bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mercury-Photosensitized Reaction of Acetylene
Authors: Shida Shoji , Tsukada Masao 
Published: July 2006

Abstract
The mercury-photosensitized reaction of acetylene has been studied with equimolar mixtures of C2H2 and C2D2 under various conditions of pressure, temperature, and additives. It is shown that the distribution of isotopically substituted benzenes can be explained by a modified excited state mechanism equally as well as, or more favourably than by the free radical mechanism. The results on deuterium-acetylene mixtures photosensitized by Hg(3P1), however, suggest that benzene is also formed by the reaction of hydrogen atoms and acetylene molecules. The rates of benzene formation and of the polymer formation increased gradually with pressure in low pressure region to attain a maximum and then decreased. Argon very strongly inhibited the benzene formation and, to a less extent, the polymer formation. The primary process is explained by assuming the formation of a transient complex of a triplet mercury atom and an acetylene molecule.
The Electronic Spectra of the Anion Radical Salts Derived from Halogen-substituted p-Benzoquinones
Authors: Iida Yôichi 
Published: July 2006

Abstract
The anion-radical salts derived from p-chloranil, 2,5-dibromo-3,6-dichloro-1,4-benzoquinone, and p-bromanil were prepared. The absorption spectra in an acetone solution and the diffuse reflection spectra of the solid salts were examined. These solid salts were then classified into three groups, namely, those showing the spectrum of the anion-radical monomer, those showing a strong charge-transfer band characteristic of the solid salts, and, finally, those showing not only the spectrum of the anion-radical monomer but also an intermolecular charge-transfer band. The mode of intermolecular interaction in these anion-radical salts was discussed according to this classification. Their magnetic behaviour was also speculated upon on the basis of the charge-transfer interaction.
Molecular Structure and the Effect of Large-Amplitude Vibration of Carbon Suboxide as Studied by Gas Electron Diffraction
Authors: Tanimoto Mitsutoshi , Kuchitsu Kozo , Morino Yonezo 
Published: July 2006

Abstract
The molecular structure of carbon suboxide, C3O2, has been studied by the sector-micro-photometer method of gas electron diffraction. The C=O and C=C distances (rg) have been determined to be 1.1632±0.0013 Å and 1.2894±0.0022 Å, respectively, where the uncertainties represent estimated limits of error. The observed mean amplitudes for three nonbonded atom pairs and their shrinkages are found to be much larger than those expected for ordinary molecules, with linear framework. A usual harmonic approximation up to the quadratic terms of displacements cannot account for the observed values in this molecule. This indicates that the πu bending vibration ν7 has a very low frequency (an effective frequency being about 68 cm−1) and that this vibration is essentially a bending motion of the valence angle of the central carbon atom, in agreement with recent spectroscopic studies. The effect of the large-amplitude vibration on mean amplitudes and shrinkages has been studied in detail by using a model, which assumes that atomic motions take curvilinear paths in the ν7 vibration with the valley in the potential surface running along the loci of fixed bond lengths. The potential function for this bending motion has been estimated by a least-squares analysis on the observed structural parameters. The potential function is given by V(Q7)=(23±5)Q74−(100±31)Q72 (cm−1), where the uncertainties representing random standard errors take the upper and lower signs in the same order and Q7= sin α⁄0.145 (amu1⁄2 Å). The potential rises steeply with increasing angle of bending, α=1⁄2[180°∠–(C=C=C)], and appears to have a small hump at α=0. This “quasi-linear” potential function is consistent with the recent experimental estimates by Seip et al. within experimental errors, but the double-minimum nature of the potential is subject to a further critical examination by other experimental methods.
The Precise Coulometric Titration of the Acidic Primary Standard using Amperometric End-point Detection
Authors: Yoshimori Takayoshi , Matsubara Ikuko 
Published: July 2006

Abstract
The sensitive amperometric end-point procedure (Anal. Chem., 23, 1662 (1951)) with an antimony electrode is used in the titrations of acids. The cyclic voltammetric curves of the electrode indicate the possibility of the use of the above method for the titration of acids. The purities of potassium biphthalates (primary standard substances) are determined directly by precise coulometric titration with this end-point location. The standard deviations of the results (99.999%) are 0.007 or 0.008%. The purity of the benzoic acid prepared as the standard material for the calorimeter is also determined by this method. The standard deviation of these results (99.993%) is 0.009%.
Dielectric Relaxation of Esters in Benzene Solutions
Authors: Krishnaji  , Srivastava S C , Nath Dina 
Published: July 2006

Abstract
Dielectric relaxation times and distribution parameters of three esters in benzene solutions have been evaluated using three methods, viz., Cole-Cole arc plot method, Higasi’s single frequency method and the Gopal Krishna method. Three microwave frequencies have been used to determine a′ and a″ apart from the static and optical frequencies for a0 a∞. The distribution parameters obtained from Cole-Cole arc plot and Higasi’s method are in good agreement showing that the sploes a′ and a″ have been determined accurately. In these esters the values of the distribution parameter are high. Since the dipole-dipole interactions are negligible in dilute solutions, the higher values of the distribution parameter suggests the existence of multiple relaxation processes.
The Reactions of Phosphonium Ylides and Oxosulfonium Methylide with Sulfenamide Derivatives
Authors: Mukaiyama Teruaki , Kumamoto Takanobu , Fukuyama Shinichi , Taguchi Takeo 
Published: July 2006

Abstract
It was found that vinyl sulfide derivatives were obtained in good yields by the reactions of carbonyl compounds with α-phenylthioalkylidenetriphenylphosphorane. Phosphorane was prepared by the equimolar reaction of alkylidenetriphenylphosphorane and N-phenylthio-N-methylacetamide. It was established that, differing from the case of alkylidenetriphenylphosphorane, di-methyloxosulfonium methylide reacted with N-phenylthiophthalimide and N-phenylthiosuccin-imide to give N-bis(phenylthio)methylphthalimide and N-bis(phenylthio)methylsuccinimide, re-specitively.
The Friedel-Crafts Reaction of 2,3-Dimethylbenzofuranyl Ketones and the Corresponding Carboxylic Esters
Authors: Kawase Yoshiyuki , Okada Tomoko , Miwa Toshio 
Published: July 2006

Abstract
The acetylation of methyl 2,3-dimethyl-4- and -7-benzofurancarboxylates was carried out by the action of acetyl chloride and aluminum chloride in carbon disulfide at room temperature to afford the 6-acetyl compounds; these compounds were converted to keto-acids by hydrolysis, and then to the known dicarboxylic acid or to the known 6-acetylbenzofuran. The alkylation of acetyl and methoxycarbonyl derivatives of 2,3-dimethylbenzofuran was carried out by the action of n- or iso-propyl bromide and aluminum chloride in carbon disulfide at reflux temperature, both the bromides furnishing the same isopropylated product. The crude products from the 4-acetyl- and 4-methoxycarbonyl-benzofurans could not be purified, but 2,3-dimethyl-6-isopropyl-4-benzofurancarboxylic acid was obtained by the hydrolysis of the product from the latter. In the cases of 5-acetyl- and 5-methoxycarbonyl-benzofurans, the isopropylation occurred at the 7-position and the products were converted to the same carboxylic acids, while the isopropylation occurred at the 4-position in the cases of 6-acetyl- and 6-methoxycarbonylbenzofurans, and diisopropylation occurred in the case of 7-methoxycarbonylbenzofuran.
Chemical Species Produced from Iodine in Stretched PVA Sheets
Authors: Djojosubroto Harjoto , Tanizaki Yoshié , Hoshi Toshihiko 
Published: July 2006

Abstract
A qualitative dichroism analysis has been made on chemical species produced from iodine in stretched sheets of polyvinyl alcohol. The absorption bands at 290 mμ and 360 mμ have been attributed to the bent triiodine ion, and the transition moments of these bands have been found to be parallel to each other. From the optical density ratio (Rd) curve, the presence of a hidden band at about 420 mμ has been pointed out, and the band has been assigned to the absorption by the linear triiodide ion. Three different chemical species are absorbed in the visible region. By comparing the Rd values, the numbers of iodine atoms in the respective species have been estimated.
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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.