate equation is expressed as follows: −d[epoxide]⁄dt=k2[C0][epoxide], where [C0] is the initial concentration of the catalyst and [epoxide] is the instantaneous concentration of the epoxide at time t. The rate constants (k2) decreased in the order, CH3OH&gt;C2H5OH&gt;n-C3H7OH&gt;i-C3H7OH. The entropies of activation decreased in the same order, while the energies of activation were not appreciably changed. A plot of logk2 against 1/D (D, the dielectric constant of the mixture of each alcohol and the epoxide) was found to be linear, its slope being −61.2. The results support the fact that the reaction is bimolecular.
Cyclizations of Thioureas with a Hydroxy Group at the β-Position of the N-Substituent. I. Reaction with Cupric Acetate
Authors: Iwakura Yoshio , Kaya Tadahiro , Kurita Keisuke 
Published: July 2006

Abstract
The reaction of 1-(3-phenoxy-2-hydroxypropyl)-3-phenyl-2-thiourea (thiourea I) with cupric acetate was investigated. The desulfurization reaction by the cupric ion proceeded in refluxing ethanol to yield 2-anilino-5-phenoxymethyl-2-oxazoline. At room temperature, thiourea I and cupric acetate gave a copper complex and the oxazoline. When the complex was heated in ethanol, the same oxazoline and thiourea I were obtained, along with inorganic copper compounds. On the basis of an investigation of the structure of the complex and the decomposition of the complex, the reaction mechanism involving copper-complex formation was discussed. On the other hand, the reaction of 1-(3-phenoxypropyl)-3-phenyl-2-thiourea with cupric acetate under the same conditions gave 1-(3-phenoxypropyl)-3-phenyl-3-acetylurea.
Synthesis of [9]Heterophanes from 2-Cyclododecenone
Authors: Fujita Shinsaku , Kawaguti Takeyuki , Nozaki Hitosi 
Published: July 2006

Abstract
[9](3,5)Pyrazolophane (V) and 11-methyl[9](2,4)furanophane (IX) were prepared from 2-cyclododecenone (I) and their spectral properties were discussed. A new route to I from cyclododecanone is described.
The Dipole Moments of α,ω-Alkanediols
Authors: Toshiyasu Yoshio , Kimura Ko , Fujishiro Ryoichi 
Published: July 2006

Abstract
The electric dipole moments of α,ω-alkanediols such as HO–(CH2)n–OH (n being varied from 2 to 5) were measured both in dioxane and in a mixed solvent of dioxane with carbon tetrachloride at 25°C. The observed dipole moments increase with the increasing n until n=4, and then decrease for n=5, while the calculated dipole moments based on the vector addition of group moments on the assumption of the random coil model for alkane chains increase monotonously as n increases from 2 to 5. It is concluded that for both propanediol and butanediol the conformations forming the intramolecular hydrogen-bond which have the larger dipole moments contribute appreciably to the observed dipole moments. The dipole moment of pentanediol is close to the calculated one for the random coil model, whereas that of ethylene glycol suggests the existence of the intramolecular hydrogen-bond. Population analysis of the hydrogen-bonded species in solutions is also given.
The Effect of Adsorbed Amines on the ESR of Copper Oxide
Authors: Ueda Hisashi , Todo Naoyuki 
Published: July 2006

Abstract
The effect of several additives on the ESR of copper oxide was studied. Among the additives studied, amines and NH3 had peculiar effects on the ESR spectra. From the spectrum formed by NH3 it is concluded that the (Cu–NH3)2+ complex cation is formed on the surface of a CuO particle. The formation of this complex cation obeyed a pseudo-flrst-order rate and can be interpreted in terms of the surface reaction between the exposed Cu2+ and NH3. Among the amines studied, only primary amines gave ESR spectra which provide evidence for the existence of (Cu-amine)2+complex cations. The foregoing fact and the results obtained on the three isomers of chloroaniline indicate that a strong s-character of the lone-pair orbital is needed if an amine molecule is to occupy a surface defect of the O2−, by which the Cu2+ is exposed on the surface, thus forming a complex cation. By these facts, the d-orbital of Cu2+, which can overlap with the nitrogen lone pair of the amine molecule, is concluded to be dz2. The three principal values of the g-tensor for the (Cu–NH3)2+complex cation depend greatly on the temperature, indicating that this cation has some rotational and vibrational motions below 130°C, at which point Cu2+ and NH3 dissociate.
Mechanism of Redox Surface Reaction between Wüstite and CO2 or CO
Authors: Kurihara Seiichi , Fueki Kazuo , Mukaibo Takashi , Wada Yasuo 
Published: July 2006

Abstract
The redox reaction between thin wüstite foil and CO2 or CO was studied by means of a microbalance in a temperature range 900–1075°C. It was found that the reaction at the gas-wüstite interface is rate-controlling and that the reaction rate is expressed as
V_ox=k_OP_CO2a_O^-m/3 and V_red=k_O’P_COa_O^n/3
where aO is the oxygen activity of wüstite, and m and n are 2.1–2.2 and 0.8–1.2, respectively. On the basis of the theory by Kobayashi and Wagner, the most predominant mechanism is concluded to be
CO_2+2\ominus\ightleftarrowsCO+O^2-
Actigation energies for kO and kO′ were 35+3 and 32+3 kcal/mol, respectively.
Ionic Processes in the Radiolysis of Nitrous Oxide. The Effect of Electron Scavenger and Rare Gas Setisitization
Authors: Takao Satoshi , Shida Shoji 
Published: July 2006

Abstract
The effect of electron scavenger (SF6) on the radiolysis products of N2O was examined. The sensitization of N2O by various rare gases was also measured. In the presence of an electron scavenger we got 3.0 for the value of −ΔG(−N2O) in good agreement with the value of G(e−) for N2O. In the experiments of Xe or Kr containing small amounts of N2O, the G(−N2O) values were nearly equal to the respective G(e−) values for the rare gases, and the addition of SF6to the Xe-N2O system almost completely inhibited nitrogen formation. The results show that one electron decomposes just one molecule of N2O. This fact can not be accounted for by the hitherto assumed mechanism, and a new mechanism involving N2O− is proposed for ionic processes in the radiolysis of N2O. In the N2O-rare gas mixtures of various compositions, the sensitized yields of N2O decomposition per 100 eV energy absorbed by rare gases were divided into two groups, e.g., the yields from He, Ne mixtures were about twice as large as those from Ar, Kr and Xe mixtures. This result is discussed in terms of charge transfer and the Penning ionization.
Anodic Process of Thiosulfate at a Dropping Mercury Electrode
Authors: Murayama Teisuke , Sawaki Toshiko , Sakuraba Shukichi 
Published: July 2006

Abstract
In the anodic process of thiosulfate at a dropping mercury electrode, the formation of a species Hg(S2O3)34− is considerable even in dilute solution. An equation of current-potential curve is derived with proper consideration for the formation of the species. The successive stability constant of Hg(S2O3)34− was calculated to be 3×102 (at 25°C and an ionic strength of 0.2) by comparing the equation with experimental results.
An Internal-Reference Method for the Determination of Rubidium by Photon-Activation Analysis with Strontium Used as the Reference Element
Authors: Tsai Hui-Tuh , Kato Toyoaki , Oka Yoshinaga 
Published: July 2006

Abstract
We have studied a method for the determination of rubidium by activation analysis with brems-strahlung photons, with strontium used as the internal-reference element. This method is based on the γ-ray spectrometric measurement of the 84Rb activities produced by the 85Rb(γ,n) reaction and on the comparisons of those activities with that of 83Rb arising from strontium as a result of the (γ,p) reaction. The yields of various photonuclear reactions in rubidium and in strontium have also been examined as a function of bremsstrahlung maximum energies up to 60 MeV, and the best conditions for the determination of rubidium are proposed. When the maximum energy was set at 18 to 20 MeV, no interfering reactions occurred; a rubidium content down to about 2 μg can be determined accurately. A comparison of solid-state and scintillation γ-ray spectrometry in this method has also been included with respect to the sensitivity and the selectivity.
Oxidation of N,N′-Diarenesulfonylhydrazines
Authors: Kohara Yoshio , Kobayashi Michio , Minato Hiroshi 
Published: July 2006

Abstract
N,N′-Diarenesulfonylhydrazine was oxidized with several oxidizing regents, but diarenesulfonyl diimide was not isolated. Diarenesulfonyl diimide produced immediately decomposed with evolution of 1 mol of nitrogen, and afforded the corresponding sulfonyl bromide, α-disulfone and sulfonic acid. Plausible mechanisms of decomposition were discussed.
Studies of Peptide Antibiotics. XXL Synthesis of Tyrocidine C
Authors: Kuromizu Kenji , Izumiya Nobuo 
Published: July 2006

Abstract
A cyclic decapeptide, cyclo-(l-Trp-d-Trp-l-Asn-l-Gln-l-Tyr-l-Val-l-Orn-l-Leu-d-Phe-l-Pro-), having the amino acid sequence of natural tyrocidine C has been synthesized. Chemical and biological properties of this product have been described. An antibiological activity of the product toward Gram positive microorganisms was found to be nearly the same degree as that of tyrocidine B.
Studies on Aminosugars. XXV. The Synthesis of Position Isomers of α-d-Glucopyranosyl-2-deoxystreptamine
Authors: Nishimura Yoshio , Tsuchiya Tsutomu , Umezawa Sumio 
Published: July 2006

Abstract
Racemic O-isopropylidene derivative of N,N′-diethoxycarbonyl-2-deoxystreptamine was glucosidized with 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosyl chloride to afford two kinds of position isomers of α-glucoside, which led to 4-O-(α-d-glucopyranosyl)- and 6-O-(α-d-glucopyranosyl)-2-deoxystreptamine. Structural assignments were made by the determination of Δ[M] of the glucosides in a tetramminecopper(II) sulfate solution.
The Mössbauer Effect in Triethyltin Phenyl Derivatives
Authors: Watanabe Noriyuki , Niki Eiji 
Published: July 2006

Abstract
Substituent effect of triethyltin phenyl derivatives was investigated by means of the 119Sn Mössbauer effect. The isomer shifts obtained for these compounds fall into the range −0.15–−0.18 mm/sec with respect to Pd119mSn source. p-Cl and m-Cl derivatives show broadened spectra, which may be ascribed to an unresolved quadrupole splitting. This small quadrupole interaction may be interpreted in terms of the partial ionicity of the bond formed between tin and carbon in phenyl group.
The Crystal Structure of a Colored Complex, C7H7OHg·C7H6O2N, Obtained in the Millon Reaction of p-Cresol
Authors: Kobayashi Yoshiko , Iitaka Yoichi , Kido Yasumasa 
Published: July 2006

Abstract
The crystal structure of the complex of 2-mercuri-4-methylphenol and 2-nitroso-4-methylphenol obtained in the modified Millon reaction was determined using three-dimensional X-ray diffraction data. The complex crystallizes in triclinic system, space group P\bar1, with a unit cell of dimensions a=10.26 Å, b=22.71 Å, c=5.61 Å, α=97.2°, β=93.1°, γ=91.1°, containing four complex molecules. Each of the two crystallographycally independent complex molecules both having essentially the same structure, forms a dimer with its nearest neighbor related by a center of symmetry through a pair of hydrogen bonds. The mercury atoms adopt a planar four-fold coordination with nitrogen, carbon and two oxygen atoms.