bluuebunny/crossref_metadata_2025 huggingface dataset:
Role of Chlorine in β-FeOOH on Its Thermal Change and Reactivity to Sulfur Dioxide
Authors: Ishikawa Tatsuo , Inouye Katsuya
Published: July 2006

The state of Cl in β-ferric oxide hydroxide (β-FeOOH) was examined by X-ray diffraction, IR absorption, chemical analysis, DTA, and TGA. The adsorption of SO2 was determined as a measure of the surface activity. No influence of Cl contained in the crystal appeared in the X-ray diffraction patterns and surface area. The absorption bands at 640 and 840 cm−1 in IR spectra showing the deformation vibration of OH group diminished with the decrease of Cl content. It was shown that the path for β-FeOOH to transform into α-Fe2O3 by heating differentiates from the sample including more than 11.5% Cl/Fe to one including less than 11.5% Cl/Fe. This critical Cl content is equal to the amount of Cl when Cl fills up the characteristic tunnels existing in the β-FeOOH crystal. Cl in β-FeOOH interferes both its transformation into α-Fe2O3 and the recrystallization of resultant α-Fe2O3. These effects were explained by the stabilization of the β-FeOOH structure by Cl in tunnels and the bonding between Cl and Fe. The amount of chemisorbed SO2 was lowered by Cl which was adsorbed on outer surfaces.
Lanthanide-Induced Nuclear Magnetic Resonance Shifts and Molecular Structure of l-Azetidine-2-Carboxylic Acid. II. Determination of Molecular Conformation
Authors: Inagaki Fuyuhiko , Takahashi Seizo , Tasumi Mitsuo , Miyazawa Tatsuo
Published: July 2006

Lanthanide-induced shifts (LIS) in 1H NMR spectra of l-azetidine-2-carboxylic acid were observed in D2O solution using Pr(III), Nd(III), and Eu(III) nitrates as shift reagents. By taking the LIS of one of the protons as reference, the shift ratios for the other four protons were calculated. The shifts ratio obtained were nearly constant for the three lanthanide ions, except for that with respect to the α proton which is located closest to the lanthanide ion. This indicates that the contribution of the contact shift is appreciable only for the observed LIS of the α proton and is negligible for the LIS’s of the β and γ protons. The constancy of shift ratios assures, in addition, that the magnetic tensor is axially symmetric. Therefore, the LIS’s of the β and γ protons may be used for the structure determination. For the β and γ protons, the ratios of LIS’s intrinsic to the lanthanide-substrate 1:1 complex were corrected for the contribution of diamagnetic shifts due to complex formation which were estimated by the use of La(III) nitrate. The line broadening induced by Gd(III) was also observed. The structure analysis based on these data shows that the four-membered ring of l-azetidine-2-carboxylic acid is puckered with the dihedral angle of 25° and the carboxylate is in the equatorial position.
Metal(II)-Ion Promoted Hydrolysis of Glycylglycine
Authors: Nakata Toshio , Tasumi Mitsuo , Miyazawa Tatsuo
Published: July 2006

The hydrolysis of glycylglycine was studied in the presence of Cu(II) and Zn(II) at various pH values between 3.4 and 6.3. Glycine produced by the hydrolysis and remaining glycylglycine were trimethylsilylated and their relative quantities were determined by gas-liquid chromatography. The reaction is promoted by both metal ions. In the presence of Cu(II) the pH-rate profile has a maximum at pH ca. 4.4, whereas in the presence of Zn(II) the rate increases as pH becomes higher. These kinetic results are discussed in terms of the structures of metal(II)-glycylglycine complexes in aqueous solution.
The Thermal Changes in Gels of the SiO2–Al2O3–In2O3–H2O System
Authors: Kasai Mitsuhiro , Kudo Yoshiyuki , Hamada Shuichi
Published: July 2006

The synthesized coprecipitated gels in the SiO2–Al2O3-In2O3n-π*–H2O system showed an allophane-like pattern in the DTA except for the indium-rich gels. The exothermic peak temperature in the DTA was lowered from 980 to 940 °C with an increase in the indium content, while that on mixed gels was scarcely lowered at all. A new small exothermic peak around 880 °C in the DTA was observed in the coprecipitated gels with more than 11.93 wt% of In2O3; it was considered to be due to the structural change in the gels which arose from the formation of the indium (III) oxide. The firing products of the coprecipitated gels were identified as mullite, indium (III) oxide, and indium (III) silicate. The mullite formed in the coprecipitated gels included indium ions at 900 °C, accompanied by an increase in its unit cell volume, while the indium ions were almost entirely removed from the mullite lattice at 1200 °C.
The Structures and Thermal Behaviors of Bivalent Metal Succinates in the Solid State
Authors: Nagase Kenzo , Yokobayashi Hiroko , Muraishi Kazuo , Sone Kozo
Published: July 2006

The relations between the structures and thermal behaviors of the succinates of Mg(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) were studied. In the case of the copper salt, the dehydration of its dihydrate began easily at room temperature. However, the tetrahydrates of Mg, Co, and Ni held their waters more tightly, and changed from crystalline to amorphous state in the course of dehydration which began at 50–60 °C. The anhydrous salts of Mg and Co recrystallized at 306 and 272 °C, respectively, with a sharp exotherm on each DTA curve. The cobalt salt showed stepwise color changes, pink \xrightarrowdehydration bluish violet \xrightarrowrecrystalllzation pink. PbC4H4O4 exhibited a phase transition from tetragonal to cubic at 160 °C with ΔH=2.5 kJ/mol and ΔS=5.9 J/deg·mol. The phase transition was reversible and seems to be accompanied with a conformational change of the succinate ion.
The Radical Formation of Polyethylene by Tesla Discharge
Authors: Yokohata Akira , Harakon Katsuyuki , Takimoto Kazuto , Tsuda Satoru
Published: July 2006

The ESR spectra of polyethylene discharged by a Tesla coil in an atmosphere of various gases were observed. An alkyl radical showing a six-line spectrum was formed in the Tesla discharge at 77 K, whereas a polyenyl radical was mainly produced by the discharge with an increase in the duration time; these facts showed that the effects of the Tesla discharge were similar to the γ-irradiation up to a high dose.
Group Interactions in Polyelectrolytes. IX. The Amination Kinetics of Chloromethylated Polystyrene in Binary Mixed Solvents
Authors: Kawabe Hiroshi
Published: July 2006

All the aminations of chloromethylated polystyrene (CMPS) and benzyl chloride with i- and s-butylamine in N,N-dimethylformamide (DMF), in dioxane, and in DMF-dioxane mixtures conformed to the ordinary second-order kinetics. The activation parameters in the pure solvents revealed that the much higher amination rate in DMF than in dioxane was due to both the lower value of ΔH\eweq and the higher value of ΔS\eweq in DMF. The rate of amination in DMF–dioxane was investigated as a function of the composition of the mixed solvent. The observed rate constants in DMF–dioxane mixtures fell substantially on the curves calculated on the basis of Kondo and Tokura’s theory concerning reaction rates in binary mixed solvents. It is suggested in this paper that the higher rate of amination in DMF is due to the strong solvation of the activation complex in DMF to form an addition product, and that it is also due to the relative increase in the configurational entropy of the reaction system at the transition state from dioxane to DMF.
A Study on Anode Effect in KF–2HF System. I. ESCA Spectra of Carbon and Graphite Anode Surfaces
Authors: Imoto Hiroki , Nakajima Tsuyoshi , Watanabe Nobuatsu
Published: July 2006

The ESCA spectra of carbon and graphite electrodes, used as an anode in the molten KF–2HF system at 100 °C, indicated that a (CF)n film was formed on the surface of the electrodes. This may give strong support to the assumption that the anode effect in molten KF–2HF is caused by the formation of (CF)n on the carbon and graphite electrodes.
A Semi-empirical Calculation of the Substituent Effect on the 1H Chemical Shift of Benzene
Authors: Niwa Jun
Published: July 2006

The applicability of a semi-empirical expression for obtaining the relative 1H chemical shifts in substituted aromatic side-chains, which was presented in the preceeding paper (J. Niwa, This Bulletin, 48, 118 (1975)), has been examined for ring protons of monosubstituted benzenes.
An ESR Study of Diborane Anion Radicals in the Adsorbed State
Authors: Sogabe Kunihisa , Hasegawa Akinori , Miura Masaji
Published: July 2006

The ESR spectra were examined for diborane anion radicals, B2H6−, formed when diborane adsorbed on several kinds of adsorbents was irradiated with γ-rays at 77 K or diborane adsorbed at 77 K on adsorbents pre-irradiated with γ-rays at 77 K. The radicals in the adsorbed state were compared with those in an argon matrix, previously reported.
The Back-extraction Behavior of Chelate Compounds. II. Some Aspects of the Secondary Dithizonate of Copper
Authors: Honjo Takaharu , Unemoto Toshiyuki , Kiba Toshiyasu
Published: July 2006

The behavior of secondary copper dithizonate in carbon tetrachloride, chloroform, 1,2-dichloroethane, benzene, monochlorobenzene, o-dichlorobenzene, and nitrobenzene has been investigated by a kinetic study of the back-extraction of the copper ion in order to clarify the extraction mechanism and to ascertain the chemical form of this chelate.
The Reaction of Acetylenecarboxylic Acid with Amines. XVII. The Addition of Dialkyl Acetylenedicarboxylates to Several Carcinogens
Authors: Iwanami Yasuo
Published: July 2006

Hazardous carcinogens, α-naphthylamine (I), benzidine (II), 2′,3-dimethyl-4-aminoazobenzene (o-aminoazotoluene) (III), 2-amino-l-naphthol (IV), and 4-methylaminoazobenzene (V), easily reacted with esters of acetylenedicarboxylic acid (VI and VII) to give addition products, whose carcinogenicity could possibly be changed.
The Photolysis of α-Haloketones. II. The Intramolecular Reactions of 9-α-Bromopropionylanthracene
Authors: Matsumoto Tamotsu , Sato Masanori , Hirayama Satoshi
Published: July 2006

The main photolysis products of 9-α-bromopropionylanthracene were identified as 2-methyl-1-aceanthrenone and 9-vinylanthryl ketone. The yield of 9-bromoanthracene was very small. A significant solvent and temperature dependence was noted on the yields of these products. The photolysis at −196 °C resulted in the formation of almost 100% of 9-vinylanthryl ketone.
The Catalytic Hydrogenolysis of Alkyl-substituted Aziridines
Authors: Sugi Yoshihiro , Nagata Mitsuru , Mitsui Sekio
Published: July 2006

Alkyl-substituted aziridines were hydrogenolysed, mainly at the less-substituted C–N bonds over Raney Ni, to yield β-amines. This hydrogenolysis occurred with the retention of the configuration. The differences in behavior between aziridines and oxiranes may be ascribed to the difference in polarisation between C–N and C–O bonds in the transition state of the hydrogenolysis.
The Reaction of N-Hydroxylamino Compounds with Triphenylphosphine and CCl4
Authors: Ohashi Takehisa , Appel Rolf
Published: July 2006

In the reaction of triphenylphosphine with N-p-toluene-N-hydroxylamine and CCl4, p-azotoluene and p-azoxytoluene were formed as the main products. On the other hand, in the reaction using N-p-toluenesulfonyl-N-hydroxylamine, sulfonyliminophosphorane was obtained.
Photochemical Reactions of 3,3-Bis(dialkylamino)acrylophenones and 3-Dibenzylaminopropiolophenone
Authors: Aoyama Hiromu , Hasegawa Tadashi , Nishio Takehiko , Omote Yoshimori
Published: July 2006

The photolysis of 3,3-bis(dialkylamino)acrylophenones 1a, b, and c gave the 3a, b, and c pyrroles respectively. 3-Dibenzylaminopropiolophenone (2) reacted with water upon irradiation to give N,N-dibenzylbenzoylacetamide (5), whereas the addition of acetic acid to 2 proceeded without irradiation.
Lactone Carboxylic Acids. IX. Base-Catalyzed Rearrangement of Ethyl α-Hydroxyaminoaconate Leading to the Formation of Isoxazolines
Authors: Torii Sigeru , Ukida Masasi , Tanaka Hideo
Published: July 2006

The syntheses of 4-ethoxycarbonyl-3-methoxycarbonyl-5,5-pentamethylene-Δ2-isoxazoline (2b) and its 4-hydroxy and 4-acetoxy derivatives (3a and 3b) by the base-catalyzed rearrangement of ethyl γ,γ-pentamethylene-α-hydroxyaminoaconate (1) were described.
A New Synthesis of Pyrimido[4,5-e][1,2,4]triazines from 5,5-Dibromopyrimidines
Authors: Sugimoto Takashi , Matsuura Sadao
Published: July 2006

A new method for the synthesis of pyrimido-[4,5-e][1,2,4]triazines from 5,5-dibromopyrimidines was studied. Condensation of dibromopyrimidines (1a, b) with aminoguanidine or its analogues gave the 6,8-dioxo series (5) of the pyrimidotriazine, and aminodibromopyrimidines (2a, b) gave the 6-amino-8-oxo series (6).
The Dipole Moments and Conformations of cis-2-Styrylfurans and cis-2-Styrylthiophenes
Authors: Gruttadauria Salvatore , Pappalardo Giuseppe C , Scarlata Giuseppe , Torre Michele
Published: July 2006

Electric dipole moments at 25 °C in benzene have been measured for cis-2-styrylfurans and -styrylthiophenes which are chloro- and nitro-substituted in 2′-, 3′-, 4′-position. Results of dipole moment analyses in conjunction with UV spectroscopic data have been discussed in terms of preferred conformations for these compounds.
The Effect of the Hydrostatic Pressure on the Hydrogen-bond Formation between Phenol and Dioxane in Hexane
Authors: Suzuki Keizo , Tsuchiya Masao
Published: July 2006

The near-UV absorption spectra of phenol-dioxane in n-hexane were observed under hydrostatic pressures up to 1480 atm and at 30 °C. With an increase in the pressure, the spectra shift toward the longer wavelength side and the amount of the hydrogen-bonded phenol increases. The equilibrium constant for (Remark: Graphics omitted.) was obtained, and the volume change accompanying the hydrogen-bond formation was estimated to be −3.0–−3.4 cm3/mol.
Enthalpies of Combustion of Organic Compounds. I. 8-Quinolinol
Authors: Sakiyama Minoru , Nakano Toshiro , Seki Syûzô
Published: July 2006

A rotating-oxygen-combustion bomb calorimeter equipped with a platinum lined bomb has been constructed and calibrated. The enthalpy of combustion of 8-quinolinol(c) was determined. Thermodynamic quantities obtained are as follows: ΔEc°=−4458.90±1.60, ΔHc°=−4460.76±1.60 and ΔHf°=−81.24±2.00 kJ mol−1 for the crystalline state and ΔHf°=27.6±2.6 kJ mol−1 for the gaseous state.
Isotropic Rayleigh Light Scattering in Two-component Systems. The Interdependence of the Concentration and the Density Scattering
Authors: Shiokawa Yoshinobu , Suzuki Shin
Published: July 2006

The isotropic Rayleigh ratios in two-component systems are discussed in terms of the fluctuation of the thermodynamic quantities. It is found that the isotropic Rayleigh ratio, Ris, is the sum of the concentration scattering, Rc, due to fluctuation of the concentration and the so-called density scattering, Rd:

R_is=R_c+R_d

Thus, the cross-term of the concentration scattering and the density scattering, suggested by Bullough, is not included in the above expression. Our conclusion is confirmed by the determination of the molecular weight of sucrose.
Apparent Viscosities of Ferric Oxide–Water Suspensions
Authors: Moriyama Noboru
Published: July 2006

The effects of various types of anionic surfactants and inorganic phosphates on the apparent viscosities of ferric oxide–water suspensions of high pigment concentrations are examined. The additions of surfactants or inorganic phosphates to the suspensions cause depressions in their apparent viscosities from values of more than 10000 centipoise (cP) to about 10 cP. The concentration of the surfactants or the inorganic phosphates required to depress the apparent viscosity, which is designated as C0, is highly dependent upon the alkyl-chain length of the 1-1-type surfactants, the degree of the polymerization of the surfactants of the type of the vinyl copolymers and the degree of the condensation of the surfactants of the type of the formalin condensates or inorganic phosphates. With the 1-1-type surfactants, the values of the C0 decrease with the increases in the alkyl-chain length, and the surfactants with much shorter alkyl-chain lengths, such as Na octyl sulfate, linear-chain Na hexylbenzene sulfo-nate, and Na butyl-naphthalene sulfonate, have no marked viscosity depression effects. With the formalin condensates and the inorganic phosphates, the values of C0 decrease with the degree of condensation. With the vinyl copolymers, the C0 show smallest values at the appropriate degree of polymerization, e.g., about 10–40 for the Na salt of polyacrylic acid. Both the absolute value of the zeta potential and the amount of adsorption increase remarkably in the concentration regions showing marked viscosity depressions. The viscosity depressions of the suspensions upon the additions of the surfactants or inorganic phosphates can be qualitatively explained by taking into account the contributions of the zeta potential values and concentrations to the dispersion-coagulation of the pigment particles.
The Adsorption of the Ampholytic Surfactant and the Anionic Surfactant at the Nitrogen–Solution Interface from the Mixed Aqueous Solution
Authors: Nakamura Akio
Published: July 2006

The amounts of adsorption of an ampholytic surfactant, N-dodecyl-β-alanine(NDA), and an anionic surfactant, sodium alkylsulfate(SAS), at nitrogen-solution interface from aqueous equimolar mixtures of them were measured directly by the radiotracer method, using tritiated and non-tritiated samples of NDA and 35S-labeled and non-labeled samples of SAS: sodium tetradecylsulfate(STS), sodium dodecylsulfate(SDS), and sodium decylsulfate(SDeS). The adsorption of both components of the mixed systems was observed at concentrations lower than those for the systems containing each component alone. A stronger adsorption of NDA than that of SAS was observed for all mixed systems. The overall area per alkyl chain at the maximum adsorption was about 26 Å2 for each system, showing the adsorbed layer to be in a highly condensed state. Electrophoresis measurements, together with surface tension measurements of NDA-SDS systems and the elemental analysis of the precipitates from concentrated NDA-SDS solutions, suggested the presence of a 1 : 1-complex formed between NDA and SDS. The Gibbs adsorption isotherm for the binary system was derived. The calculated amounts of adsorption agreed with the observed values. A linear relationship was found to hold between the logarithm of the constants of complex formation and the number of carbon atoms of SAS. A free energy of the complex formation of −0.50 kcal per mole of the methylene group was found.
The Intramolecular Dynamic Behavior of Tetraaryl Allyl Radicals
Authors: Watanabe Kohji
Published: July 2006

The electron spin resonance (ESR) and the electron nuclear double resonance (ENDOR) spectra of tetraaryl allyl radicals have been observed. A comparison of the ENDOR spectra of α,α,γ,γ-tetraphenyl allyl, α,α-diphenyl-γ,γ-dianisyl allyl, and α,α,γ,γ-tetraanisyl allyl revealed that the four aryl groups are not equivalent, but are apparently to be classified into two types with different conformations in their molecular frameworks. The molecular orbital calculations on the basis of this model have shown a fairly good agreement with the observed spectra. The temperature dependence of the ENDOR spectra at −60∼−110 °C were analyzed, assuming mutually different twisting angles for the allyl skeleton. The activation energy of the torsional vibration of the allyl skeleton is estimated to be about 2.5 kcal/mol. The ESR spectra of α,α,γ,γ-tetraphenyl allyl and α,α-diphenyl-γ,γ-diphenylene allyl change drastically with the temperature at around +115°C and show a marked line-width alternation effect. It is concluded from the results that the torsional vibration becomes vigorous with an increase in the temperature and that the allyl skeleton begins to rotate internally at high temperatures. The activation energy of the internal rotation of the allyl skeleton has been estimated to be about 15∼20 kcal/mol. The temperature-dependent hyperfine splitting of the methine proton has also been explained by assuming a model of the internal rotation of the allyl skeleton.
CNDO/2 Calculations on the Configurations of the Ion-molecule Complexes. The NH4+–CH4, H3O+–CH4 and NH4+–H2 Systems
Authors: Tanaka Kazuyoshi , Yamabe Tokio , Kato Hiroshi , Fukui Kenichi
Published: July 2006

The optimized configurations of several ion-non polar molecule complexes (NH4+–CH4, H3O+–CH4 and NH4+–H2) have been discussed by the use of the CNDO/2 method. The results for NH4+–CH4 and H3O+–CH4 turn out to be quite different from those previously proposed by the calculations based on the classical electrostatic model. It may be demonstrated that these systems are stabilized by a kind of hydrogen bond where the charge transfer effect from a neutral molecule to a cation plays an important role, according to the configuration analysis.
The Effects of Anionic and Cationic Surfactants on the Ion Flotation of Cd2+
Authors: Kobayashi Koichi
Published: July 2006

The ion flotation of Cd2+ ions has been investigated from the surface chemical point of view in comparison with the case of Cu2+ ions reported previously. The effects of the change in the pH, the anionic and cationic surfactants, and bentonite on the flotation rate have also been studied. Sodium α-sulfolaurate proved to be one of the best surfactants among the anionic surfactants used for removing Cd2+ ions, showing as high as a 97% removal. About 97% of the Cd2+ ions could be floated in the region of pH 11.3 when a cationic surfactant was used with bentonite, regardless of the exact surfactant used. The addition of bentonite reduced the foam formation and liquid hold-up, resulting in effective bubble flotation. This behavior was as a whole similar to that of Cu2+ ions. However, in all the flotation systems tested, the flotation rate increased sharply at about pH 8, and the flotation rate vs. pH curve for Cd2+ shifted towards a more alkaline region than that for Cu2+, because of the stronger basic nature of the former. Also, the flotation rate of Cd2+ ions for the Cd2+-anionic surfactant systems attained a steady value after about 7 min, longer than the 2-min gas flow required in the case of Cu2+ ion flotation. The adjustment of the pH using ammonia gave a lower rate of flotation than in the case of flotation using sodium hydroxide.
Studies of the Removal of Cd2+ Ions by Adsorbing Particle Flotation
Authors: Kobayashi Koichi
Published: July 2006

The conditions for the removal of Cd2+ ions from an aqueous solution by adsorbing particle flotation using bentonite and a cationic surfactant has been investigated. It has been found that the most suitable method was to conduct notation in the region of the coagulation notation of bentonite. The addition of polyacrylamide (PAA) extended not only the region of coagulation flotation towards lower and higher hexadecyltrimethylammonium chloride (HTAG) concentrations tested, but also increased the flotation efficiency (expressed as the percentage of ions removed from the total solution). The selective flotation from an aqueous solution containing two kinds of metal ions was also investigated. Each metal ion could be floated from the solution with the pH of the metal hydroxide formation. By selecting proper conditions, it was possible to remove each metal ion separately from a mixed solution.
Effects of the Tension and Viscosity on the Rate of Growth of Black Soap Films
Authors: Yamanaka Teruko
Published: July 2006

The additional tension and the rate of growth of black films formed from aqueous solutions of polyoxyethylated nonionic surfactants and sodium dodecylsulfate, which contain inorganic electrolytes in high concentrations, were measured for the large vertical films drawn from these solutions. It was found that the rate of growth of black films was proportional to the additional tension in both systems. The reciprocal of the slope of each line was concluded to be a viscosity parameter, since the additional tension acted as the driving force for the growth of black films, and the viscosity parameter, as the resistance. The effect of added glycerol on the rate of growth of black films was compared with that of electrolytes for the films of nonionic surfactants. The former affected both the viscosity parameter and the additional tension, while the latter showed an effect on only the additional tension.
Dielectric Behavior of Water Molecules Adsorbed on Iron(III) Oxide Hydroxides
Authors: Kaneko Katsumi , Serizawa Mamoru , Ishikawa Tatsuo , Inouye Katsuya
Published: July 2006

The change in the dielectric constant of α-FeOOH, β-FeOOH, and γ-FeOOH with the amount of adsorbed water was examined at 30.0 °C in the frequency range 200 Hz–100 kHz for the purpose of clarifying the mechanism of water adsorption. The adsorption isotherms belong to the BET II type. The sample with the adsorbed water shows a particular dispersion of the dielectric constant with frequency in the low frequency range. The dispersion was ascribed to the transition between different orientational directions of the dipole moment of the adsorbed water. The change in the dielectric constant with the amount of adsorbed water for each iron(III) oxide hydroxide was interpreted in relation to the surface structure of predominant faces of crystals, in particular the number and position of hydroxyls on crystal surfaces. The following adsorption process was suggested below the monolayer adsorption coverage for each iron(III) oxide hydroxide. For α-FeOOH, water molecules are adsorbed on the (100) planes in three successive steps. For β-FeOOH, water molecules are primarily bound in the tunnels existing in the crystal along a direction parallel to the c-axis and then are adsorbed on the cracked tunnels exposing to the outer surface. For γ-FeOOH, water molecules are adsorbed on the (010) planes in two steps.
Theoretical Calculations of the Raman Intensities by the Vibronic Method
Authors: Shinoda Hiroyuki
Published: July 2006

The values of the transition moment of Raman scattering have been calculated according to the formula derived from the vibronic expansion approach. The calculations have been performed for the symmetry coordinates of several small molecules and for the normal vibrations of methane. The electronic wave functions were calculated by the CNDO/2-CI method. The calculated results are large in comparison with the experimental ones. The calculated Raman intensities for the symmetric stretching vibrations were almost all contributed by the term A in the vibronic expansion theory. From the calculated results for the normal vibrations of methane, it was found that the vibronic method used in this work leads to more appropriate values than those obtained from the polarizability theory which was used in the previous paper.
The Rapid Determination of Heavy Metals in Sediment by Means of X-ray Fluorescence Analysis Modification of the X-ray Intensity Using Scattered Radiation
Authors: Tanaka Hideki , Hashizume Genzo
Published: July 2006

The present method was developed as a way of modifying intensity using the mass-absorption coefficient of the matrix, which is itself obtained from the measurement of the intensity at an arbitrary scattered wavelength. This modification, derived from the simplified equation by the utilization of the known matrix composition, has been empirically demonstrated, and it has been applied to various river-sediment samples. Repeated analyses on copper and zinc in representative sediments were carried out, and the average (\barx) and the coefficient of the variation (c.v.) obtained by the present method and by the atomic-absorption method were compared. In the former method, \barx=1,550 μg/g, c.v.=4.25% on copper, \barx=4,400 μg/g, and c.v.=7.11% on zinc; in the latter method, \barx=1,500 μg/g, c.v.=9.87% on copper, \barx=4,330 μg/g, and c.v.=13.03% on zinc.
The Mechanism of Thermal Reactions in Apatites–Silica–Water Vapor Systems
Authors: Monma Hideki , Kanazawa Takafumi
Published: July 2006

The reactions of fluor-, hydroxy-, and chlorapatites with silica in the presence of water vapor have been studied under various conditions−i.e., various amounts of added silica, various temperatures (up to 1300°C), and various heating times and water-vapor pressures (0.6–760 mmHg). As the pressure increased, the decomposition rate of hydroxyapatite with silica decreased considerably. Fluorapatite and chlorapatite were found to be decomposed with silica after being partially defluorinated or dechlorinated. In the case of fluorapatite, no effect of silica addition was recognized under a low water-vapor pressure (0.6 mmHg). This effect was observed under a high water-vapor pressure (760 mmHg), accompanied by rapid increases in the fluorine volatility and the destruction rate of the apatite in their time-dependence plots. In the reaction using chlorapatite, a similar effect was found under both low and high pressures. The results for the defluorination and dechlorination could mostly be interpreted by assuming the following changes: (1) halogen-oxyapatite formation, (2) the substitution of hydroxyl ions for halogen ions, and (3) the decomposition of apatite with silica.
Preparation and Reaction of Some Di-tert-butylnitroxidopalladium(II) Complexes, PdX(But2NO)L (L=PPh3, AsPh3, P(OPh)3; X=C1, Br, I)
Authors: Okunaka Masaaki , Matsubayashi Gen-etsu , Tanaka Toshio
Published: July 2006

PdX(But2NO)L (L=PPh3, AsPh3, P(OPh)3; X=Cl, Br, I) was isolated by the reactions of [PdCl(But2NO)]2 with L and by the halogen exchange reactions of the chloro complexes with LiBr·H2O or NaI. PMR and IR spectra revealed that PdX(But2NO)(PPh3) and PdX(But2NO)(AsPh3) exist as only one geometrical isomer with the halogen atom trans to the oxygen atom of the nitroxide ligand, while two isomers of PdX(But2NO)[P(OPh)3] coexist in solution. The reaction of PdX(But2NO) (PPh3) (X=Cl, I) with triphenylphosphine was found to give Pd(PPh3)4 together with Pd X2(PPh3)2 and Bu2NO·. A similar reaction proceeded between PdCl(But2NO)[P(OPh)3] and triphenylphosphite to yield Pd[P(OPh)3]3, while a not well-defined complex [PdCl(AsPh3)2]n was obtained in the reaction of PdCl(But2NO)(AsPh3) with triphenylarsine.
On the Selectivity in the Catalytic Hydrogenation of Methylacetylene on Group VIII Metals
Authors: Yoshida Noritetsu , Hirota Kozo
Published: July 2006

The reaction of methylacetylene with hydrogen and deuterium was studied over five Group VIII metals (Pd, Pt, Rh, Ir, and Ru) at 25°C. Among these metals, palladium was the most selective for the propylene formation; the selectivity varied from metal to metal (Pd>Pt>Rh>(Ni)>Ru>Ir). A new result was obtained over ruthenium; the isomerization of methylacetylene to allene occurred simultaneously with the hydrogenation over only this metal. In the reaction with deuterium, the stereoselectivity of the metals was investigated on the products by analyzing them by the microwave spectroscopic and mass spectrometric methods. Only three hydrogen atoms were deuterated in the propylene produced over Ni, Pd, and Pt; in conformity with the above, the deuterated positions of propylene-d1 and -d2 were limited to three in the methylene and methylidyne groups. No such tendency was observed for Ir, Rh, and Ru, where the methyl hydrogens were also deuterated. The relative yield of the cis-1,2-d2 species, always the most abundant product, decreased in this order: Pd>Pt>Ir>Ru>(Ni)>Rh at 70% conversion. A reaction mechanism which explains the relative yields of isotopic isomers of deuteropropylenes except for the methyl-deuterated species was proposed, assuming an adsorbed radical as an intermediate. The calculated isomer distributions based on the scheme coincided well with those observed in the cases of Pd, Pt, and Ni, but not in those of Ir, Rh, and Ru.
Photoelectron Spectra of Substituted Naphthalenes
Authors: Utsunomiya Chikatoshi , Kobayashi Tsunetoshi , Nagakura Saburo
Published: July 2006

The photoelectron spectra (PES) of 1- and 2-substituted naphthalenes (naphthols, aminonaphthalenes, N,N-dimethylaminonaphthalenes, acetylnaphthalenes, and cyanonaphthalenes) were measured in the region from 6 to 20 eV. The observed PES were assigned with the aid of the CNDO/2 calculations and the substituent effect. The lower energy bands of the compounds with the electron-donating group were found to be due to the ionization from the orbitals caused by the interaction of the highest three occupied π orbitals of the naphtha ene ring with the nonbonding orbital of the substituent group. The second bands of the 1-substituted naphthalenes are commonly assigned to π orbitals almost completely localized on the naphthalene ring. The dimethylammo group of 1-dimethylaminonaphthalene was found to be twisted to a great extent from the ring plane.
The Reaction of Cycloalkanones with Copper(II) Halides. II. The Reaction of Cyclohexanones with Copper(II) Bromide
Authors: Nishizawa Kyoko , Satoh J Yasuo
Published: July 2006

The reaction of cyclohexanones with copper(II) bromide gave polybrominated cyclohexanediones in all cases except for the case of 3,5-dimethylcyclohexanone. Moreover, in this reaction, a pyrocatechol and a phenol derivative were obtained from 4-methyl- and 3,5-dimethylcyclohexanone respectively. The mechanism of this reaction was discussed.
NMR Studies of the Conformations of 3-Aryl-1,2,3-oxathiazolidine 2-Oxides
Authors: Yamada Fukiko , Nishiyama Tomihiro , Samukawa Hiroshi
Published: July 2006

Proton magnetic resonance spectroscopy has been used to investigate the conformations of a series of 3-aryl-1,2,3-oxathiazolidine 2-oxides. Their conformations were assigned on the basis of the vicinal coupling constants between four methylene protons at the C-4 and C-5 positions. The oxathiazolidine 2-oxides prefer twist-envelope forms, and their conformations vary with both the situation and the nature of the ring substituent. Postulated collision complexes based on the data of the observed solvent-shifts can also be explained in terms of the differences in the conformations.
A Study of the Kinetic Resolution of Dl-Propylene Oxide with Optically Active Co(I)(salen) Type Complexes
Authors: Aoi Haruhiko , Ishimori Michihiro , Tsuruta Teiji
Published: July 2006

An optically active Co(I)(salen) type complex, lithium N,N′-bis-(salicylaldehyde)-1(R),2(R)-1,2-trans-cyclohexanediiminatocobaltate (I), was prepared by reducing the Co(II) complex, N,N′-bis-(salicylaldehyde)-1(R),2(R)-1,2-trans-cyclohexanediiminatocobalt(II), with butyllithium. The structure of the Co(I) complex was determined by means of its absorption and circular dichroism (CD) spectra. d-Propylene oxide was found to react preferentially (e.g., <>=68% in a dioxane solution) in a kinetic resolution of Dl-propylene oxide using the above Co(I) complex as a catalyst. On the contrary, l-propylene oxide reacted selectively when Lewis acids were added to the system of the lithium Co(I) complex. The Lewis acids were demonstrated to interact with the Co(I) complex and to play a significant role in the asymmetric selectivity of the Co(I) species.
Component Amino Acids of the Antibiotic Longicatenamycin. Isolation of 5-Chloro-d-tryptophan
Authors: Shiba Tetsuo , Mukunoki Yasuo , Akiyama Hitoshi
Published: July 2006

An amino acid composition of the pep tide antibiotic longicatenamycin was investigated. Four new amino acids, i.e., thero-β-hydroxy-l-glutamic acid, l-2-amino-5-rnethylhexanoic acid, l-2-amino-6-methylheptanoic acid, and l-2-amino-7-methyloctanoic acid, which were reported by Shoji et al., were reconfirmed by comparison with the synthetic specimens. Racemic forms of the latter three amino acids were synthesized through acetaminomalonate method. Furthermore, 5-chloro-d-tryptophan was newly isolated from the hydrolyzate of the antibiotic. This structure was assigned by NMR, MS and ORD. A steric configuration of this amino acid was certified by degradation to d-aspartic acid through ozonization. 5-Chloro-Dl-tryptophan was synthesized from 3-cyanopropionaldehyde and p-chlorophenylhydrazine by Fischer’s indole synthesis.
Selenocyanatodethallation in Organothallium(III) Compounds
Authors: Uemura Sakae , Toshimitsu Akio , Okano Masaya , Ichikawa Katsuhiko
Published: July 2006

Substitution of thallium moiety in organothallium(III) compounds by selenocyanate is reported. Arylthallium (III) compounds react with KSeCN and CuSO4·5H2O or with Cu(SeCN)2 in dioxane to give aryl selenocyanates in good yields. Alkoxythallates of styrene react smoothly with KSeCN in methanol to afford 1-alkoxy-1-phenyl-2-selenocyanatoethanes almost quantitatively. The oxyselenocyanation of terminal oleflns is conducted by the in situ oxythallation of olefins, followed by the reaction with KSeCN.
Behaviour of Some Selenium Bases in Disulphuric Acid. Conductometric and Cryoscopic Studies of Selenides, Selenoxides and Selenones in Disulphuric Acid
Authors: Bali Ashok , Malhotra K C
Published: July 2006

Dimethylselenoxide is fully ionized in disulphuric acid whereas diphenyl selenoxide and its nitro derivatives behave as weak bases. In the case of selenones, alkyl selenones are completely ionized in disulphuric acid, diphenyl selenone and its nitro derivatives behave as weak electrolytes. From the extent of protonation it is observed that selenones are stronger bases than the corresponding sulphones. Amongst the selenides, diphenyl selenide is sulphonated whereas its nitro derivatives behave as weak bases in it.
Mössbauer and Magnetic Study of Mononuclear and Oxo-bridged Binuclear Iron(III) Complexes of 1,10-Phenanthroline and 2,2′-Bipyridine
Authors: Garg V K , David P G , Matsuzawa Takao , Shinjo Teruya
Published: July 2006

The oxo-bridged binuclear iron(III) complexes [L2(NCS)Fe–O–Fe(NCS)L2]2+ (L=1,10-phenanthroline or 2,2′-bipyridine) were prepared recently in spite of the earlier report that they could not be prepared. The unperturbed and perturbed Mössbauer spectral and magnetic susceptibility data on these compounds are reported here and compared with those for the well characterized oxo-bridged compounds [L2XFe–O–FeXL2]2+ (X=Cl−, Br−, SO42−,/2 or NO3−). The effect of Fe–X bond (X=Cl−, Br−, SO42−/2, NO3−, or NCS−) on the Mössbauer parameters was investigated, and the results are discussed in terms of the bonding properties of these anionic ligands. The data indicate that the electronegativity of the X ligands has no significant effect on the Mössbauer parameters. Another system, the mononuclear iron(III) complexes [FeL2(NCS)2](NCS), investigated in this work showed no Mössbauer resonance at or above 223 K and below this temperature the unperturbed spectra exhibited a broad asymmetric singlet. Magnetic susceptibilities and magnetically perturbed Mössbauer spectra indicated that iron(III) ion in these mononuclear complexes was paramagnetic with S=5⁄2.
A Fluorometric Determination of Zinc in Portland Cement with 8-Quinolinethiol
Authors: Watanabe Kunihiro , Kawagaki Ky\={o}z\={o}
Published: July 2006

A method for the fluorometric determination of zinc in cement with 8-quinolinethiol is presented. o-Phenanthroline and sodium thiosulfate have been found to be useful as masking reagents of interfering ions.
Synthesis of trans-Dibromo-bis{(2-pyridyl)methylamine} and -bis {S-1-(2-pyridyl)ethylamine} cobalt(III) Complexes
Authors: Suzuki Toshishige M , Watanabe Yoshiko , Fujita Junnosuke , Saito Kazuo
Published: July 2006

Light green crystals of trans-dibromo-bis{(2-pyridyl)-methylamine} and -bis{S-1-(2-pyridyl) -ethylamine}cobalt(III) bromide have been prepared. The latter complex shows a circular dichroism (CD) spectrum enantiomeric with that of the corresponding S-propylenediamine complex in the first absorption band region.
The Photolysis of Dimethyl Diazomalonate in Alcohols. The Detection of Triplet Carbene
Authors: Ando Wataru , Hagiwara Tsuneo , Migita Toshihiko
Published: July 2006

The photolysis of dimethyl diazomalonate n alcohols gave the O–H insertion product of biscarbomethoxycarbene and dimethyl malonate as the major products. The dimethyl malonate might be formed by the hydrogen abstraction of a triplet carbene.
The Optical Rotatory Dispersion and Circular Dichroism of Levoglucosenone
Authors: Ohnishi Akio , Takagi Eriko , Kat\={o} Kunio
Published: July 2006

The ORD and CD of levoglucosenone were measured in order to elucidate its abnormally large [α]dvalue of −524°. The complicated pattern observed was considered to contain three Cotton effects—at 357, 231 and 207 nm; the first one at 357 nm seems to be responsible for the large [α]d value.
Temperature-Dependent Infrared Study on l- and Dl-α-Alanine
Authors: Kaneko Norio , Takahashi Hiroaki , Higasi Keniti
Published: July 2006

Infrared spectra from 4000 to 30 cm−1 of l- and Dl-α-alanine and their N-deuterated analogues were measured at temperatures ranging from 295 to 100 K. Highly temperature-dependent bands were observed at 972 cm−1 (at 100 K) for l-α-alanine and 975 cm−1 for Dl-α-alanine. The temperature dependence of the half-widths of these bands indicates that above 200 K the vibrational modes are considerably modulated by some motions, possibly arising from breaking of hydrogen bonds. These bands are thus assigned to the first overtone of the NH3+ torsional mode.
Studies on Bond Character in Phosphorus Ylides by Combustion Heat and X-Ray Photoelectron Spectroscopy
Authors: Sen\={o} Manabu , Tsuchiya Shinji , Kise Hideo , Asahara Teruzo
Published: July 2006

In order to clarify the electron structure of carbonyl-stabilized phosphorus ylides, measurements of X-ray photoelectron spectroscopy (XPS) and combustion heat were performed. NMR and IR spectra were also measured as complementary methods. The results suggest that carbomethoxymethylenetriphenylphosphorane has a major contribution of polar bond (\overset+P—\overset−C) structure, whereas benzoylmethylenetriphenylphosphoranes have a larger contribution of covalent bond (P=C). A dπ–pπ interaction in the P–C bond was interpreted for XPS and NMR. The data for heat of combustion suggest that a large contribution of the polar bond structure brings about stabilization of the ylide molecule. These results show that XPS and combustion heat measurements are useful means for the analysis of ylide bonding.
The Free Energy of Transfer from a Binary to a Ternary Solution by the Isopiestic Measurements
Authors: Uedaira Hatsuho
Published: July 2006

A new method of calculating the free energy of transfer of a solute from a binary to a ternary solution on the mole fraction scale from isopiestic measurements is reported. It was proved that only the new method is consistent.
Stereoisomers of the Bis(l-hydrogenaspartato)trimethylenediaminecobalt(III) Complex
Authors: Kojima Yoshihiro
Published: July 2006

The bis(l-hydrogenaspartato)trimethylenediaminecobalt(III) complex has been prepared by the reaction of the trans-[CoCl2(tn)2]+ complex with l-aspartic acid, and its eight stereoisomers have been separated by an ion-exchange chromatographic method. The six isomers are trans(O)-Λ and -Δ, cis(O)cis(N)-Λ and -Δ and trans(N)-Λ and -Δ isomers, in which either aspartate ion forms the five-membered chelate ring through an N atom of the amino group and an O atom of the α-carboxylate group. The remaining isomers are Λ- and Δ-trans(O) ones containing a five-membered chelate ring and a six-membered ring of l-aspartate ions. On the other hand, stereoselective formations have been found in the Λ,Δ, and Λ isomers for the trans(O), cis(O)cis(N), and trans(N) isomers respectively. It has become apparent that these stereoselectivities agree with those found for the corresponding l-pn and en complexes, while the orders of the formation amounts for the three geometrical isomers disagree.
Effect of Various Additives on Color Center Formation and Brightness Depreciation of Calcium Halophosphate Phosphors
Authors: Narita Kazuo , Tsuda Nobuyuki
Published: July 2006

Color center formation and brightness depreciation by 185 nm radiation were studied in calcium halophosphates containing various additives. Partial bleaching experiments show that the depreciation of plaque brightness is due to the absorption of 254 nm radiation by color centers, the reabsorption of luminescence by color centers being unimportant. In unactivated Ca halophosphates, the stronger the 185 nm absorption of additives, the weaker the color center formation. In Sb- and Mn-activated Ca halophosphates, however, no clear relation is found between the 185 nm absorption of additives and the brightness depreciation. The effect of cesium on improving lamp performance is described.
Ketyl Radicals Formed in Grignard Reaction. III. Steric Effects on the Formation of Radicals
Authors: Okubo Masao
Published: July 2006

In the reaction of benzophenone with phenylmagnesium bromide, the concentration and life-time of the ketyl radical were influenced greatly by the substitution of ortho-hydrogen atoms of both the two reactants by methyl group. From the results of visible absorption and ESR measurements and also of product-analysis, the ketyl radical was considered to be a common intermediate towards normal and abnormal reaction products. The existence of an equilibrium between monomeric and dimeric states of the ketyl radical was also proposed.
Photoreduction and Photoaddition of N-Acetyldiphenylmethyleneamine in Alkylbenzenes
Authors: Asao Shuichiro , Toshima Naoki , Hirai Hidefumi
Published: July 2006

Irradiation of N-acetyldiphenylmethyleneamine (II) in toluene solution gave N-(1,1,2-triphenylethyl)acetamide and N-(1,1-diphenylmethyl)acetamide in 11% and 4.4% yields, respectively. The former is an addition product of toluene to the C=N bond of imine II, and the latter a hydrogenation product of II. The same kind of addition and hydrogenation products as those in toluene were obtained on irradiation of imine II in ethylbenzene, cumene, o-, m-, and p-xylene, mesitylene, p-methoxytoluene, and p-cyanotoluene, respectively. Two kinds of competitive reaction processes are proposed from the results of the substituent effects for the phenyl ring of toluene, the effect of the additives such as sensitizers and quenchers, and the dependence of the photoreaction yields on the concentration of the additive. The photoreaction proceeds not only by the “chemical sensitization” mechanism derived from the ketyl radical of benzophenone, a hydrolyzed product of II, but also by the mechanism through the excited state of II itself.
The Sesquiterpenes of Ginseng
Authors: Yoshihara Kazuo , Hirose Yoshio
Published: July 2006

The sesquiterpenes of ginseng have been studied. From the volatile oil, fifteen compounds were characterized. Three of those compounds, α-panasinsene,β-panasinsene and β-neoclovene, were new compounds and were characterized in this paper. Panasinsenes are considered as intermedial compounds in isomerization of caryophyllene to neoclovene.
Proton Magnetic Resonance of Metal Ammine Complexes. IV. Paramagnetic Anisotropy of Cobalt(III) Ions as Exemplified in Proton Chemical Shifts
Authors: Yoneda Hayami , Sakaguchi Ushio , Nakashima Yoshiaki
Published: July 2006

A theory is presented which couples the proton chemical shift induced by the paramagnetic anisotropy with the chemical shift of the central cobalt-59 nucleus. The theory has been successfully applied to twenty cobalt-(III) α-aminocarboxylate complexes. It is shown that it can be used not only to assign proton NMR signals but also to determine the structure of the complex and, in certain cases, the conformation of ligand molecules.
A Novel Preparation of Enamine Phosphonates from Ketene O,N-, S,N- and N,N-Acetals with Diethyl Phosphite
Authors: Fukuda Masahiro , Kan Kazuhito , Okamoto Yoshiki , Sakurai Hiroshi
Published: July 2006

1-Dimethylamino-1-methoxy-1-alkenes (ketene O,N-acetals), 1-dimethylamino-1-ethylthio-1-alkenes (ketene S,N-acetals) and 1,1-bis(dimethylamino)ethylene (ketene N,N-acetal) reacted with diethyl phosphite to give the corresponding (E)-diethyl 1-dimethylamino-1-alkenylphosphonates. Although ketene diethylacetal (ketene O,O-acetal) reacted with diethyl phosphite to give diethyl 1,1-diethoxy-1-ethylphosphonate, 1,1-bis(ethylthio)-1-alkenes (ketene S,S-acetals) did not react with diethyl phosphite.
The Structure of Yuzurimine-C
Authors: Yamamura Shosuke , Irikawa Hajime , Okumura Yasuaki , Hirata Yoshimasa
Published: July 2006

The structure of yuzurimine-C, one of the yuzurimine-type alkaloids, was unambiguously determined on the basis of chemical evidences coupled with its spectral data. Particularly, application of the 13C NMR spectra plays an important role in the structural elucidation.