bluuebunny/crossref_metadata_2025 huggingface dataset:
Ultrasonic and Thermodynamic Study on Solute-Solvent Interaction. Binary Mixtures of 1,2-Dichloroethane with Benzene, Toluene, p-Xylene and Cyclohexane
Authors: Kiyohara Osamu , Arakawa Kiyoshi
Published: July 2006

The sound velocity and density of binary mixtures of benzene, toluene, p-xylene and cyclohexane with 1,2-dichloroethane (DCE) as a common component were measured at temperature 20–40°C, and the excess molar volume and excess compressibility of these systems were calculated. They were found to be positive. The excess compressibility is independent of temperature in the DCE-benzene system. Thermodynamical properties and the nature of intermolecular interaction in the systems were discussed. It has been shown that there is a certain weak attraction between DCE and aromatic molecules, and that there is no complex formation viz., hydrogenbonding or change transfer complex. It has been proposed that the interaction between gauche form of DCE and aromatic molecules is of electrostatic nature (dipole-induced dipole or hyperpolarizability).
An Application of the Phase-inversion-temperature Method to the Emulsification of Cosmetics. I. Factors Affecting the Phase-inversion Temperature
Authors: Mitsui Takeo , Machida Yasuhiko , Harusawa Fuminori
Published: July 2006

Recently, the PIT (phase-inversion-temperature) system was originated and developed by Shinoda and his collaborators as a guide to surfactant selection. In order to apply the PIT system to the cosmetic field, the effects of various factors on the PIT have been reinvestigated using cosmetic materials. POE alkyl ethers, whose distribution of EO chain lengths is broad, are widely used in cosmetics. In such a case, the effect of the distribution of the EO chain lengths is important. When a surfactant with a distribution of EO chain lengths was used, the PIT was lowered by an increase in the concentration of the surfactant, but when a monodisperse surfactant without any distribution was used, the PIT scarcely varied with the concentration of the surfactant. In the case of the surfactant with a distribution of EO chain lengths, however, if the ratio of oil to surfactant was kept constant, the PIT scarcely varied with the ratio of oil phase to water phase. This relationship can be used in estimating the PIT in the case of the practical production of an emulsion.
Some Aspects of Gaseous TCNE Complexes Including the Butene-TCNE
Authors: Aihara Jun-ichi , Tsuda Motoyuki , Inokuchi Hiroo
Published: July 2006

The absorption spectra of the gaseous olefin-TCNE complexes were successfully observed for the first time: the absorption maximum of the butene-TCNE complex was found at 28700 cm−1. The CT band of the methyl derivatives was shifted to a higher-energy region because of their steric effect. The systematic collection of the gaseous data made it possible to estimate the magnitude of the steric effect.
Effect of Pressure on the Solubility of Diketopiperazine in Water
Authors: Suzuki Keizo , Tsuchiya Masao , Kadono Hideki
Published: July 2006

Diketopiperazine (DKP) was used as a model compound to investigate hydrogen bond interactions between the peptide bond and water under high pressure. The solubility of DKP in water was measured as a function of pressure up to about 6000 atm at 15,25 and 35°C. It was observed that the solubility decreases with increasing pressure up to about 4500 atm, and then increases above this pressure. The solubility follows a simple exponential dependence upon pressure at least below 4500 atm. The volume change ΔV accompanying the dissolution of DKP in water is obtained from this pressure dependence of the solubility. The values of ΔV are 5.2 and 5.9 ml/mol at 25° and 35°C, respectively. These values coincide well with those obtained from dilatometric measurements at 1 atm. The reason why the solubility is inverted at the pressure above and below 4500 atm is ascribed to the change of water structure brought about by the compression. The effect of pressure on proteins reported in the previous paper is discussed in relation to the present solubility results.
Force Constants and Average Structures of AsF3 and AsCl3 as Determined by Electron Diffraction and Spectroscopy
Authors: Konaka Shigehiro
Published: July 2006

The general quadratic potential constants of AsCl3 have been determined by the use of a combination of the mean amplitudes observed by gas electron diffraction and the vibrational frequencies. Those of AsF3 have been determined from the mean amplitudes, the centrifugal distortion constants given by microwave spectroscopy and the Coriolis coupling constants and the vibrational frequencies given by infrared spectroscopy on the basis of the molecular structure newly-determined by electron diffraction. By using these potential constants, zero-point average structures have been derived from the rg structures obtained by electron diffraction. The results have been found to be consistent with the average rotational constants, Bz, derived from the effective rotational constants, B0, observed by microwave spectroscopy according to the theory of vibration-rotation interactions. The final results, obtained by the use of a combination of the electron diffraction and microwave data, are:

& r_z(As-Cl)=2.1621±0.0009 Å, θ_z(ClAsCl)=98°38’±22’

& r_z(As-F)=1.7080±0.0004 Å, and θ_z(FAsF)=95°58’±17’.

Formulas for calculating the sum of perpendicular mean amplitudes for pyramidal XY3-type molecules have been derived and used to reduce rg to rz.
Stochastic Model for Chemical Relaxation
Authors: Ishida Kenji
Published: July 2006

The stochastic formulation of chemical rate equations requires that the process of chemical relaxation should be accompanied with the fluctuation of chemical composition. It is shown that the factor Γ, which Eigen and de Maeyer introduced in the thermodynamic analyses of chemical relaxations, may be interpreted as the fluctuation of chemical composition.
Spectrophotometric Determination of Diphenhydramine in Pharmaceutical Preparations
Authors: Tsubouchi Masahiro
Published: July 2006

A spectrophotometric method is proposed for the determination of diphenhydramine in pharmaceutical preparations. The method is based on an addition-compound formation between diphenhydramine and the tetrabromophenolphthalein ethyl ester in 1,2-dichloroethane. Beer’s law is obeyed over the range of 2.0×10−6–1.0×10−5m of diphenhydramine at 594 mμ. Optimum conditions are described. The effect of diverse substances and the composition of the colored species were also investigated.
Photoinduced Reactions. XLIII. Photochemical Reactions of 4-Hydroxy-2,5-cyclohexadienones
Authors: Ogura Katsuyuki , Matsuura Teruo
Published: July 2006

Irradiation of 2,4-di-t-butyl-4,5-dihydroxy-2,5-cyclohexadienone (V) in methanol afforded a β-diketone (VIII) in a 68% yield. Diketone VIII was also formed on photolysis of a suspension of V in petroleum ether (62%) and an aqueous alkaline solution of V (56%). Photolysis of 2,4-di-t-butyl-4-hydroxy-5-methoxy-2,5-cyclohexadienone (VI) in various solvents yields IXa as a main product. On irradiation of VI in methanol, XI which might be formed by the addition of methanol to IXb was also isolated. Irradiation of 2,4,6-tri-t-butyl-3-methoxy-4-hydroxy-2,5-cyclohexadienone (VII) in a variety of solvents gave a cyclopentadienone (XIII) in high yields. It is reasonable to assume that the cyclopentadienone XIII is formed by elimination of methanol from a 2-cyclopentenone derivative (XII). The formation of XIII from VII was sensitized by benzophenone and acetophenone, and quenched by piperylene. The mechanisms of these reactions are discussed.
The Paramagnetic Species Formed on the Surfaces of Various Oxides by Naphthalene Derivatives
Authors: Ueda Hisashi
Published: July 2006

The ESR intensities from the paramagnetic species formed by mixing a naphthalene derivative with an oxide powder were studied after the mixture had been heated at various temperatures. The measurements were made at 20°C. As additives 1-nitronaphthalene, 1-naphthol, 1,4-naphtho-quinone, naphthalic acid, 1-naphthylamine, l-nitroso-2-naphthol, naphthalene, triphenylene, and anthracene were used. As oxides, alumina, Al2O3-MoO3, silicagel, TiO2, MgO, MoO3, CuO, and ZnCrO4 were used. The ESR intensities obtained by the first six oxides depended only on the ioni-zation potential of the additives, while those obtained by CuO and ZnCrO4 did not. The ESR intensities obtained when 1-naphthol was mixed with alumina samples with various surface areas-were exactly proportional to the surface areas of the alumina specimens used. It was concluded that, in the first six oxides, the additives are chemisorbed by the oxides at the active-oxygen anion sites on the surface. The introduction of either NH3 or N2O onto the adsorbed species formed on Al2O3-MoO3 particles decreased (in the case of NH3) or increased (in the case of N2O) the ESR intensities. From these facts, it is concluded that a cationic complex, (naphthalene derivative+-O2−), is formed on the surface of these six oxides. In the case of GuO, the presence of (Cu+-naphthyl-amine+) is concluded.
Studies of Tritylated Sucrose. I. Mono-O-tritylsucroses
Authors: Otake Toshiki
Published: July 2006

Two isomeric mono-O-tritylsucroses were isolated from a mixture of tritylated sucrose which had been obtained by the reaction of sucrose and trityl chloride in the ratio of 1 : 1.2 by mole. The structures of these two isomers were established by the application of gas chromatography and NMR spectroscopy to appropriate derivatives. One of the two substances is 6′-mono-O-tritylsucrose, and the other is 6-mono-O-tritylsucrose, which is crystallized as white needles. The detritylation of mono-O-trityl-O-acetylsucroses yielded hepta-O-acetylsucroses, which were confirmed by a study of their NMR spectra to be 2,3,4,6,1′,3′,4′- and 2,3,4,1′,3′,4′,6′-hepta-O-acetylsucrose. No migration of the acetyl group on the sucrose molecule was observed during the detritylation procedure.
The Synthesis and Reaction of α,β-Unsaturated α-Nitrocarboxylic Esters
Authors: Shin Chung-gi , Masaki Mitsuo , Ohta Masaki
Published: July 2006

Synthetic studies of α,β-unsaturated α-nitrocarboxylic esters and the corresponding α-amino compounds are described. When α,β-unsaturated carboxylic ester was treated with fuming nitric acid, two products, α,β-unsaturated α-nitrocarboxylic ester and α-hydroxy-β-nitrocarboxylic ester, were formed. The former was converted into β-methoxy-α-nitrocarboxylic ester by treatment with methanol in the presence of a base such as sodium methoxide or sodium acetate. Reduction of β-methoxy-α-nitrocarboxylic esters with aluminum amalgam and the subsequent distillation of the products afforded α,β-unsaturated α-aminocarboxylic esters and α-hydroxyamino-β-methoxycarboxylic esters, which were confirmed by their N-phthaloylglycyl derivatives.
Intramolecular Hydrogen Bonds. XV. Intramolecular Interaction in N-Alkylaminoalkanonitriles
Authors: Mori Nobuo , Asabe Yoshihiro , Tatsumi Junko , Tsuzuki Yojiro
Published: July 2006

The νNH values of monomeric alkylmethylamines in carbon tetrachloride solutions are associated with the rotational isomerism about the N–C bond. In the series of N-alkylaminoalkano-nitriles, the intramolecular hydrogen-bonding interaction of the NH group with the π-electrons of the CN group was deduced on the basis of the νNH values and a model examination; in the α-series, the NH group probably interacts exclusively, and in the β-series it partially interacts, but in the γ-series it shows no interaction.
Radiative Lifetime Measuements of Some Excited States of N2+ and CH
Authors: Sawada Tsuguo , Kamada Hitoshi
Published: July 2006

Time-sampling technique has been applied to radiative lifetime measurements. The time resolution of the apparatus was about 10 nsec. The excited molecules were produced by electron bombardment of N2 and CH4. The measured lifetimes of N2+(B2Σu+), CH(A2Δ) and CH(B2Σ−) are (6.5±0.5)×10−8 sec, (4.3±0.2)×10−7 sec and (7.6±0.4)×10−7 sec, respectively. Band oscillator strengths have been computed on the assumption that the electronic transition moment is constant in the range in which the transition takes place.
The Distribution of the Acid Strength on Zeolite Catalyst — Estimation from the Heats of Adsorption —
Authors: Okamoto Yasuaki , Imanaka Toshinobu , Teranishi Shiichiro
Published: July 2006

The distribution of the acid strength on two zeolites, 13X and 10X, and on the copper form of X-type zeolite were estimated from the differential heats of n-butylamine adsorption in a benzene solution. The acid sites on these zeolites were revealed to have two kinds of acid strengths, that is, the cation-dependent one and the cation-independent one. The former corresponds to the stronger acid strength, and the latter, to the weaker. The IR spectra of the residual surface OH groups on these catalysts were also investigated. The strongest acid sites on each zeolite were considered to be those of the cation-dependent OH group which has the lowest frequency. The interaction between surface OH groups and immersed benzene was assumed to be a π-type hydrogen bond.
Electron Spin Resonance Study on Radical Anions of Acridine and Its Halogen Derivatives
Authors: Konishi Shiro , Niizuma Shigeya , Koizumi Masao
Published: July 2006

ESR spectra of radical anions produced by bringing 9-chloro-, 2,7-dibromo-9-chloro-, and 2,4,5,7-tetrabromo-9-chloroacridine into contact with alkali metal (sodium and potassium) in tetrahydrofuran were measured at room temperature and/or at lower temperatures, and the analysis of them was made by means of a simulation method. Hyperfine coupling constants of acridine anion radicals, produced by the similar method in tetrahydrofuran and also by the electrolytic reduction in acetonitrile with the flow method, were determined, taking those of halogen derivatives into consideration. ESR spectra of acridine and 9-chloroacridine anion radical were found to involve the coupling of sodium, showing that these radicals were in the form of ion pair. The coupling constants of bromoacridine anion radicals did not give any difference between the sodium and the potassium reduction. The couplings of halogen atoms were not observed. Good agreement was obtained between the coupling constants calculated from spin densities and those determined experimentally. In general, the solution of radical anions of halogenides gradually yields brownish aggregates at lower temperatures (−20∼–30°C), their ESR spectra becoming weaker and unresolved. The temperature change is reversible and qualitatively resembles the behavior of acridine anion radical.
The Phosphorescence Bands of Anthraquinone in Crystalline Solvents at 77°K
Authors: Kuboyama Akira
Published: July 2006

The phosphorescence bands of anthraquinone in the solvents used in this work are all safely assigned to the π*→n bands on the basis of their short lifetimes. In n-paraffins (n-hexane, n-heptane, and n-octane), two phosphorescence bands which are close to each other are found. Considering the dependence of the relative intensities of these two phosphorescence bands on the carbon-numbers of the n-paraffins, it is assumed that the longer- and the shorter-wavelength bands are due to the anthraquinone molecules with the C–O bond axis parallel to and perpendicular to the longitudinal axis of the planar zig-zag form of the n-paraffin molecules in the n-paraffin crystals respectively. In chloroform and dioxane, a broad phosphorescence band shows a blue-shift relative to the corresponding band in the alkane solvents. In chloroform a sharp phosphorescence band was also observed for a solution which was rapidly cooled. This sharp band is assumed to be due to the anthraquinone molecules with a certain geometry relative to the surrounding chloroform molecules.
Electrical Conductivity of Graphite Bromine Lamellar Compounds
Authors: Sasa Tadashi , Takahashi Yoichi , Mukaibo Takashi
Published: July 2006

Polycrystalline graphite was allowed to react with bromine vapor, and the change of its electrical conductivity during the course of bromination and debromination was studied. The graphite was found to behave in two different ways depending on the process of bromination. When the vapor pressure of bromine was changed stepwise, following the equilibrium line of bromine absorption of graphite, the electrical conductivity showed a reversible change. On the other hand, when a graphite sample was brominated with the saturated vapor, an increase of the electrical conductivity steeper than that of the former case was observed. These results were discussed in relation to the structural analysis of the brominated graphite. A metastable phase of graphite bromide, the electrical conductivity of which remained unchanged in spite of a considerable increase of absorbed bromine, was found. The electrical conductivity of the residue compounds was also investigated, and a steep decrease was observed at high concentrations of bromine.
Chemi-ionization of Cs*(82P1⁄2) with Cs and Foreign Gases
Authors: Ono Yoko , Koyano Inosuke , Mori Yuji , Tanaka Ikuzo
Published: July 2006

Chemi-ionization has been studied by the collision of the excited atom of cesium (82P1⁄2), whose energy is lower by 0.7 eV than its ionization energy, with cesium, rare gases or simple molecules. The mechanisms for the chemi-ionization, and quenching processes occurring simultaneously were set up and the cross sections of the processes have been determined. Since the pressure effects of added gases to the absorption coefficient of Cs at 3888 Å from the He lamp could not be neglected, suitalbe corrections were made.
Electronic States of p-Chloranil and Its Anion-Radical as Revealed by Their Infrared Spectra
Authors: Iida Yoichi
Published: July 2006

The infrared spectra (650–4000 cm−1) of p-chloranil and its anion-radical were measured. Appreciable frequency differences between their corresponding bands were noted. The fundamental frequencies were assigned, and the simple UBFF’s were determined for both the neutral and anion-radical molecules. Their stretching force constants for the bonds in the conjugated systems are related to the bond orders. The values of the bond orders thus obtained for p-chloranil and its anion-radical were in good agreement with those evaluated by the molecular-orbital calculation, except for the C=O bond in the anion-radical. In view of these results, it was concluded that the difference in the infrared spectra between these two molecules was almost entirely attributable to the difference in their electronic structures caused by an odd electron on the p-chloranil anion-radical. The bond lengths were also estimated on the basis of the bond orders. It was shown that the application of this method might bring valuable knowledge on the molecular and electronic structures of ion-radicals as well as of neutral molecules in general.
The Effect of Impurities upon the Physical Properties of Silica Gel by the Heat-Treatment
Authors: Muroya Masaaki , Kondo Seiichi
Published: July 2006

The effects of various kinds of inorganic salts upon the physical properties of silica gel heated in the range up to 1200°C were studied. We measured the polymorphic behavior by means of X-ray diffraction, the simultaneous measurement of the differential thermal analysis, and the thermogravimetric analysis, and the specific surface area by means of the BET N2 method and by means of studying the water-adsorption capacity. The cationic impurities which were found to have strong effects upon the physical properties mentioned above are Na+, K+, Ca2+, Pb2+, Cd2+, Zn2+, and Sb3+. Cations such as Al3+, Cr3+, Mn3+, and Co2+ were shown to have weak but positive effects upon the physical properties of silica gel.
Spectroscopic Studies of Polynuclear Complexes. II. Preparation and Optical Resolution of μ-Amido-μ-superoxo and μ-Amido-μ-peroxo Tetrakis(α-di-imine)dicobalt(III) Ions
Authors: Sasaki Yoichi , Fujita Junnosuke , Saito Kazuo
Published: July 2006

New binuclear cobalt(III) complexes of the type, [L2Co(μ-NH2,O2)CoL2](ClO4)n, where L is 1,10-phenanthroline or 2,2′-bipyridyl, and n=3 and 4, correspond to the so-called μ-peroxo and μ-superoxo form, respectively, were prepared and resolved into their optical isomers. Their absorption spectra have been compared with those of analogous ethylenediamine complexes and the structures have been discussed. The absolute configuration of these complexes has been determined by their circular dichroism spectra. The μ-peroxo complexes seem to be more stable than the corresponding μ-superoxo complexes in aqueous solution.
4-Alkyloxazolidinedione. VI. The Polymerization of α-Amino Acid N-Carboxy Anhydride
Authors: Oya Masanao , Tomizawa Mayumi , Uno Keikichi , Iwakura Yoshio
Published: July 2006

The relationships between the polymerization solvents and the conformation of the polypeptides formed were studied on the basis of the infrared absorption spectra and the X-ray diffraction diagrams of the polymers. Poly-l-α-amino-n-butyric acid and poly-l-n-valine, prepared in dimethylsulfoxide (DMSO) as a polymerization solvent, formed β-conformation, but the respective polypeptides obtained in acetonitrile had an α-conformation. The conformational structure of poly-l-α-amino-n-butyric acid changed from β to α upon reprecipitation from a solution in dichloroacetic acid with ether. On the other hand, the conformational structure of poly-Dl-α-amino-n-butyric acid did not change upon reprecipitation from a solution in formic acid and dichloroacetic acid.
Liquid Phase Chlorination of Olefins with Cupric Chloride. II. Stereochemistry of the Reactions of 2-Butenes and Cyclohexene
Authors: Koyano Takashi
Published: July 2006

Chlorination of cis-and trans-2-butenes with cupric chloride yields a mixture of meso- and dl-2,3-dichlorobutanes with meso/dl ratio of about 60/40, which is almost independent of the starting olefin configuration. For cyclohexene, trans-1,2-dichlorocyclohexane is accompanied with the cis-dichloride, the amount of which depends upon the solvent polarities. In all cases the starting olefins and the product dichlorides are sufficiently stable under the reaction conditions. The results indicate that open ionic intermediates are involved in the chlorination of simple olefins in liquid phase reaction.
Structure and Reactivity of α,β-Unsaturated Ethers. XI. Cationic Copolymerization and Acetal Addition of cis- and trans-Sthyl Ethyl Ethers
Authors: Okuyama Tadashi , Asami Nobuhiro , Fueno Takayuki
Published: July 2006

The cationic copolymerization between cis- and trans-styryl ethyl ethers in methylene chloride was investigated in the temperature range from −70 to 0°C with boron trifluoride etherate as catalyst. It was found that at lower temperatures the trans ether is more reactive than its cis isomer, although the relative reactivities are reversed at 0°C. Addition reactions of various acetals to cis- and trans-styryl ethyl ethers were carried out at 0°C with the same Lewis acid as catalyst. The relative cis-trans reactivities are largely dependent on the bulkiness of an attacking oxycarbonium ion. It was concluded that the cis isomer, which is electronically more reactive toward cations, is liable to suffer adverse steric effect, especially when the attacking carbonium ion is bulky.
Charge-Transfer Interaction and Chemical Reaction. II. Interaction of s-Triaminobenzene with Several Electron Acceptors
Authors: Yamaoka Tsuguo , Nagakura Saburo
Published: July 2006

The charge-transfer interaction was studied for systems including s-triaminobenzene as electron donor. The formation of 1 : 1 stable outer (π,π) complexes at room temperature was observed for the systems including s-trinitrobenzene, trininitrotoluene and tetracyanobenzene as electron acceptors. From the analysis of the observed absorption intensities and peak positions of charge-transfer bands, the equilibrium constants of these complexes were determined and the ionization potential of s-triaminobenzene was estimated to be 7.3–7.4 eV. Chloranil was found to form a stable outer (π,π) complex with s-triaminobenzene only at low temperature, and to be led to a substitution reaction by raising the temperature. The spectrum of the reaction intermediate, the inner (σ) complex of s-triaminobenzene with chloranil, was observed at ∼500 mμ. A tentative reaction mechanism was proposed.
Steric Structure of l-Proline Oligopeptides. IV. Proton Magnetic Resonance Studies of l-Proline Oligopeptides
Authors: Okabayashi Hirofumi , Isemura Toshizo
Published: July 2006

The NMR spectra of t-amyloxycarbonyl-l-proline oligopeptides were measured and compared with those of two poly-l-prolines, I and II. The α-CH resonance peaks of the oligopeptides were observed at sheilding values of 5.2 and 5.4 ppm, values which were in accord with those of the α-CH resonance peaks of the poly-l-prolines I and II, respectively. The behavior of the α-CH peaks was related to the conformation of the l-proline oligopeptides. Moreover, the contribution of the two terminal l-proline residues to the α-CH resonance peaks was discussed.
High Resolution NMR Study of Vinyl Chloride-Ethylene Copolymers
Authors: Misono Akira , Uchida Yasuzo , Yamada Kunikazu
Published: July 2006

The high resolution NMR spectra of vinyl chloride-ethylene copolymers obtained by trialkylboron catalyst have been analyzed. The copolymer composition could be determined from the resonance peak area, and the monomer reactivity ratios thus obtained were in good consistency with those determined from the results of elementary analysis. The fine structure of the copolymers have been elucidated in terms of the run number concept, and the distribution of dyads as well as the average sequence lengths of the monomer unit have been determined. It was found that the observed values fitted theoretical values, indicating that a terminal model holds in this copolymerization.
Studies on the Effect of Some Anionic Detergents on the Stability of Emulsions Stabilised by Partially Flocculated Sols
Authors: Jain S P , Srivastava S N
Published: July 2006

A partially flocculated Fe(OH)3 sol has been used as an emulsifying agent to stabilize toluene/water system. The electrophoretic mobilities of the emulsion thus obtained in the presence of different anionic detergents have been measured microelectrophoretically and from these values the zeta potentials have been calculated. At the charge reversal concentrations the adsorption and free energy constants were calculated. From the surface potential values the repulsion and attraction energies were evaluated which clearly showed that the flocculation occurrs in the secondary minima. The operating van der Waals constant A has been estimated by correlating the results of degree of aggregation obtained haemocytometrically with the theoretical values. It was found to be 1.05×10−12 erg. The values of interfacial tension have been reduced by the addition of these detergents which are directly connected with the chain length of the detergent and adsorption characteristics.
Surface Activities of Nonionic Polymeric Surfactants
Authors: Nakamura Masao , Sasaki Tsunetaka
Published: July 2006

The relationship between surface activity and molecular structure has been studied for the nonionic polymeric surfactants which have 2,3,4 or 6 branches of polypropylene glycol-polyethylene glycol (PPG-PEG) chain in their molecules. A linear relation, 1⁄Δγ=A+B·x⁄y has been found to hold for each series, where Δγ is the surface tension depression of surfactant solution of a given concentration from that of water, x⁄y is the molecular structure index, in which x is the weight percent of PEG group in a molecule and y is the molar weight of PPG part, and A and B are constatns. Constant A, being equal to 0.025 cm/dyn, is independent of the concentration and the number of PPG-PEG branches and corresponds to the reciprocal of surface tension lowering of an aqueous solution of infinitely large PPG polymer. Constant B decreases linearly with the logarithm of molar concentration, and increases with the number of branches. It also depends on the hydrophilic nature of the central group of molecule.
The Mechanism of the Reaction between Molecular Hydrogen and the Electron Donor-Acceptor Complexes (1:1 and 1:2) of Various Aromatic Hydrocarbons with Sodium
Authors: Ichikawa Masaru , Soma Mitsuyuki , Onishi Takaharu , Tamaru Kenzi
Published: July 2006

The mechanism of the reaction between molecular hydrogen and the electron donor-acceptor complexes (A−Na+ and A=2Na+) of various aromatic hydrocarbons (A) with sodium were studied kinetically and spectroscopically. The relative activity of each electron donor-acceptor (EDA) complex for the hydrogen uptake was associated with its electronic properties, especially with the reduction potential of its anion. It was found that the hydrogen molecule reacts more readily with stronger electron-donating EDA complexes, whose anions have higher reduction potentials. It was also suggested that, on the hydrogen adsorption over the A−Na+ and A=2Na+ films (or in their solutions), the corresponding monohydroanion complexes (AH−Na+) and NaH were produced as follows :

&2A^-Na^++H_2=AH^-Na^+NaH+A

&A^=2Na^++H_2=AH^-Na^++NaH

The behavior of AH−Na+ was closely correlated with the localization energies of electrons in the anions of the aromatic hydrocarbons.
Evaluation of Softness from the Stability Constants of Metal-ion Complexes
Authors: Misono Makoto , Saito Yasukazu
Published: July 2006

Utilizing the dual parameter equation we derived previously, we have evaluated quantitatively softness or class (b) character of metal ions on the basis of the original criteria of soft-hard classification, viz., the stability of metal-ion complexes. Various softness parameters proposed so forth have been proved insufficient to describe softness quantitatively, although they are useful for a rough classification of metal ions into soft and hard acids. Discussion is also given concerning origin of softness, especially from the viewpoint of its closs correlation with the solvation effect.
An Electron Spin Resonance Study of the 5,12-Dihydrotetracene Radical Anion and Its Ion Pairs with Alkali Metal Cations
Authors: Iwaizumi Masamoto , Isobe Taro
Published: July 2006

The 5,12-dihydrotetracene radical anion and its ion pairs with alkali-metal cations have been Investigated by electron spin resonance (ESR). It has been found that the frequency of the inversion of the radical molecule is >>108 Hz and that the unpaired electron is distributed between the benzene and naphthalene rings. Such a distribution of the unpaired electron between the two conjugated systems is assumed to occur via a hyperconjugation mechanism. On the other hand, it was observed that the proton hyperfme splittings of the radical anion are appreciably affected by the association of an alkali-metal cation. In the case of the 5,12-dihydrotetracene-potassium ionpair in THF, the hyperfine components of the methylene protons show an alternating line-width effect. On the basis of the observed effects of the alkali metal cations, a model of the ion-pair structure is proposed, and the alternating line-width effect is explained in terms of an intramolecular migration of the potassium ion from one side of the molecular plane to the other. The activation energy of this motion of the potassium ion has been estimated to be 3.1±0.2 kcal.
The Radiolysis of Liquid Nitrogen Containing Hydrocarbons. II. Acetonitrile Formation from the Solution of Ethylene
Authors: Oka Takefumi , Sato Shin
Published: July 2006

The 60Co γ-radiolysis of liquid nitrogen containing ethylene has been reinvestigated in order to elucidate the mechanism of the formation of nitrogenous products. When the conversion of ethylene was 10%, the G-values of hydrogen cyanide and acetonitrile were 0.21±0.03 and 0.05±0.01 respectively. The isotopic distributions in acetonitrile, n-butane, and acetylene were examined by using an equimolar mixture of C2H4 and C2D4 as the solute. From the analysis of these distributions, it has been concluded that acetonitrile is produced mainly from the reaction between nitrogen atoms and ethyl radicals.
Sound Velocity in Polyoxyethylene(6)laurylether Aqueous Solution
Authors: Nomoto Otohiko , Endo Harumi
Published: July 2006

The sound velocity and density of polyoxyethylene(6)lauryether and its aqueous solutions are measured, and the adiabatic compressibility is computed from these results. The virtual sound velocity was calculated in ideal mixtures by using Kudriavtsev’s formula, and above 33°C for ideal suspensions by the use of the equation of Urick and Ament for dispersed systems. Some deviations in the experimental velocity from the calculated value are ascribed to the interaction energy of mixing. This energy, or the heat of the hydration of a nonionic surfactant, is obtained as a function of the temperature. The diagrams of the density, sound velocity, and adiabatic compressibility vs. the temperature at various concentrations always exhibit a common crossing point, nearly at the cloud point. It may thus be concluded that the measurements of the sound velocity and density give a new method for determining the cloud point.
The Interaction of Oxygen with Organic Molecules. III. Electron Transfer between Oxygen and Aromatic Amines Studied by Flash Technique
Authors: Hori Mitsufusa , Itoi Hiroyasu , Tsubomura Hiroshi
Published: July 2006

Flash photolysis of aniline derivatives in various solutions has been studied in oxygenated and deoxygenated conditions. Absorption spectra of the triplet states appeared in deoxygenated liquid paraffin solutions, but no transient absorption was observed in the oxygenated liquid paraffin solutions. Transient spectra, due to the cations of the anilines, were observed in deoxygenated ethanol solutions, but none in oxygenated ethanol. In highly polar solvents—acetonitrile, water, and formamide—either deoxygenated or oxygenated, the cation was observed. In the case of oxygenated solutions, the initial yield of the cation was found to be proportional to the intensity of the flash light, indicating that the ionization is a one-photon process. These results, together with the previous findings that the photo-ionization of organic molecules in solutions are caused by the two-step, biphotonic excitation processes strongly suggest that the charge transfer states are formed between the aromatics and the oxygen molecule, either by direct excitation or via the interaction of excited anilines and the ground state of oxygen, and the charge transfer states then lead to the solvated cations and anions in highly polar solvents. The decay of the ions have been found to follow the second order kinetics.
The Photometric Determination of Minute Amounts of Iodine in Silicate Rocks
Authors: Yonehara Norinobu , Yoshida Minoru , Iwasaki Iwaji
Published: July 2006

A rapid and sensitive method for the determination of minute amounts of iodine in silicate rocks has been developed. A rock was fused with potassium hydroxide, and the cake was treated with water and sulfuric acid. The iodine in the solution was reduced to iodide by sodium sulfite, and was then oxidized to free iodine by sodium nitrite. The free iodine thus obtained was extracted with carbon tetrachloride and then back-extracted with a sodium hydroxide solution. The iodine in this aqueous layer was determined photometrically by a method based on the catalytic effect of iodine on the color-fading of ferric thiocyanate. By the proposed method, amounts of iodine as low as 0.007 μg in a 1-g sample of silicate rocks can be determined. Application to some igneous rock samples gave results with a relative standard deviation of less than 7.2%, except for very low concentrations.
Reactions of Potassium Iron Carbonylate with Olefins and Alkyl Halides
Authors: Masada Hiromitsu , Mizuno Mitsuyuki , Suga Sohei , Watanabe Yoshihisa , Takegami Yoshinobu
Published: July 2006

Potassium iron carbonylate, KHFe(CO)4, reacted with ethyl acrylate, crotonate, 3-butenoate, styrene, and α-olefins at 40–70°C under an atmosphere of carbon monoxide. Methylmalonate was selectively obtained from the acrylate by treatment of the reaction mixture with an alcoholic iodine and hydrogen chloride solutions. Dipotassium iron carbonylate, K2Fe(CO)4, reacted with β-bromopropionate to give mainly methylmalonate. Isomerization of β-ethoxycarbonylpropionyliron carbonylate to the α-isomer occurred readily in contrast to isomerization of acylcobalt carbonyl. Both crotonate and 3-butenoate gave ethylmalonate as a major product and methylsuccinate and glutarate as minor ones. The results suggest that α-ethoxycarbonylbutyliron carbonylate is more predominant than the corresponding β- and γ-isomers in equilibrium state. This is in striking contrast to the case of acylcobalt carbonyl. Styrene yielded two isomeric aldehydes, α- and β-phenylpropionaldehydes. Ethyl caproate and enanthate were obtained from 1-pentene and 1-hexene, respectively in poor yield.
Polyamino-Zucker. V. Modellreaktionen zur Aminierung cyclischer Nitrodiole
Authors: Nakagawa Toshio , Sakakibara Tohru , W. Lichtenthaler Frieder
Published: July 2006

On treatment of lr,3c-diacetoxy-2t-nitrocyclohexane (3) or its 1,3-dimesyloxy analogue 4 with primary amines or ammonia, nitrodiamines (5–11) are obtained via an elimination-addition mechanism. Similar aminations of lr-methyl-1-nitrocyclohexane-2c,6c-diol (15) or its di-O-acetate 16 give C-methyl branched nitrodiamines (12–14), which are also formed by reaction of glutaraldehyde with nitromethane and amines. Structures and conformations of the products obtained were deduced from IR and NMR data.
Metal(II) Complexes of Ethylenediaminemonoacetic Acid (EDMA). Polarographic Studies of Cadmium(II) and Lead(II)-EDMA Complexes
Authors: Fujii Yuki , Ueda Teiko , Kodama Mutsuo
Published: July 2006

In the present paper, the d.c. polarographic behavior of cadmium(II) and lead(II) ions in ethylenediaminemonoacetate (EDMA) solutions was studied systematically. Since these metal(II) ions in an EDMA solution behave reversibly in a polarographic electrolysis, the compositions and the stability constants of cadmium(II)- and lead(II)-EDMA complexes could be estimated successfully from the shift of the half-wave potential of these metal(II) ions due to the complex formation with EDMA. The cadmium (II) ion was found to form complexes of 1-to-1 and 1-to-2 compositions with EDMA, and the electrode reaction mechanism was established to be:

(Remark: Graphics omitted.)

The successive formation constants of cadmium(II)-EDMA complexes, (K1)cdx and (K2)cdx were determined to be 3.01×108 and 5.65×104 respectively. On the other hand, the lead(II) ion forms only one complex with 1-to-l composition. In the presence of the chloride ion, the lead(II) ion was found to form a mixed ligand complex involving the chloride ion as well as a normal complex, PbX+, and the electrode reaction could be formulated as:

(Remark: Graphics omitted.)

The equilibrium constants, (K1)Pbx(=[PbX+]/([Pb2+]·[[X−])) and KpbxCl(=[PbXCl0]/([PbX+]·[Cl−])), were determined to be 1.69×108 and 1.01×10 respectively. The effect of the zinc(II) ion on the half-wave potential of the cadmium(II) ion in an EDMA solution was also studied. From the positive shift of the half-wave potential due to the presence of the zinc(II) ion, the formation constant of the zinc(II)-EDMA complex with a 1-to-1 composition was estimated to be 1.58×108.
The Stereochemistry of Hydrogenation and Hydrogenolysis. XI. The Stereochemistry of the Reduction of 3-Methyl-4-chromanone
Authors: Hanaya Kaoru
Published: July 2006

3-Methyl-4-chromanone (VIII) was reduced with a metal hydride complex, by the Meerwein-Ponndorf method and by catalytic hydrogenation. When VIII was reduced with a metal hydride complex and the Meerwein-Ponndorf method, trans-3-methyl-4-chromanol (IX) was produced as the main product. In the catalytic hydrogenation, VIII gave a cis-3-methyl-4-chromanol (X) as the main product over Raney nickel, but over the palladium catalyst the trnas isomer was larger than the cis isomer. These results indicate that, on Meerwein-Ponndorf and metal hydride reductions, the more stable product was formed as the main product; in the catalytic hydrogenation over the Raney nickel catalyst, VIII seems to be adsorbed mainly on the opposite side of the methyl group of the C-3 position and is hydrogenated to give the cis isomer, whereas, over the palladium catalyst, hydrogenation seems to proceed under the effect of “product development control over the catalyst” and the trans isomer is produced in a high yield.
Hammett Correlation in Mass Spectra. Substituent Effects for the Migratory Aptitude of the Aryl Group in the Unimolecular Ion Decomposition of Diaryl Sulfones
Authors: Nagai Toshikazu , Maeno Tetsuo , Tokura Niichiro
Published: July 2006

The migratory aptitude of the aryl group in the unimolecular ion decomposition reaction of p-substituted diaryl sulfones has been examined. Both electron-donating and -withdrawing substituents showed to be capable of increasing the migratory aptitude. On the other hand, a kinetic treatment allowed a satisfactory Hammett correlation (ρ=0.3) on the total abundances of the fragment ions. The energy of the cleaved bond and the production stability were shown to be important factors in the effect of the substituent on the ion decomposition.
Chemical Reactivity of Adamantane and Related Compounds
Authors: Fujimoto Hiroshi , Kitagawa Yoshihiko , Hao Hideyuki , Fukui Kenichi
Published: July 2006

The chemical reactivity of hydrogens in adamantane and substituted adamantanes has been calculated. The results of calculation have shown that the bridgehead hydrogens are most reactive toward electrophilic reagents or radicals. The chemical reactivity of hydrogens in diamantane, triamantane, and tetramantane has also been predicted. A discussion has been made of the stable configuration of the 1-adamantyl cation, radical, and anion and of the nature of the back-side conjugation between the two tertiary carbons in these species. A mode of the electrocyclic polymerization of p-quinodimethane to form polyamantane has been predicted on the basis of the symmetry properties of the frontier orbitals in the pi and sigma parts of p-quinodimethane.
Studies on Aminosugars. XXIV. The Facile Elimination of the Derivatives of a Pyranosid-4-ulose
Authors: Tsuchiya Tsutomu , Suo Kiyohiko , Umezawa Sumio
Published: July 2006

Methyl 3-azido-3-deoxy-α and β-d-xylopyranoside are prepared. The oxidation of the 2-O-benzoylated derivative of the above-mentioned α-anomer with the Pfitzner-Moffatt reagent leads to the facile elimination of the elements of benzoic acid and the formation of the 4-azido derivative of 5,6-dihydro-α-pyran-5-one. The 3-ethoxycarbonylamido derivative obtained from the above mentioned 3-azido derivative is oxidized similarly to afford the 4-ethoxycarbonylamido derivative of 5,6-dihydro-α-pyran-5-one. The mechanisms of these elimination reactions are discussed.
Kinetics and Mechanism of the Silver Catalysed Oxidation of Malic Acid by Potassium Peroxydisulphate
Authors: Agrawal G L , Bhattacharya Arun K
Published: July 2006

Preliminary experiments showed that the reaction between malic acid and potassium peroxydisulphate is very slow. The reaction rate becomes a measurable value at 25°C by introducing the Ag+ ion as a catalyst. The total order of the reaction has been found to be nearly unity. The effect of the concentration of catalyst and malic acid has been studied. The temperature coefficient of the reaction between the temperature range of 30 and 45°C is 1.76 and the mean value of the energy of activation is 10.9 kcal. The frequency factor and entropy of activation are 16.8×105 sec−1 and −41.1 e.u. respectively. The probable mechanism for the reaction has been suggested.
n-π* Electronic Emission Spectrum of o-Methoxybenzaldehyde Vapour
Authors: Srivastava M P , Singh O N , Singh I S
Published: July 2006

The n-π* vapour emission spectrum of o-methoxybenzaldehyde has been excited in transformer discharge in flowing vapours of benzene and the substance. In the spectrum the C=O stretching frequency is the most prominent and its found to form progression of bands. The entire spectrum has been analyzed in terms of several ground state frequencies.
Comparison of the Recoil Reactions in the 80mBr-CH4 and 82mBr-CH4 Systems
Authors: Tachikawa Enzo
Published: July 2006

The reactions of 80Br and 82Br excited by the isomeric transition processes with CH4 have been compared with each other. Similar reaction processes; energetic and thermal ionic, are involved in both cases. However, the isotope effect appears in the energetic process to form CH3Br, but not in the thermal ionic process to form CH3Br and CH2Br2. The difference in the γ-transitions of 80mBr and 82mBr to the ground states is responsible for the above results. It is concluded that at least a part of the recoil Br atoms enter chemical combinations with surrounding molecules within 10−8sec, the life-time of the excited 80Br atom. Furthermore, the yield of CH380Br, lower than that of CH382Br, is discussed on the basis of the different kinetic energies achieved on the Br atoms.
Thinning of Nonionic Detergent Films
Authors: Yamanaka Teruko
Published: July 2006

The effect of added electrolytes on the thinning of single vertical film formed from nonionic detergent solution has been studied. Addition of the electrolytes did not show an appreciable effect on the thinning of the film in the region of interference fringes. Specific effects of anions upon the “blackening time” (the time necessary for turning the total film area completely into a black film) were observed similarly to those on the cloud point. The order of magnitude of these effects followed the lyotropic series, which may be explained qualitatively by the effects on the dehydration of detergent molecules and on the electrical double layer of the film. The effect of the electrolytes on aqueous ionic detergent film was also examined. It was mainly explained by their influence on the electrical double layer.
Kinetics of Alkaline Hydrolysis of Esters. II. Unsaturated Esters and Oxalic Esters
Authors: Sharma R C , Sharma M M
Published: July 2006

The kinetics of alkaline hydrolysis of some typical esters, with unsaturation in the alkyl and the acyl portions, was studied. It was found that, in general, unsaturation results in enhancing the rate as compared to that of the corresponding saturated esters, provided that there is no conjugation between the double bond and the carboxyl carbonyl group. Oxalic esters hydrolyze relatively very fast due to the close proximity of the two ester groups. Rate constants for the alkaline hydrolysis of di-n-propyl-, di-isopropyl-, di-n-butyl-, di-s-butyl-, dicyclohexyl- and di-β-chloroethyl oxalates were obtained by using the theory of mass transfer accompanied by fast pseudo first-order reaction (diffusion method).
Far-Infrared Spectra and Lattice Vibrations of Barium Chloride Dihydrate
Authors: Fukushima Kunio , Kataiwa Hiroaki
Published: July 2006

The far-infrared spectra of barium chloride dihydrate and its deutero analog were measured in the region of 60–4000 cm−1. The assignment of the infrared bands due to crystal water and crystal heavy water was made on the basis of the band frequency shift associated with deuteration. The optically-active lattice vibrations were calculated in order to assign the far-infrared bands and elucidate the nature of the vibrations.
Microwave Spectra of o-Difluorobenzene in the Excited Vibrational States
Authors: Hatta Aritada , Kozima Kunio
Published: July 2006

The microwave spectra of o-difluorobenzene in various excited vibrational states have been measured in the frequency region from 10- to 30-GHz. The R- and Q-branch transitions of the a-type have been assigned. The rotational constants for the ν1=1 state are A=3254.77, B=2226.85, and C=1324.67 MHz, and those for the ν2=1 state are A=3269.76, B=2220.48, and C=1322.94 MHz. The inertial defects in the excited states have been used in order to make vibrational assignments. It is very probable that the ν1 and the ν2 mode are the out-of-plane vibration of A2 and the in-plane vibration of A1 respectively.