bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dielectric Constant Measurement on Organic Crystalline Powder
Authors: Ishii Kikujiro , Kinoshita Minoru , Kuroda Haruo 
Published: July 2006

Abstract
The microwave cavity perturbation method was applied for the measurement of the dielectric constants for polycrystalline samples of ten aromatic compounds (naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, durene, acenaphthene, biphenyl, and p-terphenyl.) The method is shown to give a reasonable result, if the effect of the second order perturbation term is properly included and if Böttcher’s equation is carefully applied in transforming an apparent dielectric constant obtained on a powder sample into the mean dielectric constant of a crystal. The nature of the ordinarily used cavity perturbation equation and of Böttcher’s transformation equation is discussed in this respect. The obtained mean dielectric constants are; naphthalene 2.87, anthracene 3.12, phenanthrene 2.96, pyrene 3.14, chrysene 3.09, perylene 3.34, durene 2.55, acenaphthene 2.94, biphenyl 2.88, and p-terphenyl 2.98. The molecular polarization calculated from these values agreed quite well with the values estimated from the bond polarization given by Le Fèvre et al.
Photoelectron Spectra and Sum Rule Consideration. Higher Alkyl Amines and Alcohols
Authors: Katsumata Shunji , Iwai Toshio , Kimura Katsumi 
Published: July 2006

Abstract
Photoelectron spectra of higher alkyl amines and alcohols (Me, Et, n- and i-Pr, and n-Bu) have been measured with the 584 Å line of helium. Seven photoelectron bands corresponding to p-type MO’s were identified for ethylamine and ethanol. Nine bands were observed for n- and i-propylamine and n- and i-propanol, and eleven for n-butylamine and n-butanol, in addition to the first C2s bands appearing at about 19 eV. The sum rule previously proposed by Kimura et al. has further been applied to the compounds studied here. Total sums of vertical ionization energies in the region below 18 eV have been found to be well reproduced by the sums of appropriate energies estimated for the p-type localized MO’s, using Koopmans’ theorem. Information on orbital character has also been obtained from the sum rule in each symmetry species.
Isocyanide-phosphine Complexes of Cobalt(I)
Authors: Otsuka Sei , Rossi Michele 
Published: July 2006

Abstract
Diamagnetic penta-coordinate Co(I) complexes of formula, [Co(p-CH3C6H4NC)4(PPh3)]X (1) and [Co-(p-CH3C6H4NC)3(PPh3)2]X (2) (X=Cl−, Br−, I−, ClO4−, BPh4−) were obtained from CoX(PPh3)3 or CoX2(PPh3)2. Their 1H NMR spectra served to deduce the trigonal bipyramidal structure. The aromatic ring proton NMR spectra and the IR CN stretching absorptions of radial modes were discussed in terms of the dπ-pπ back bonding.
The Magnetic Properties of Iron(II) Complexes with 2-(2′-Pyridyl)imidazole and Its Derivatives
Authors: Sasaki Yoshihiro , Shigematsu Tsunenobu 
Published: July 2006

Abstract
The magnetic susceptibilities and Mössbauer spectra of iron(II) complexes of 2-(2′-pyridyl)imidazole (PI), 2-(6′-methyl-2′-pyridyl)imidazole (6-MPI), and 2-(2′-pyridyl)benzimidazole (PBI) have been measured in the 4.2–298 K temperature range. The results show that Fe(II)(PI)3(ClO4)2H2O and Fe(II)(PBI)3(ClO4)2H2O have a spin equilibrium between 1A1 and 5T2, while Fe(II) (6-MPI)3(ClO4)2H2O does not have such an equilibrium. The temperature dependence and magnitude of the magnetic data for Fe(II)(PBI)3(ClO4)2H2O and Fe(II)(6-MPI)3(ClO4)2H2O have been calculated by using a parametric Iigand-field approximation. The results indicate that the orbital splittings of the 5T2 ground state due to trigonal distortion are −2000 and −800 cm−1 for Fe(II) (6-MPI)3(ClO4)2H2O and Fe(II)(PBI)3(ClO4)2H2O respectively.
Energetic Reactions of 80Br Activated by (I. T.) Process in C3H8-C2H6 and C3H8-CH3Br Systems
Authors: Numakura Kenshi , Tachikawa Enzo 
Published: July 2006

Abstract
In order to examine the relative importance of the thermal ionic process in the reactions of 80Br from the (I. T.) process with C3H8, we chose C2H6 or CH3Br as diluents. Some assumptions have made in estimating the yield-variation of products from the diluents: 1) the rate of the reduction of the yields of the products from C3H8caused by the addition of the diluent is the same for all of the products and 2) the ionic yield is zero over the whole range of concentrations of C3H8. With these assumptions, the analysis of the results shows that the contribution of the thermal ionic process in these binary systems has only minor importance; the products are, essentially, formed via energetic processes. It is also found that the ratio of n-C3H780Br/i-C3H780Br per bond basis seems to decrease from 1.1±0.1 on the addition of the diluent. This indicates that the formation of i-C3H780Br is a lower energy process, relative to that of n-C3H780Br in the present reaction system.
Syntheses and the Beckmann Fission of Cyclic α-Hydroxyimino Ketones
Authors: Kataoka Mutsuo , Ohno Masaji 
Published: July 2006

Abstract
A convenient method for the preparation of α-hydroxyimino cycloalkanones has been established by the reaction of cycloalkanones and nitrosyl chloride. ω-Cyanocarboxylic acids or their derivatives were obtained in good yield by the Beckmann rearrangement of these α-hydroxyimino ketones.
Reaction of 4-Picoline N-Oxide with Acetic Anhydride as Studied by Chemically Induced Dynamic 13C Polarization (CIDNP)
Authors: Iwamura Hiizu , Iwamura Michiko , Imanari Mamoru , Takeuchi Makoto 
Published: July 2006

Abstract
The 13C spectrum taken during the reaction of 4-picoline N-oxide with acetic anhydride at 110 °C in the NMR cavity (23.5 kG) shows a pair of emission lines at 15.8 and 154.4 ppm and enhanced absorption at 29.6 and 125.0 ppm (TMS-based). The signals are found to be due to 4-ethylpyridine formed as a minor product of the reaction and are interpreted in terms of the memory effect of the polarization induced in the precursor 4-picolyl-acetoxy radical pair.
The N→O and N→S Migrations of the s-Triazinyl Groups of N,N-Di-s-triazinyl Derivatives of o-Aminophenol and o-Aminothiophenol
Authors: Tsunoda Shigeo , Shiojima Takeo , Hashida Y\={o}ji , Sekiguchi Shizen , Matsui Kohji 
Published: July 2006

Abstract
N,N-Bis(dichloro-s-triazinyl)-2-aminophenol reacted with an excess of dimethylamine or methylamine to give N,O-bis(s-triazinyl)-2-aminophenol and N-s-triazinyl-2-aminophenol upon the aminodechlorination, N→O migration, and cleavage of the s-triazinyl group. However, N-(dimethoxy-s-triazinyl)-N-(dichloro-s-triazinyl)-2-aminothiophenol reacted with an excess of dimethylamine to give merely a disulfide of N-s-triazinyl-2-amino-thiophenol upon the aminodechlorination and cleavage of the dimethoxy-s-triazine nucleus. On the other hand, N,N-bis(s-triazinyl)-arylamines containing no ortho-OH or -SH group were stable to the attack by amines, while phenoxy-dimethoxy-s-triazine or phenylthio-dimethoxy-s-triazine reacted readily with dimethylamine to give dimethylamino-dimethoxy-s-triazine upon the fission of phenol or thiophenol. From these resutls, the reactions of the N,N-bis(s-triazmyl) derivatives of both o-aminophenol and o-aminothiophenol with amines to give the corresponding N-s-triazinyl derivatives are considered to proceed by means of an intramolecular nucleophilic attack by the phenoxide or thiophenoxide anion on the s-triazine ring carbon to give the N,O- or N,S-bis(s-triazinyl) derivative upon the N→O or N→S migration of the s-triazinyl group, followed by the cleavage of the O- or S-s-triazinyl group to give the final product. However, when the intermediary derivative is stable to amine, the intermediate is obtained as the major final product.
Counterion Effect in the Electron-Transfer Reactions between a Tetracyanoethylene Radical Anion and Its Neutral Molecule
Authors: Ogasawara Masaaki , Takaoka Hidetoshi , Hayashi Koichiro 
Published: July 2006

Abstract
The rates of homogeneous electron-transfer reactions between radical anions and neutral molecules were studied in a variety of tetracyanoethylenide systems in order to obtain information concerning the counterion effect on the electron-transfer reactions. The estimated values of the rate constants had the same order of magnitude at room temperature for all the systems, while the activation energies and the preexponential factors were markedly dependent on the natures of the counterions and the solvents. The obtained results are discussed in terms of the forms and structures of the radical anions.
Reaction between Methyl-p-tolylmethoxysulfonium Salt and Nucleophiles
Authors: Tsumori Kuniaki , Minato Hiroshi , Kobayashi Michio 
Published: July 2006

Abstract
The reactions of methyl-p-tolylmethoxysulfonium ion with such nucleophiles as tertiary amines, triphenylphosphine, thiophenolate anion and p-toluenesulfinate anion were investigated. The points of attack vary with nucleophile; the sulfonium ion receives nucleophilic attacks at its methoxy oxygen, methoxy carbon, sulfonium sulfur, S–CH3 hydrogen or O–CH3 hydrogen atoms. Optically active methyl-p-tolylmethoxysulfonium ion was also synthesized, and its reactions with benzylethylphenylamine, benzylmethylphenylphosphine and benzyl ethyl sulfide were studied. In the cases of the amine and the sulfide, the methylated products had optical activity. Thus, the methoxysulfonium ion can act as an optically active methylating agent.
Studies on Aminosugars. XXXV. Syntheses of 3′,4′-Dideoxyneamine and 3′- and 4′-O-Methylneamines
Authors: Jikihara Tetsuo , Tsuchiya Tsutomu , Umezawa Sumio , Umezawa Hamao 
Published: July 2006

Abstract
3′,4′-Dideoxyneamine and 3′- and 4′-O-methylneamines have been prepared from neamine via 5,6-O-cyclohexylidene-tetra-N-methoxycarbonylneamine (2).
The Methylenation of Several Allylbenzene-1,2-diol Derivatives in Aprotic Polar Solvents
Authors: Fujita Harushige , Yamashita Masataro 
Published: July 2006

Abstract
The aprotic polar solvents, such as DMF (N,N-dimethylformamide) and DMSO (dimethyl sulfoxide), accelerated very effectively the methylenation of 1,2-dihydroxy-4- (I), 1,2-dihydroxy-3,4-dimethoxy-5- (II), and 1,2-dihydroxy-3-methoxy-5-allylbenzene (III) in the presence of bronze and cupric oxide as catalysts.
Preparation of Reinforcing Fillers from Japanese Acid Clays with Lime and by Calcination. II. Optimum Conditions for the Preparation of Good Hard Clays and Evaluation of Their Reinforcing Properties
Authors: Rai Hideki , Yamada Junkichi 
Published: July 2006

Abstract
In order to find the optimum conditions for the preparation of good reinforcing filler from Matsune (M) and Nakajo (N) acid clays with lime and by calcination, investigations were carried out by changing the amount of alkali (1.25–60% CaO), the temperature of thermal treatment (110–800 °C) and the subsequent mechanical disintegration time (6–24 hr). The required conditions were found to be: amount of alkali, 3% for M and 6% for N; calcination at 600 °C for 1.5 hr; disintegration time around 18 hr. The deviation in the optimum amount of alkali was attributed to the difference of mineralogical constituents. The products pulverized gave the SBR-1502 compounds good reinforcing properties comparable to those of Dixie Clay. Investigation was also carried out on the influence of manual and mechanical mixing of the raw materials, the mode of disintegrating the calcined matter by either wet ball-milling or dry pulverization, and the effect of sieving the pulverized product in wet or dry state on the reinforcing properties of the prepared fillers. A variable loading test with hard clay M up to 150 PHR proved that its reinforcing properties are comparable to those of the reference filler. The maximum reinforcement for the elastomer was found to be about 50 PHR for hard clay M and about 100 PHR for the reference filler.
The Intensity in the Resonance Raman Effect. I. The Diatomic Molecule in the Harmonic Potential Approximation
Authors: Kobinata Shunsuke 
Published: July 2006

Abstract
The formulas for the Raman intensities of fundamental and n-th overtones were investigated theoretically, starting from the Kramers-Heisenberg dispersion formula and referring to a diatomic molecule in a harmonic potential approximation. The derived formulas were then applied to fifteen overtone bands of iodine, which have been observed in gas, and to the exciting frequency dependence of the fundamental and the first overtone intensities of iodine in a CHCl3 solution. It was shown that the formulas quantitatively explain the trend of the observed data well.
Polarographic Studies of Some Porphyrins and Metalloporphyrins in N,N-Dimethylformamide
Authors: Kakutani Tadaaki , Totsuka Shoji , Senda Mitsugi 
Published: July 2006

Abstract
Electrochemical behavior of protoporphyrin IX dimethylester (PPDM), mesoporphyrin IX dimethylester(MPDM), Fe(III)Cl-protoporphyrin, Ni(II)-, Cu(II)-, Co(II)-, Zn(II)- and Mn(III)Cl·H2O–PPDM was investigated in dimethylformamide by use of AC polarography, cyclic voltammetry and DC polarography. These porphyrins and divalent metal complexes of PPDM gave, for the most part, three reduction waves. The first and second waves were reversible one-electron steps in each case, but the third step was an irreversible one. Mn(III)-complex gave four reduction waves and one oxidation wave. The first three reduction waves were one-electron steps and the oxidation wave was identified as that due to chloride anion. Fe(III)-complex gave five reduction waves and one oxidation wave. The first two reduction waves were one-electron steps. All these compounds showed specific adsorption at the potential more positive than −1.1 V vs. SCE. Assignment of the reduction steps of the metalloporphyrins is described. The observed order of increasing negative half-wave potentials is discussed in terms of Zerner and Gouterman’s molecular orbital calculation.
Kinetics of Hydrogen Electrode Reaction on Mercury. I. Theoretical Part. Non-steady State Analysis for the Electrochemical Mechanism
Authors: Katayama Akiko , Kita Hideaki 
Published: July 2006

Abstract
Potentiostatic and potentiodynamic transients are theoretically analysed on the basis of the electrochemical mechanism for the hydrogen electrode reaction. The interface was assumed to consist of the metal surface, the plane on which the adsorbed intermediate of H2+(a) stays, and the diffuse double layer. The repulsive force between the intermediates was introduced by proportional approximation. From the results the depolarization observed in Tafel plots is understood as a non-steady state phenomenon, and observation by the potential-sweep method offers information on both the features of the adsorbed intermediate and the kinetics of the step preceding the rate-determining step.
Kinetics of Hydrogen Electrode Reaction on Mercury. II. Experimental Part. Elucidation of Non-steady State by Constant Potential and Linear Potential-sweep Methods
Authors: Katayama Akiko , Kita Hideaki 
Published: July 2006

Abstract
Potentiostatic and potentiodynamic experiments on Hg in 1 M HCl, HBr, and HI solutions were carried out to elucidate transient phenomena of the electrochemical mechanism of the hydrogen electrode reaction. The results obtained by both methods agree with the analysis of the non-steady state based on the electrochemical mechanism. The large effect of anions on the transient phenomena is satisfactorily interpreted by the change of repulsive force energy between H2+(a)’s on electrode, which is caused by the presence of specifically adsorbed anions in various degrees. The potential-sweep method reveals features of the step preceding the rate-determining step and gives the value of the repulsive force energy between H2+(a)’s as expected by the analysis.
Molecular-symmetry Reduction in CmHm−2 Cata-condensed Nonalternant Hydrocarbons
Authors: Toyota Azumao , Nakajima Takeshi 
Published: July 2006

Abstract
On the basis of the second-order Jahn-Teller effect and the semiempirical SCF MO method, we examined the energetically most favorable molecular-symmetry groups and geometrical structures with respect to C–C bond lengths of the CmHm−2 cata-condensed nonalternant hydrocarbons. In the 4n π-electron systems the first excitation energies in the fully-symmetrical nuclear arrangements were predicted to be significantly smaller than a certain critical value, and a molecular-symmetry reduction accompanied by a marked double-bond fixation in the peripheral carbon skeleton to occur. On the other hand, in the 4n+2 π-electron systems, such energies were found to be considerably large for small members and to decrease rapidly with the number of carbon atoms, resulting in the molecular-symmetry reduction for members larger than a certain critical size. The electronic spectra were calculated using the most stable geometrical structures obtained by the SCF MO method.
Electrochemiluminescence of 9,10-Dichloroanthracene at Low Temperatures
Authors: Matsumoto Tamotsu , Sato Masanori , Hirayama Satoshi 
Published: July 2006

Abstract
The electrochemiluminescence (ECL) of 9,10-dichloroanthracene in methylene chloride was investigated at temperatures as low as −60°C. The cation was quite stable and the anion was unstable at room temperature. The anion, however, increased its stability as the temperature decreased and below ca. −40°C it was essentially stable. Temperature was also found to have great influence on the relative intensity of the two spectral components of the ECL of 9,10-dichloroanthracene. By lowering the temperature the components at the longer wavelength increased strongly compared with the other component. When the ECL was observed by applying a rectangular potential, the intensities of the two components decayed exponentially with the same decay constant. Therefore, it was concluded that the emission at the longer wavelength originated not from the products of electrolysis but from the excimer and that the primary process to produce these two emissions was the same.
The Electronic Absorption Spectra of Würster’s Cation Radicals and Their Dimerization in Solution
Authors: Nakayama Shigeki , Suzuki Keisuke 
Published: July 2006

Abstract
The visible and ultraviolet absorption spectra of the p-phenylenediamine cation (PD+), the N,N-dimethyl-p-phenylenediamine cation (DMPD+), and the N,N,N′,N′-tetramethyl-p-phenylenediamine cation (TMPD+) in the presence and in the absence of an excess counter anion (X−=Br−, Cl−, and ClO4−) are studied at low temperatures. Analyses of the data show that these cation radicals are in an equilibrium represented by 2R++X−\ightleftharpoonsR++2X− (or, more exactly, 2R++0.7X−\ightleftharpoonsR++2(X−)0.7). It is found that the absorption maxima of the dimer and the value of the heat of dimerization are independent of the kind of counter anion. It is concluded that PD+ and DMPD+ form strong dimers (heat of dimerization, ΔH=−8.0 and −8.2 kcal/mol respectively) and that TMPD+ forms a relatively weak one (ΔH=−5.6 kcal/mol). The features of the dimer spectra reflect the strength of the interaction of the radical in the dimer. In a strong dimer, the spectrum in the low-frequency region consists of a strong intermolecular charge-transfer band (C band) and a weak local excitation band (R′ band), and the frequency shifts of the local excitation bands in the dimer (R′ and Y′ bands) from corresponding bands in the monomer (R and Y) are large. On the other hand, the spectrum in the weak dimer consists of relatively weak C and strong R′ bands, and the shifts of the R′ and Y′ bands are small. A model of the dimer is proposed in which the two cations are arranged in a parallel manner and are surrounded by the ionic atmosphere of the counter anions.
Photoelectron Spectra and Orbital Structures of Higher Alkyl Chlorides, Bromides, and Iodides
Authors: Kimura Katsumi , Katsumata Shunji , Achiba Yohji , Matsumoto Hiroshi , Nagakura Saburo 
Published: July 2006

Abstract
High-resolution photoelectron spectra of alkyl halides RX (R=ethyl, n-propyl, and n-butyl; X=C1, Br, and I) were measured with the 584 Å line of helium. In the region below about 17 eV, six bands were observed for each of the ethyl halides, eight bands for each of the n-propyl halides, and ten bands for each of the n-butyl halides. All the observed vertical ionization energies were plotted against Pauling’s electronegativity of the halogen atom, indicating that there are approximate linear relationships. Assuming Koopmans’ theorem, total and partial sums of experimental orbital energies were calculated using the observed ionization energies for the individual alkyl halides and found to be well reproduced by calculating the sums of empirical orbital-energy values for several localized orbitals such as n(X.), n′(X), σ(C–X), σ(C–C), π(CH3), π′(CH3), and π(CH2). From a comparison of the experimental and calculated partial orbital-energy sums, assignments of the photoelectron bands to the localized molecular orbitals were made for each of the alkyl halides.
Ion-selective Electrode Membranes Responsive to Maleic and Phthalic Acids
Authors: Jyo Akinori , Yonemitsu Morihisa , Ishibashi Nobuhiko 
Published: July 2006

Abstract
Ion-selective electrodes responsive to maleic and phthalic acids were prepared. The organic solvent solution of the ion-pair of the objective monovalent acid anion with a Crystal Violet or a tris(bathophenanthroline)-iron(II) ion was used as the electrode membrane. The responses of both electrodes were linear down to 10−4–10−4.5 M, with an ideal Nernstian slope of 57–58 mV per activity decade at 20 °C. Together with the potential slope, the pH dependence of the potential showed that the electrode responded to the monovalent anion of maleic or phthalic acid. The interferences of acetate, benzoate, and chloride were extremely low, whereas iodide and perchlorate interfered greatly. The maleic acid electrode works well without the interference of fumaric aicd. The phthalic acid electrode also functions without any interferences by isophthalic or terephthalic acid.
Derivatographic Studies on Transition Metal Complexes. XII. Thermal Olation of Hydroxoaquo Cobalt(III) and Chromium(III) Complexes Containing Amino Acids in Solid Phase
Authors: Tsuchiya Ryokichi , Uehara Akira , Kyuno Eishin 
Published: July 2006

Abstract
The thermal olation of the following four types of complexes in a solid phase was investigated by means of derivatography: 1) cationic complexes, [Co(OH)(n3-o)(H2O)]X, 2) anionic complexes, M[Co(OH)(n-o3)-H2O)], 3) double complexes, [Co(OH)(n3-o)(H2O)][Co or Cr(OH)(n-o3)(H2O)] and 4) neutral complexes, [Co(OH)(n-o)2(H2O)], where n3-o, n-o3 and (n-o)2 denote gly-en (glycinate ion and ethylenediamine) or dtma (diethylenetriaminemonoacetate ion), the analogues of nta (nitrilotriacetate ion) and α-amino acid ions, respectively. The thermal data such as initiation temperature, enthalpy change and activation energy of the olation were estimated from the respective derivatograms. From the results the effect of various ligands or counter ions (outer-sphere ions) on the olation was discussed.
Pressure Effect Determined with Use of the Nondispersive Infrared Gas Analyser
Authors: Niki Eiji , Yonezawa Tsutomu 
Published: July 2006

Abstract
The pressure effect of nitrous oxide and nitric oxide due to nitrogen gas was investigated with use of a nondispersive infrared gas analyser. The results are in line with the theoretical curves derived from the Elsasser theory. The calculated expression is partly improved and the error of calculations is estimated in regard to carbon dioxide.
Infrared Spectra of Some Transition-metal (Fe, Co, Ru, and Ir) Nitrosyl (14NO and 15NO) Complexes
Authors: Miki Eiichi , Mizumachi Kunihiko , Ishimori Tatsujiro , Okuno Hisateru 
Published: July 2006

Abstract
Twelve 15NO-complexes of iron, cobalt, ruthenium, and iridium were prepared. The correlations of the isotopic shifts of their IR spectra with a metal–(NO) bond angle were investigated. For several nitrosyl complexes, the absorption bands due to the skeletal vibrations between the metal and the NO group were clearly assigned. Of the two absorption bands in the region 250–650 cm−1, the absorption band with a smaller isotopic shift could be assigned to the metal–(NO) stretching vibration and that with a larger isotopic shift to the metal–(NO) bending vibration.