bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intramolecular Participation of Sulfide Linkage in the Reactivity of Carbene and Diazoalkanes. I. Alkylcarbenes and Diazoalkanes Bearing Alkylthio, Arylthio, and Allylthio Groups on a-Carbon
Authors: Ojima Iwao , Kondo Kiyosi 
Published: July 2006

Abstract
α-Alkyl- and α-arylthioalkylcarbenes were thermally or photochemically generated from the corresponding ketones according to a modification of the Bamford-Stevens method. The carbenes thus generated were found to form labile episulfonium ylides, which then rearranged to vinyl sulfides. The episulfonium ylides were trapped with diethyl maleate and dimethyl fumarate. An α-allylthioalkylcarbene was generated by the photolysis of α-allylthioacetophenone tosylhydrazone in the presence of sodium methoxide at −70°C; this afforded α-allylthiostyrene exclusively. A smooth thio-Claisen rearrangement of the resulting α-allylthiostyrene was also observed. 3-Thiabicyclo[3.1.0]hexane was obtained when α-allylthioacetophenone tosylhydrazone was decomposed thermally at 150°C, or photochemically at 10°C in the presence of bases. The mechanisms of these new reactions are also discussed.
A Kinetic Study of the Mutarotation of d-Xylose by the Polarographic Method
Authors: Ikeda Tokuji , Senda Mitsugi 
Published: July 2006

Abstract
The polarographic behavior of d-xylose in several buffer solutions was investigated. The rate constants, k1, k2, k−1, and k−2, of the mutarotation of α-d-xylose, assumed as α\oversetk1\undersetk−1\ightleftharpoonsγ\oversetk2\undersetk−2\ightleftharpoonsβ, were calculated by the use of Wiesner’s method, but with a modified equation for the polarographic current. The overall mutarotation rate constant, ko, which is denned by ko=(k1k−2+k−1k2)⁄(k−1+k−2), was also determined. The rate constants, ko, k1, and k2, were analyzed as a linear function of the buffer concentration. It was revealed that the catalytic effects of the buffer salts were mainly due to their basic components for all the buffer salts investigated. The Bronsted plots of k1 and k2 for all the basic components gave straight lines with the same slope of 0.42. The rate constants for several amines deviated from the slope; this deviation was ascribed to the steric hindrance caused by their large molecular sizes.
The Nucleophilic Photo-substitution Reaction of Anthraquinone Derivatives. I. The Photo-amination of Sodium 1-Amino-4-bromoanthraquinone-2-sulfonate
Authors: Inoue Haruo , Hida Mitsuhiko , Tuong Tran Dinh , Murata Takashi 
Published: July 2006

Abstract
The photo-amination reaction of sodium 1-amino-4-bromoanthraquinone-2-sulfonate (I) was studied. The experimental results may be summarized as follows: 1) The photo-reaction is evoked by the absorption of light corresponding to the first absorption band (490 nm) of (I); 2) no dark reaction is observed: 3) aromatic amines appeared not to photo-react with (I); 4) the larger the polarity of the solvents used, the greater the yield of the product; 5) in the absence of oxygen, the photo-reaction was stopped. The possible reaction schemes were discussed.
The Palladium-catalyzed Arylation of 4-Chromanone Enol Esters. A New Synthesis of Isoflavanones
Authors: Saito Ryu-ichi , Izumi Taeko , Kasahara Akira 
Published: July 2006

Abstract
Heck’s reaction of 4-chromanone enol esters with arylpalladium compounds in acetic acid afforded isoflavanones in a high yield. The structural elucidation of these products was accomplished by spectral inspections.
One-Electron Reduction of Carbonium Ions. III. The Effect of Added Anions on the Rate of Reduction of the Tropylium Ion with Cr(II)
Authors: Okamoto Kunio , Komatsu Koichi , Tsukada Susumu , Murai Osamu 
Published: July 2006

Abstract
The one-electron reduction of tropylium fluoroborate with Cr(II) was carried out in aqueous solution containing various anions (Cl−, Br−, SO42−, HSO4−, BF4− and ClO4−) which were added as proton acids or as sodium salts, and the reaction rate at 25°C was measured by the use of the flow method. It was found that Cl−, Br−, and SO42− exhibit the characteristic rate-accelerating effect, whereas BF4− and ClO4− show a slight rate-retarding effect. From the extrapolation of the anion concentration to zero, it was indicated that this reaction can proceed even in the absence of added anions. From these findings, together with the results of chemical and spectrophotometrical analyses of the Cr(III) species, it was concluded that the reduction of the tropylium ion with Cr(II) proceeds through an electron-transfer step where the anion (Cl−, Br−, or SO42−) or the water molecule acts as a weakly interacting electron-transfer bridge. This mechanism is essentially analogous to the “inner-sphere mechanism” known in the field of inorganic metal complex chemistry.
A Study on the Kinetics and Mechanism of the Oxidation of Carbon Monoxide over Zinc Oxide
Authors: Choi Jae Shi , Kim Bo Won 
Published: July 2006

Abstract
A kinetic study on the oxidation reaction of carbon monoxide has been carried out between 260 and 350°C by means of the static method using n-type ZnO semiconductor as a catalyst under various oxygen and carbon monoxide pressure. The order of reaction between 260 and 320°C was found to be 1.5, with dPCO2⁄dt=kPCO·PO21⁄2. The Roginsky-Zeldovitsch equation, dPCO2⁄dt=ke-ap, fits well at 350°C. The mechanism of the reaction can be explained by the n-type character of ZnO.
The Electron-scavenging Process in 3-Methylhexane Glass at 77 K Studied by ESR
Authors: Oka Koichi , Yamazaki Hideo , Shida Shoji 
Published: July 2006

Abstract
The effect of various additives, i.e., nitrous oxide, sulfur hexafluoride, methyl chloride, and sulfur dioxide, on the yield of the trapped electrons produced in the γ-irradiated 3-methylhexane (3MHX) glass at 77 K have been investigated by the ESR technique. The yields of the trapped electrons were reduced by the addition of all the solutes examined; the efficiency of electron scavenging was found to be in the order of SF6&gt;CH3Cl&gt;N2O&gt;SO2. The concentration dependence of the electron scavengers showed that the efficiency of the electron scavenging in the glassy state had values intermediate between those in the gas and liquid phases. The high efficiency observed in the glassy state suggests that the non-solvated electrons before being trapped move about rapidly in the glassy matrix as the form of quasi-free electrons. The ESR-power saturation of the trapped electrons was considerably reduced by the addition of N2O; a possible mechanism of the relaxation of the ESR is proposed.
Metal Complexes Containing Six-membered Chelate Rings. III. Preparation and Structure of Mono- and Bis(2,4-Pentanediamine)cobalt(III) Complexes Containing Acetylacetonate or Oxalate Ion
Authors: Mizukami Fujio , Ito Haruko , Fujita Junnosuke , Saito Kazuo 
Published: July 2006

Abstract
New cobalt(III) complexes [Co(acac)2(2,4-ptn)]+, [Co(acac)(2,4-ptn)2]2+ and [Co(ox)(2,4-ptn)2]+ have been synthesized, resolved into optical isomers and their structures determined; 2,4-ptn=optically active (RR and SS) and meso (RS) 2,4-pentanediamine, acac=acetylacetonate ion, ox=oxalate ion. The patterns of circular dichroism spectra of these complexes in the first absorption band region are very similar to those of the corresponding α-diamine cobalt(III) complexes.
Heterocyclic Azomethine Compounds and Their Reduction Products as Analytical Reagents. I. Syntheses and Acid Dissociation Constants of Picolinaldehyde 2-Hydroxyanil and Its Derivatives and Their Reactions with Metal Ions
Authors: Otomo Makoto , Kodama Kazunobu 
Published: July 2006

Abstract
Picolinaldehyde 2-hydroxyanil and its methyl, chloro and nitro derivatives at the 5-position of benzene nucleus were synthesized for the purpose of investigating their applicability as an analytical reagent. The acid dissociation constants were determined by means of potentiometric titration in aqueous dioxane of various concentrations. It was found that the basicity of donor atoms of the parent compound increases with the introduction of a methyl group and decreases with that of a chloro or nitro group. The three compounds other than the nitro derivative are light-colored and react with many divalent metal ions in slightly basic media to form strongly colored chelates, which can be extracted into organic solvents such as partially halogenated hydrocarbons. The distribution coefficients of the three compounds between chloroform and water were also determined spectrophotometrically, that of the chloro derivative being the largest.
The Synthesis and The Configuration of 3-Aminotetrahydrothiophene-3-carboxylic Acids
Authors: Hatanaka Minoru , Ishimaru Toshiyasu 
Published: July 2006

Abstract
Several monomethylsubstituted 3-aminotetrahydrothiophene-3-carboxylic acids have been synthesized from the corresponding 3-ketotetrahydrothiophenes by the Strecker and the Bucherer-Bergs syntheses. In each case, the former synthesis leads to one stereoisomer, and the latter, to the opposite stereoisomer. The configurations of 3-amino-2-methyltetrahydrothiophene-3-carboxylic acids have been determined by a study of the NMR spectra; the others have been estimated on the basis of these results. The configurations do not contradict those first assigned to the alkyl substituted 1-amino-1-cyclohexanecarboxylic acids.
Kinetic Studies of Fast Reactions in Aqueous Solutions of Amylamine by Means of Ultrasonic Absorption
Authors: Nishikawa Sadakatsu , Yasunaga Tatsuya , Takahashi Kojiro 
Published: July 2006

Abstract
The ultrasonic absorptions in aqueous solutions of amylamine were measured in the frequency range of 3.5–220 MHz and in the concentration range of 0.01–3.06 M. Two kinds of relaxations were observed. One was attributed to the 5A–A5 reaction of non-ionized molecules of amylamine, and the rate constants were determined from the concentration dependence of the relaxation time at various temperatures. The thermodynamic parameters were determined from the temperature dependence of the rate and equilibrium constants. The other was attributed to hydrolysis, which is a diffusion-controlled reaction. In order to clarify the relation between the stability of the aggregate and the length of the hydrophobic group, the ultrasonic absorptions in aqueous solutions of propylamine were also measured. The excess absorption due to the association-dissociation reaction was not observed; only that due to hydrolysis was observed. It was deduced from this investigation that the aggregate formed by the hydrophobic bonding exists in the aqueous solutions of normal amines, the carbon numbers of which are more than 4.
Stereoselectivity in Mixed Tris-type Complexes of Cobalt(III) with l-Proline and l- or d-Aspartic Acid
Authors: Matsuda Toshitsugu , Shibata Muraji 
Published: July 2006

Abstract
Mixed complexes with l-proline and l- or d-aspartic acid, [Co(l-pro)3−n(l-(or d-)asp)n]n− (n=1,2), have been prepared and separated into a number of stereoisomers by means of ion-exchange chromatography. The structures of the isomers have been characterized by various spectral data. As to the [Co(L-pro)(d-asp)2]2− and [Co(l-pro)2(d-asp)]− complexes, all of three possible mer-isomers have been isolated in their Δ-forms. The formation ratios among the isomeric species in the reaction system have been estimated spectrophotometrically. Marked differences in stereoselectivity have been found between the l-aspartato complexes and the corresponding d-aspartato complexes. These selectivities have been qualitatively explained in terms of the interaction between the dangling β-carboxylate group in a chelated aspartate ion and the adjacent ligand.
A-Substituted 5β-Steroids. V. Syntheses and Some Reactions of 1-Oxygenated 5β-Cholestanes
Authors: Satoh J Yasuo , Misawa Katsumi , Takahashi T Tomoyoshi , Hirose Masakatsu , Horiuchi C Akira , Tsujii Shin-ichiro , Hagitani Akira 
Published: July 2006

Abstract
1-Oxygenated 5β-cholestanes were synthesized in good yield from 3-oxygenated 5β-cholestane through 5β-cholest-1-en-3-one. The reaction of 1β,2β-epoxy-5β-cholestan-3-one with hydrogen halide occurs with a normal ring cleavage resulting in the formation of 2-halo-5β-cholest-1-en-3-one. The reaction of 1β-hydroxy-5β-cholest-2-ene with chromium trioxide gave the allylic rearrangement product, 5β-cholest-1-en-3-one. The oxidative acetylation and bromination of 5β-cholestan-1-one is described.
The Carbonylation of Alcohols Catalyzed by Cu(I) Carbonyl
Authors: Souma Yoshie , Sano Hiroshi 
Published: July 2006

Abstract
In conc. H2SO4 containing the Cu(I) compound, alcohols react with carbon monoxide at room temperature and atmospheric pressure to produce tert-carboxylic acids in high yields. Primary carboxylic acid is not formed. It is assumed that the unstable Cu(I) tricarbonyl ion, Cu(CO)3+, is transiently formed in conc. H2SO4. An amount of the Cu(I) compound as small as 0.2 mol/1 is sufficient. The catalyst is effective at H2SO4 concentrations above 80%. The reaction rate decreases with a decrease in the H2SO4 concentration. At H2SO4 concentrations of less than 80%, no carboxylic acids are obtained.
Charge-transfer and Proton-transfer in the Formation of Molecular Complexes. VII. Complex Isomerism in Several Anilinium Alkyl-substitiited Picrates
Authors: Inoue Nobuaki , Matsunaga Yoshio 
Published: July 2006

Abstract
o-Chloroanilinium and o-bromoanilinium methylpicrates are obtainable not only as yellow-colored salts, but also as unstable, monotropic reddish-orange forms. Spectroscopic studies have revealed that the latter are charge-transfer complexes composed of the aniline molecule acting as an electron-donor and the acid molecule acting as an acceptor. Similar monotropic forms have been found in combinations of dimethylpicric acid with o-iodo-aniline, o-bromoaniline, and N,N-dimethylamino-p-benzaldehyde.
Small-angle Electron Scattering by Gases. CS2 and CCl4
Authors: Nagashima Makoto , Konaka Shigehiro , Iijima Takao , Kimura Masao 
Published: July 2006

Abstract
The small-angle scattering intensity of 40 keV electrons by CS2 and CCl4 molecules has been measured by the use of a counting unit. The experimental intensities have been compared with the theoretical values for the independent-atom-model, and an analysis of the comparison has shown the consistency of the present results with Tavard’s energy relation. The difference intensity, Δσ(s), of CCl4 has shown oscillatory behavior resulting from the distortion of charge distribution due to chemical-bond formation.
Radiotracer Studies on Adsorption of Surface Active Substance at Aqueous Surface. V. Effects of Additives on the Adsorption of Tritiated Nonionic Surfactant
Authors: Tajima Kazuo , Iwahashi Makio 
Published: July 2006

Abstract
The effects of additives on the adsorption of tritiated hexaoxyethylene dodecyl monoether (TD(EO)6) at the air-solution interfaces have been determined at 30 °C. The salting-out effect has been found to follow the Hofmeister series for the sodium salts of various anions, whereas a constant amount has been found for the adsorption increase due to the addition of various chlorides varying with the type of cation. The salting-in effect is observed for denaturants such as urea, urea nitrate and guanidine nitrate, but not for di- and tri-ethylene glycols.
Electroluminescence in Pentacene Doped Anthracene Crystals
Authors: Wakayama Nobuko I , Wakayama Nobuyuki , Williams D F 
Published: July 2006

Abstract
The recombination radiation spectrum and its transient behavior were measured on a pentacene doped anthracene crystal. The recombination radiation spectrum was more sensitive to chemical or physical impurities than optically sensitized fluorescence spectrum. The intensity of both anthracene and pentacene emission was approximately proportional to the current. Anthracene or pentacene emission was found to consist of three components differing by their decay times; component 1 (decay time &lt;10−5s), components 2,3 (decay times in the millisecond region, τ2&lt;τ3). The component 1 was due to singlet excitons generated directly by carrier recombination. The component 2, the decay time of which was 2–3 ms, was due to triplet exciton annihilation, for its decay time was not affected by a reverse bias voltage and was equal to one half of the observed phosphorescence lifetime. The component 3, which was removed by a reverse bias voltage, was due to detrapped-trapped carrier recombination. Pentacene chemical impurity works as carrier traps or tirplet exciton traps. Anthracene lattice defects work as carrier traps. The SCLC measurement showed the existence of an electron discrete trap introduced by pentacene and electron and hole exponential traps. The present experimental results showed het importance of traps in the recombination process in a mixed crystal.
Vibrational Spectra and Molecular Conformations of Dialkyl Disulfides
Authors: Sugeta Hiromu , Go Akikatsu , Miyazawa Tatsuo 
Published: July 2006

Abstract
The infrared and Raman spectra of several dialkyl disulfides were measured and their conformations were discussed in relation with the characteristic S–S and C–S stretching vibrations. The infrared spectra in the solid state and the temperature dependence of Raman spectra were measured for ethyl methyl disulfide and diethyl disulfide. For ethyl methyl disulfide, the gauche-gauche isomer was more stable than the trans-gauche isomer by about 0.9 kcal/mol while for diethyl disulfide the gauche-gauche-gauche isomer was more stable than the trans-gauche-gauche isomer by about 0.6 kcal/mol in the liquid state. Only the gauche-gauche form for ethyl methyl disulfide and only the gauche-gauche-gauche form for diethyl disulfide were observed in the solid state.
The Isomerism of Metal Complexes Containing Multidentate Ligands. IV. The Cobalt(III) Complex of Linear Pentaethylenehexamine
Authors: Yoshikawa Yuzo , Yamasaki Kazuo 
Published: July 2006

Abstract
The cobalt(III) complex incorporating sexidentate linear pentaethylenehexamine(1,14-diamino-3,6,9,12-tetraazatetradecane) as the ligand was prepared by the reaction of the ligand with [CoBr(NH3)5]Br2 at room temperature in the presence of active charcoal. The resulting solution was subjected to column chromatography on SP-Sephadex, geometrical and optical isomers with four different configurations were then separated and characterized by their electronic and infrared absorption, circular dichroism, and PMR spectra. They have the chemical composition of [Co(C10H28N6)]Cl3·nH2O, n being 1.5–3.
The Photolysis of 3,3-Pentamethyleneoxaziridine
Authors: Kobayashi Yoshinari 
Published: July 2006

Abstract
The ultraviolet irradiation of 3,3-pentamethyleneoxaziridine (1) gave two classes of photo-products: (a) cyclohexanol and n-capronamide, the formation of which proceeds preferentially through the excited triplet state of 1, and (b) ε-caprolactam, dicyclohexylideneazine, and cyclohexanone, which are mainly furnished via the singlet state of 1. The correlation of the selectivity of (a)-class products with the triplet-state energy of the quenchers used made it possible to estimate that the lowest triplet energy of 1 was approximately 60 kcal/mol. The sensitized photolysis of 1 using sensitizers, the triplet-state energy of which was more than nearly 60 kcal/mol, gave n-capronamide predominantly. The photolytic decomposition rate of 1 was compared with those of 2-methyl-3,3-tetramethyleneoxaziridine (2), 2-methyl-3,3-pentamethyleneoxaziridine (3), and cyclohexanone oxime. The mechanism of the photolysis of 1, including homolytic N–O bond rupture, was also discussed.
The Viscosities of Aqueous Sodium Alkylsulfate and Alkyltrimethylammonium Bromide Solutions
Authors: Tanaka Mitsuru , Kaneshina Shoji , Nishimoto Wataru , Takabatake Hiroyuki 
Published: July 2006

Abstract
The viscosities of aqueous solutions of sodium alkylsulfate and alkyltrimethylammonium bromide have been measured at various temperatures from 5 to 55°C. The viscosity data have been interpreted in terms of the Jones-Dole equation, and the viscosity B coefficients for the alkylsulfate and alkyltrimethylammonium ions at various temperatures have been calculated. The B values for these ions are all positive; they decrease with an increase in the temperature and increase linearly with an increase in the alkyl-chain length. The increment of B is found to be 0.076/–CH2– at 25°C. The energy and the entropy of activation for the viscous flow at 25°C have been calculated for these ions; they increase with an increase in the alkyl-chain length. This behavior of the B coefficient, and the energy and the entropy of activation for the viscous flow may be interpreted by saying that the longer-chain ions promote the hydrogen-bond structure of water around the hydrocarbon chain of these ions, while shorter-chain ions, e.g., ethylsulfate and ethyltrimethylammonium ions, behave instead as structure breakers because of the predominance of the disordering effect on the water around the ionic head. The viscosities of micellar solutions have also been measured. The volume of micelles as a hydrodynamic moving unit in solution has been estimated.
The Primary Photochemical Process of Isoquinoline N-Oxide in Hydroxylic Solvents
Authors: Ono Isao , Hata Norisuke 
Published: July 2006

Abstract
In order to deduce the nature of the reactive state of the photochemical isomerization of isoquinoline N-oxide in methanol or water, investigations by means of steady-light irradiation and flash spectroscopy were carried out under various conditions. Transient absorptions were observed in the spectral region between 360 nm and 600 nm; they were identified as being due to a T–T transition of isoquinoline N-oxide. Experiments on both the measurements of the quantum yields and the decay kinetics of the transient species under different conditions revealed that the excited singlet state of isoquinoline N-oxide was responsible for the isomerization. The photochemical behavior in aqueous solutions at various pH values was also examined; consequently, the photochemical isomerization was found to be independent of the hydrogen ions, although it did not occur in a strongly acidic solution (pH&lt;3.0) because of the formation of the protonated N-oxide. The biacetyl-photosensitization for isoquinoline N-oxide led to the dissociation of the N–O bond instead of to isomerization.
Polarographic Studies of the Anodic Oxidation of Mercury. II. The Anodic Adsorption Wave of Ethylamine in N,N-Dimethylformamide
Authors: Matsui Yoshihisa , Date Yoshio 
Published: July 2006

Abstract
Ethylamine at concentrations lower than 0.5 him in N,N-dimethylformamide gives a diffusion-controlled anodic wave due to the reversible oxidation of the mercury to a 1:2 complex of mercury(II) with the amine. At higher concentrations, another anodic wave appears at a potential less positive than the main wave; this has been attributed to the adsorption of the oxidation product on the mercury electrode. The adsorption prewave was analyzed on the basis of Brdicka’s theory, in which the Langmurian adsorption was assumed. It was shown that the nature of the prewave can be well interpreted on the additional assumption that the adsorption coefficient of the adsorbed complex decreases exponentially as the electrode potential becomes more positive.