bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electronic Absorption Spectra and Geometry of Molecule Ions Generated from Stilbene and Related Compounds. I. Dianions
Authors: Suzuki Hiroshi , Koyano Kinko , Kunii Tosiyasu L 
Published: July 2006

Abstract
Stilbene and some of its alkyl-substituted derivatives were reduced with alkali metals to dianions in 1,2-dimethoxyethane. From comparison of the electronic absorption spectra of these dianions with one another and with the results of semiempirical SCF-MO-CI calculation of the π-electronic state, the geometries of the dianions were inferred to be as follows: (a) the preferred geometry of a sterically unhindered dianion, such as the dianion of stilbene, is probably planar or nearly planar; (b) when alkyl substituents are introduced into the central ethylenic carbon atoms, the steric interference caused by the substituents is relieved chiefly by the rotation about the central ethylenic bond; (c) the steric interference caused by ortho methyl substituents seems to be comparatively small or to be relieved by the rotation about the bonds connecting benzene rings to the ethylenic carbon atoms as well as the ethylenic bond. From the influence of alkali-metal cations on the spectra of the dianions, it was inferred that the dianions exist mainly as contact ion aggregates in which the counter-ions are located near the central ethylenic bond, one probably almost above an ethylenic carbon atom and the other almost below the other ethylenic carbon atom.
The Syntheses and Reactions of Sulfenyl-substituted Sulfonium Ylides
Authors: Hayasi Yosio , Nozaki Hitosi 
Published: July 2006

Abstract
Unstable dimethylsulfonium (phenylthio)methylide (2) is prepared in a THF solution from the corresponding sulfonium salt by treating it with n-butyllithium. Sulfenyl-substituted stable phenacylides 6a and 6b are obtained in three ways. The ylide 6a decomposes at 120°C in benzene to give (E)-9, the dimer of benzoyl(phenylthio)carbene. In contrast, the heating of 6a in ethanol affords ethanolysis products (11, 12) and ethyl benzoate. The alkylation of 6a and 6b with trimethyl- and triethyloxonium fluoroborate gives the vinylsulfonium salt 13. The ylide 2 reacts with (Z)- and (E)-1,2-dibenzoylethylene and with diethyl fumarate to give cyclopropanes, 15 and 16 respectively.
Ligand Effects in the Cooligomerization of Butadiene and Ethylene by a Nickel-based Catalyst System
Authors: Inoue Yoshio , Kagawa Teruhiko , Uchida Yasuzo , Hashimoto Harukichi 
Published: July 2006

Abstract
The cooligomerization of butadiene and ethylene catalyzed by a NiCl2–AlEt3–phosphine system was investigated. The cooligomerization product was 1,cis-4-hexadiene or/and 1,trans-4,9-decatriene. Bidentate ditertiary phosphines had remarkable effects on the reaction. The effects of ditertiary phosphines are also described.
C-C Bond Fission in Carboxamides. Kinetic Studies on Alkaline Hydrolysis of Substituted α-Nitroisobutyranilides
Authors: Sayo Hiroteru , Ohomori Hidenobu , Umeda Tsuneji , Masui Masaichiro 
Published: July 2006

Abstract
Alkaline hydrolysis of substituted α-nitroisobutyranilides, trichloroacetanilide and trifluoroacetanilide was studied kinetically at various hydroxyl ion concentrations in 10% aqueous dioxane. The formation of phenylcarbamate ion as an intermediate was confirmed on hydrolysis of the α-nitroisobutyranilides and trichloroacetanilide but not trifluoroacetanilide. All the substituted α-nitroisobutyranilides except the p-nitro derivative were found to undergo C–C bond fission exclusively. Trichloroacetanilide and the p-nitro derivative of α-nitroisobutyranilide underwent both C–C and C–N bond fission. The mechanism of C–C bond fission in the hydrolysis of α-nitroisobutyranilides was explained on the basis of the solvent isotope effect as a fast reversible addition of a hydroxyl ion followed by a rate-determining decomposition of the tetrahedral addition intermediate to form a phenylcarbamate ion and a carbanion.
Photolysis of Phenylazo p-Tolyl Sulfones
Authors: Kobayashi Michio , Fujii Sadao , Minato Hiroshi 
Published: July 2006

Abstract
Photolysis of phenylazo p-tolyl sulfone and p-chlorophenylazo p′-tolyl sulfone in aromatic solvents at room temperature was investigated. The products were analyzed, and the isomer distribution and partial rate factors in arylation of mono-substituted benzenes were determined. The results indicate that the photolysis involves formation of aryl radicals and p-tolylsulfonyl radicals.
Aromatic Arylation with Aryl Radicals. IV. The Kinetic Hydrogen Isotope Effect in the Aromatic Phenylation with Phenyl Radical
Authors: Kamigata Nobumasa , Minato Hiroshi , Kobayashi Michio 
Published: July 2006

Abstract
Anisole-4d, chlorobenzene-4d, chlorobenzene-d5, nitrobenzene-d5, m-dinitrobenzene-d4, and 1,3,5-tri-t-butylbenzene-d3 were phenylated with phenyl radical generated from PhN2BF4–NaNO2, N-nitrosoacetanilide or phenylazotriphenylmethane(PAT), and the isotope effect in these phenylations was determined. The values of kH⁄kD in the phenylations of chlorobenzene and 1,3,5-tri-t-butylbenzene are not so larger than unity, whereas that in the phenylation at the 2-position of m-dinitrobenzene with PAT was very large (∼11).
Reactive Species Produced by Laser Irradiation. The Reaction of CN Radicals with Hydrocarbons
Authors: Taki Ko , Kim Pil Hyon , Namba Susumu 
Published: July 2006

Abstract
The reactive species, CN radicals, were produced by the irradiation of the focused laser beam on the metal cyanide target. The reaction of CN radicals with low-molecular-weight hydrocarbons gave fragmented hydrocarbons and CN (and NC) compounds, while that with hydrogen gave hydrogen cyanide. From the experimental results, it seems that the products may be formed mainly by the reaction of the reactive species with fragment hydrocarbon radicals which are produced by the collision of the high-temperature reactive species (CN*) with the parent hydrocarbons.
Studies of the Synthesis of Furan Compounds. XXVII. Derivatives of 3-(5-Nitro-2-furyl)acrylonitrile
Authors: Hirao Ichiro , Kato Yasuhiko 
Published: July 2006

Abstract
In a continuation of our previous papers concerning the syntheses with 5-nitro-2-furonitrile, 2-(5-nitro-2-furyl)vinyl-1,2,4-oxadiazoles and -1,2,3-triazoles were prepared from 3-(5-nitro-2-furyl)acrylonitrile (I). When I was treated with diazomethane in ether, 4-[2-(5-nitro-2-furyl)vinyl]-1,2,3-triazole (II) was obtained. II gave N-acetyl (IIa) and N-morpholinomethyl (IIb) compounds when treated with acetic anhydride and when the Mannich reaction was utilized respectively. 3-(5-Nitro-2-furyl)acrylamide oxime (III) was prepared by the usual method from I and hydroxylamine. The treatment of III with benzaldehyde and acid anhydrides or chlorides afforded 3-[2-(5-nitro-2-furyl)vinyl]-5-phenyl-4,5-dihydro-1,2,4-oxadiazoline (IV) and O-acyl-3-(5-nitro-2-furyl)acrylamide oximes (IIIa—IIIe) respectively. The O-acyl-amide oximes were found to cyclize to 3-[2-(5-nitro-2-furyl)vinyl]-5-alkyl-1,2,4-oxadiazole (V–VII) in their thermal analyses.
A Negative Ion-molecule Reaction in Nitroethylene
Authors: Shiga Tetsuo , Yamaoka Hitoshi , Arakawa Kazuo , Sugiura Toshio 
Published: July 2006

Abstract
The formation of negative ions and the negative ion-molecule reaction in nitroethylene by electron impact have been studied. The nondissociative resonance electron capture of the nitroethylene molecule led to the formation of the molecular negative ion. The ionization efficiency curves and the appearance potentials of several fragment negative ions and the molecular negative ion were measured. The dimer negative ion of nitroethylene was found to be formed by the ion-molecule reaction between the molecular negative ion and a neutral nitroethylene molecule, and the rate constant of this ion-molecule reaction was estimated to be approximately 3.2×10−13 cc molecule −1sec−1.
The Solid Complex of Aminomalonic Acid with β-Alanine and Its Thermal Decomposition
Authors: Nishijo Juziro , Imanishi Isamu , Hashizume Genzo 
Published: July 2006

Abstract
For the crystallization of aminomalonic acid with several amino acids from an aqueous solution, solid complex formation was studied by means of an X-ray diffractometer. No complex formation of aminomalonic acid with α-alanine, dl-α-amino-n-butyric acid, l-isoleucine, l-leucine, dl-serine, dl-norleucine, α-amino-iso-butyric acid, dl-valine, dl-threonine, or dl-norvaline was observed. However, with β-alanine, the formation of a solid complex with a molar ratio of 1:1 was ascertained. When this solid complex was analyzed by the differential thermogravimetric method in air at a heating rate of 1.4°C/min, a decarboxylation reaction, accompanied by endothermic and exothermic peaks, was observed at 115–133°C. On the other hand, the decarboxylation of aminomalonic acid alone occurred in the temperature range of 112–138°C. The areas of the endothermic peak, which was attributed to the decarboxylation, and the endothermic peak, which was attributed to the crystallization energies of γ-glycine and β-alanine, were, respectively, about 3 and 3/2 times those of the peaks observed in the case of aminomalonic acid. It was also observed that the exothermic process proceeded in two steps. The X-ray analysis of the products of the decarboxylation process suggested that the complex first melted to become amorphous to X-rays, and that it was then decarboxylated to amorphous glycine and amorphous β-alanine with these subsequent crystallization. The two-step exothermic process was explained in terms of a somewhat earlier crystallization of amorphous glycine than in terms of that of the amorphous β-alanine. The activation energy of the solid complex was estimated to 119.2 kcal/mol from the thermogravimetric curve. This large value of the apparent activation energy may be considered to result because the solid complex turns to an amorphous phase much more sensitive to decarboxylation prior to decomposition, and the steep slope of the thermogravimetric curve which results from the rapid decarboxylation of the amorphous gives the large apparent activation energy.
The Crystal and Molecular Structure of Averufin
Authors: Katsube Yukiteru , Tsukihara Tomitake , Tanaka Nobuo , Ando Kazuto , Hamasaki Takashi , Hatsuda Yuichi 
Published: July 2006

Abstract
The crystal structure of averufin has been determined by means of the X-ray diffraction method. The space group is P21/a, with a=23.70 Å, b=7.24 Å, c=9.48 Å, and β=105.5°. The structure was solved by the interpretation of the three-dimensional Patterson function and was refined by the least-squares method. The molecular structure is in agreement with that proposed by Roffey and Grandjean. In the crystal, the molecules are linked to form a molecular pair by a OH···O hydrogen bond across the center of symmetry.
The Electrical Properties of Iodine Complexes of N-Methyl-and N-Ethyl-phenothiazines and Their Mixtures
Authors: Kan Kazuo , Matsunaga Yoshio 
Published: July 2006

Abstract
The electrical resistivities and Seebeck coefficients of 2: 3 iodine complexes of N-methyl- and N-ethyl-phenothiazines were measured. The former complex exhibits a resistivity of 2.0 ohm cm and an activation energy for semiconduction of 0.20 eV at 20°C. Applying the equation of Johnson and Lark-Horowitz for the Seebeck coefficient of an intrinsic semiconductor, the ratio of the electron mobility to the hole mobility in the N-methyl-phenothiazine complex was found to be 2.08 and the electron mobility was estimated as 0.23 cm2/Vsec. The resistivity of the N-ethylphenothiazine complex is 74 ohm cm, and the activation energy 0.15 eV at 20°C. In this complex, the hole appears to be more mobile by a factor of five than the electron. Lichtenecker’s logarithmic rule is observed neither by the resistivity nor by the activation energy of the mixtures of these two complexes.
The Syntheses of 3-(Carboxyalkyl)salicylaldehyde Derivatives and Their Copper Chelates
Authors: Tanaka Tsuguo 
Published: July 2006

Abstract
In order to study the influence of the side-chain carboxylic acid groups on the formation of the metal chelates, 5-bromo-3-carboxymethyl-, 5-methyl-3-β-carboxyethyl-, and 5-chloro-3-β-carboxyethyl-salicylaldehyde (2a, b c) were synthesized. The green binuclear copper chelates of these aldehydes, di-μ-aquo-bis-(5-bromo-3-carboxymethylsalicylaldehyde)-, di-μ-aquo-bis-(5-methyl-3-β-carboxyethylsalicylaldehyde)-, and di-μ-aquo-bis-(5-chloro-3-β-carboxyethylsalicylaldehyde)-dicopper (11a, b, c) yielded the green binuclear bis-ethylenediimine chelates (12a, b, c), while bis-(5-bromo-3-carboxymethylsalicylaldehyde)-, bis-(5-methyl-3-β-carboxyethylsalicylaldehyde)-, and bis-(5-chloro-3-β-carboxyethylsalicylaldehyde)-ethylenediimine (14a, b, c) gave a brown (13a) and gray-purple (13b, c) mononuclear copper chelates. The reduction of 14a, b, c with sodium borohydride yielded the ihexadentate ligands N,N′-bis-(5-bromo-2-hydroxy-3-carboxymethylbenzyl)-, N,N′,-bis-(5-methyl-2-hydroxy-3-β-carboxyethylbenzyl)-, and N,N′-bis-(5-chloro-2-hydroxy-3-β-carboxyethylbenzyl)-ethylenediamine (15a, b, c), which proved useful for the spectrophotometric determination of the copper (II) ion from solutions containing copper (II) and nickel (II) ions, and the iron (II) ion from solutions containing iron (II) and nickel (II) ions.
Hydrogenation and Hydrogenolysis. XIV. The Hydrogenation of Ethyl p-Tolyl Ether over Platinum Metal Catalysts
Authors: Nishimura Shigeo , Uramoto Masayoshi , Watanabe Tetsuo 
Published: July 2006

Abstract
The hydrogenation of ethyl p-tolyl ether (1) in ethanol has been studied with five unsupported platinum metals as catalysts, mainly with the purpose of estimating the yields of ethyl 4-methyl-1-cyclohexenyl ether (2) formed as intermediate. Except for ruthenium catalyst, the hydrogenation of 1 in ethanol was accompanied by the formation of acetal 3, ketone 4 and alcohol 5 which seem to be related to the formation of 2. The amounts of 2 and the related compounds which were desorbed from the catalyst surface have been estimated to be 32–33% for Ru, 32–34% for Rh, 72–76% for Pd, 3.7% for Ir and 4.7% for Pt, by application of both kinetic and extrapolation methods. A good agreement was obtained between the results from the two methods. The proportion of hydrogenolysis increased for the catalyst metals in the order Pd&lt;Ru&lt;&lt;Rh&lt;Ir&lt;Pt. With platinum catalyst a noticeable amount of toluene was formed along with methylcyclohexane. The hydrogenation of ethyl 4-methyl-3-cyclohexenyl ether (6), one of the other intermediates of the hydrogenation of 1, has also been studied in ethanol. Hydrogenolysis occurred extensively with palladium and rhodium catalysts, but much less with ruthenium, iridium and platinum catalysts. The hydrogenation route of 1 and its relation to hydrogenolysis and stereochemistry of hydrogenation of 1 are discussed with reference to the formation and hydrogenation of its intermediates.
Platinum(II)-Olefin Complexes Containing Amino Acids. III. Optical Inversion and Substitution of Coordinated Olefins in Optically Active trans(N)-Chloro-l-prolinato-olefinplatinum(II) Complexes in Organic Solvents
Authors: Konya Kazuo , Fujita Junnosuke , Kido Hiroaki , Saito Kazuo 
Published: July 2006

Abstract
Optical inversion of coordinated 2-methyl-2-butene and trans-2-butene in trans(N)-chloro-l-prolinato-olefinplatinum(II), trans(N)-[PtCl(l-prol)(olefin)] (nitrogen of l-prolinate ion is trans to the olefin), i.e. the interconversion between diastereoisomers (Fig. 1), has been kinetically studied in acetone by measuring the decrease in the intensity of circular dichroism (CD) in near ultraviolet region. The rate was measurable only in the presence of olefin, and can be expressed by the relation, Rate=k[complex][olefin]. The Ea and the ΔS\eweq values for the two complexes are 7.8±1.0 and 9.0±1.0 kcal/mol, and −44 and −39 entropy unit, respectively. The coordinated trans-2-butene is replaced by other olefins, 2,3-dimethyl-2-butene, 2-methyl-2-butene, trans-2-butene (optical inversion), and styrene, under similar conditions to give the same rate formula. The second order rate constant increases in the given order. The inversion seems to take place via bimolecular mechanism with excessive olefin as nucleophile. The corresponding complexes containing styrene and its para derivatives give such an inversion much faster in the absence of excess of olefin. With change of para substituents, the rate increases in the order, methoxy&lt;methyl&lt;hydrogen&lt;chloro&lt;nitro. This seems to be related with their electrondrawing ability.
Thermal Decomposition Reactions of Metal Oxalato Complexes in the Solid State. I. Thermographic Studies of Metal Oxalato Complexes
Authors: Nagase Kenzo 
Published: July 2006

Abstract
The thermal decomposition reactions of metal oxalato complexes in the solid state were studied by the TG and DSC methods. The results from TG indicated that the thermal stability of the anhydrous complex decreases approximately with the increase in the electron affinity of the central metal ion. From DSC, the complexes can be divided into two groups, giving endothermic and exothermic peaks on the decomposition of their anhydrous complexes respectively. The two enthalpy changes, ΔH, corresponding to the dehydration and to the decomposition of the anhydrous complexes, are also presented.
Magnetic Susceptibilities and Broad-Line PMR Spectra of Dichloro(pyridazine)copper(II) and Related Compounds
Authors: Emori Shuji , Inoue Motomichi , Kubo Masaji 
Published: July 2006

Abstract
The magnetic susceptibilities of CuX2L (X: halide ion, L: 1,2,4-triazole, pyridazine, phthalazine, 4-amino-1,2,4-triazole) conform to the linear Ising model or Heisenberg model, indicating the presence of linear magnetic chains in the crystals. Fermi contact shift observed in the broad-line PMR spectrum indicates the diffusion of a positive hole from a copper atom to the molecule of heterocycles. The magnitude of the exchange integrals is related to the spin densities on the atoms of the heterocycles.
The Syntheses of 5-Azidotropolones and Their Electrophilic, Nucleophilic, and Thermal Reactions
Authors: Toda Takashi , Horino Hiroshi , Nozoe Tetsuo 
Published: July 2006

Abstract
Several 5-azidotropolones were synthesized by the reaction of sodium azide with tropolone diazonium salts which has been prepared from the corresponding 5-aminotropolones. Most of the 5-azidotropolones thus obtained were stable except for the 4-alkyl derivatives. Their electrophilic substitution reactions took place at their 3- and 7-positions, and also their hydroxyl groups behaved like those of other tropolones. 5-Azidotropolone methyl ether did not react with aromatic amines, but it did with aliphatic amines and guanidine to give 2-aminotropone derivatives and 1,3-diazaazulene derivative. The thermolysis of 5-azidotropolone and its methyl ether afforded 5-aminotropolone and its methyl ether respectively; however, 5-azido-4-phenyltropolone gave indolo[3,2-d]tropolone.
The Second CMC of the Aqueous Solution of Sodium Dodecyl Sulfate. II. Viscosity and Density
Authors: Kodama Michiko , Miura Masaji 
Published: July 2006

Abstract
Our viscosity and density studies of an aqueous solution of sodium dodecyl sulfate have revealed that the 2nd critical micelle concentration (CMC) exists in addition to the 1st CMC and that the 2nd CMC is greatly influenced by such additives as sodium chloride, dodecyl alcohol, and benzene; these results are in good agreement with those obtained from the conductivity measurements described in the previous paper. The reduced viscosity of the micelle (ηsp.m/Cm) vs. Cm curve showed a knick at the concentration corresponding to the 2nd CMC as obtained by Tyuzyo and his co-workers. The molar volume of the hydrated micelle was calculated by using the equation: ηr.m=1+2.5φm+14.1φm2; it has been found to decrease at about the 2nd CMC, similarly to the partial specific volume (\barv) of SDS obtained from the density measurement. This may be attributed to a change in the micelle structure at the 2nd CMC, caused by a variation in the type of aggregation and by a decrease in the counter-ion binding by the micelle.
The Quenching of Hg(63P1) Atoms by Molecular Hydrogen as Investigated by ESR Spectroscopy
Authors: Farmer James B , Shimokoshi Kazuo 
Published: July 2006

Abstract
The gas phase electron spin resonance technique has been applied to study the quenching efficiency of Hg(63P1) mercury atoms by molecular hydrogen. The concentration of hydrogen atoms produced by the mercury photosensitized decomposition of molecular hydrogen in a flow apparatus was followed as a function of the partial pressure of hydrogen with argon, neon, and hydrogen as carrier gases. The kinetic equations derived from the reaction mechanism proposed was shown to be in agreement with the experimental observations. The total quenching rate kH was evaluated from the experimental results.
The Molecular and Crystal Structures of Two Isomeric Dihydrofukinolidol Sulfites, C15H22O5S
Authors: Furusaki Akio , Watanabé Tokunosuké 
Published: July 2006

Abstract
The molecular and crystal structures of two isomeric dihydrofukinolidol sulfites, C15H22O5S, have been studied by means of an X-ray analysis. The two sulfites, called S-1 and S-2, both crystallize in the orthorhombic space group P212121, with four molecules in each unit cell. The cell dimensions are a=12.544, b=14.457, and c=8.545 Å for S-1, and a=12.919, b=14.375, and c=8.496 Å for S-2. The reflection intensities were measured visually from equi-inclination integrating Weissenberg photographs taken with CuKα radiation. The structures were solved by the tangent formula procedure and refined by the block-diagonal-matrix least-squares method, the anisotropic thermal motions being assumed for all the atoms. The final R factor was 10.8% for S-1 and 11.2% for S-2. The absolute configurations of the molecules were determined by using the anomalous dispersion effects of the sulfur atoms for CuKα radiation. It was found that the six-membered ring containing the sulfite group in S-1 takes the chair conformation, while the same ring in S-2 has the twist boat form. The exocyclic S–O bond in the two sulfites are both axially oriented, and the other corresponding parts of the two isomers are closely similar to each other.
Vapor Pressure of a Mixed System of Asphaltene and Organic Solvent
Authors: Sakanoue Shinji , Endo Mitsuo 
Published: July 2006

Abstract
The vapor pressure of a system in which it is assumed that the maltene component in petroleum asphalt has been replaced by an organic solvent, i.e., a mixed system of an asphaltene component and an organic solvent, was measured over a wide range of composition. The experimental results were then analyzed on the assumption that such a system is a binary system and that the equation μ1=μ1°+RTln(1–v2)+(1–1⁄z)v2+χ1v22 which Flory and Huggins derived for the chemical potential of a solvent of a linear, high-polymer solution which is not relatively dilute is applicable; the volumetric ratio, z, of the asphaltene particle and solvent molecule and the value of the parameter, χ1, of the interaction of the asphaltene and solvent molecules were obtained. The above results made it clear that mixed systems of asphaltene plus chloroform and carbon tetrachloride all form a homogeneous phase over the entire composition range, but in the case of a cyclohexane system, separation into 2 phases occurs in the mixed composition range of 3.0 vol%−40 vol% asphaltene and a dilute phase of 3.0 vol% asphaltene and a concentrated phase of 40.0 vol% coexist. It may be assumed from the above results that there is a possibility of the presence of a state in which separation into 2 phases is also present in the case of asphalt.