bluuebunny/crossref_metadata_2025 huggingface dataset:
Free Radical Reactions in Organic Electrode Processes. V. Anodic Cyanation of Some Monosubstituted Benzenes
Authors: Susuki Tosaku , Koyama Kikuhiko , Omori Akira , Tsutsumi Shigeru
Published: July 2006

The anodic reaction between cyanide ions and monosubstituted benzenes in methanol has been investigated. An examination of the products has indicated that the reaction proceeded by means of the formation of nucleus-cyanated products. The solvent perhaps also participates concurrently in this anodic reaction leading to the formation of methoxylated compounds. The results offer a striking contrast in isomer distribution between these two substitutions. The substituents on the benzene rings had a pronounced effect on the yield of the cyano compounds. The reactivity of the aromatic compounds toward the anodic cyanation decreased in the following order:

anisole >> toluene > ethylbenzene > cumene >> benzene >> methyl benzoate.

These results have been interpreted as resulting from the generation of an aromatic ion radical at an anode by the loss of a π-electron from each molecule.
The Syntheses of Dimethylfuro Derivatives of 4-Hydroxycoumarins and Benzofuro[1]benzopyranones
Authors: Kawase Yoshiyuki , Nanbu Mutsumu , Miyoshi Fumihisa , Kawamura Hiroshi
Published: July 2006

4′,5′-Dimethyl-4-hydroxyfuro[2′,3′:7,8]coumarin (2) and its 3-phenyl, 3-(2-methoxyphenyl), and 3-(2,4,5-trimethoxyphenyl) derivatives (4, 5 and 6), and also their isomers, 4′,5′-dimethyl-4-hydroxyfuro[3′,2′:6,7]coumarins (14, 15, 16 and 17), were prepared by the action of ethyl carbonate or of ethyl chlorocarbonate on the corresponding 2,3-dimethyl-4- or isomeric 6-hydroxy5-benzofuranyl ketones. Two furocoumarins (2 and 14) were also obtained in poor yields by the condesnation of 2,3-dimethyl-4- or 6-hydroxybenzofuran with malonic acid. The action of hydroiodic acid on the furocoumarins 5 and 6 afforded 2,3-dimethyl-5H-benzofuro[3,2-c]furo[2,3-h][1]benzopyran-5-one (8) and its 7,8-dihydroxy derivative (9) respectively; 8 was also synthesized by building up the dimethylfuran ring on 3-hydroxy-6H-benzofuro[3,2-c][1]benzopyran-6-one, while 9 was also synthesized by the oxidative coupling of 2 with catechol. On the other hand, the action of pyridine hydrochloride on 5 caused the closure of the furan ring towards the 2-position, giving l,2-dimethyl-6H-benzofuro[2,3-b]furo[2,3-h][1]benzopyran-6-one (11), which had a new pentacylic ring system; the only demethylated compound (12) was also obtained. The structure of 11 was confirmed by its IR and UV spectra and by the formation of 12 upon its alkaline hydrolysis. The action of aluminum chloride on 5 also gave 12. Analogously, isomeric l,2-dimethyl-6H-benzofuro[3,2-c]furo[3,2-g][1]benzopyran-6-one (20) and its 8,9-dihydroxy compound (21) were also synthesized.
Sur la Structure des Dimères du N-Phényl Acétone-d-glycéraldimine
Authors: Funabashi Masuo , Yoshimura Juji
Published: July 2006

N-phényl acétone-d-glycéraldimine dimérise facilement en présence d’un soupçon de l’acide acétique et donne deux dimères, dont la structure y comprise la configuration absolue partielle a été etablie par l’analyse spectrométrique et la décomposition chimique comme étant un 4-anilino-2-(2′,2′-diméthyl-1′,3′-dioxolanne-4′-yl)-1,2,3,4-tétrahydroquinoléine-3-spiro-4″-(2″,2″-diméthyl-1″,3″)dioxolanne. Lorsqu’on hydrolyse ces dimères partiellement avec l’acide acètique aqueux á 70%, on peut isoler 1,2,3,4,5,6-héxahydro-4-hydroxy-1,5-méthano-2,6-benzoxazocine-11-spiro-4′-(2′,2′-dimethyl-1′,3′)dioxolanne avec un rendement d’environ 40% et enmême temps l’aniline est detaché. Néanmoins, le dérivé N-acétyle d’un dimère n’a pas détaché l’aniline á la même condition d’hydrolyse.
Gel Filtration of Mixtures of Surfactants on Sephadex
Authors: Tokiwa Fumikatsu , Ohki Kenji , Kokubo Isao
Published: July 2006

The gel filtrations of mixtures of sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfate (STS) have been studied for different mole ratios of STS/SDS with varying total concentrations. Above the critical micelle concentration (CMC) of the mixture, two retention volumes V1obs and V2obs were obtained from the elution curve, and the difference between V1obs and V2obs depends on the total concentrations of the mixture. The initial part of the effluent contains only STS, which means that the separation of STS from the mixture occurs after passing through the column. These results have been discussed by taking into consideration the equilibrium between monomers and micelles for the mixtures of the two surfactants. It is shown that the separation factor is determined by the CMC values of the two surfactants—the greater the ratio CMCA/CMCB (CMCA>CMCB), the greater the degree of separation.
ESR and Optical Studies of the Reaction Intermediates Produced from Phenyl Halides by Dissociative Electron Attachment in γ-Irradiated Organic Glasses at 77°K
Authors: Noda Syozi , Fueki Kenji , Kuri Zen-ichiro
Published: July 2006

ESR and optical studies have been made of dissociative electron attachment by phenyl halides and reaction intermediates produced in γ-irradiated glassy solid matrices at 77°K. Dissociative electron attachment by phenyl halides is an efficient process and the ratio of cross sections C6H5I/C6H5Br/C6H5Cl for this process in MTHF glass is 1.5/1.0/1.0. The phenyl radical produced abstracts a hydrogen atom from solvents (MTHF, 3MP) at 77°K and is stable in aqueous alkali-metal hydroxide glass. A part of 3MP radicals in a γ-irradiated solution of phenyl bromide in 3MP at 77°K disappear by a first-order process for which k=4.3×10−2 min−1. γ-Irradiated 3MP glasses containing phenyl halides exhibit the optical absorption spectra having characteristic absorption bands in the visible and UV region which are assigned to solute cations and hydrogen-adducts respectively.
Infrared and Raman Spectra of 2, 3-Dichloro-2, 3-dimethylbutane
Authors: Koide Tsutomu , Oda Tsutomu , Ezumi Kiyoshi , Iwatani Koji , Kubota Tanekazu
Published: July 2006

Infrared spectra of Cl(CH3)2C–C(CH3)2Cl were obtained over the region from 400 cm−1 to 4000 cm−1 at room temperature in the gas phase, dilute solutions, and KBr-disk. In the KBr-disk case, spectra were also obtained at lower temperatures. In the gas phase, and in the disk at lower temperatures, spectral simplifications were obtained. Raman spectra at room temperature were photographed for the crystalline sample, and also for 17–25% solutions in several solvents. The coexistence of trans-gauche isomers in the high-temperature solid phase of this compound was verified by spectral comparison between trans- and gauche-isomers. The energy difference between two isomers was estimated to be about 1.5 kcal/mol from temperature changes in the infrared intensities.
Thermal Properties of Alkali Halide Crystals with the CsCl-type Structure. I. Construction of a Calorimeter for the Temperature Region 1–20°K and Heat Capacities of Caesium Bromide and Caesium Iodide between 1.5 and 300°K
Authors: Sorai Michio , Suga Hiroshi , Seki Syûzô
Published: July 2006

An adiabatic low-temperature calorimeter, capable of measuring the heat capacities of solid or liquid between 1.4 and 21.0°K, was constructed. A mechanical thermal switch is used for cooling the sample cell, the temperature of which is measured with a doped germanium thermometer. The resistance-temperature calibration data for the resistor was fitted to a function of the form log10R=A⁄T+B+CT+DT2. By using this formula the thermodynamic temperature scale is represented to within ±0.02°K and by combining the correction curves the final deviations of the calibration data from the thermodynamic temperature scale were within ±0.003°K in the whole temperature range investigated. The heat capacity measurements of CsBr and CsI crystals were made with two kinds of adiabatic calorimeter assemblies, one for the temperature range 1.4 to 21°K and the other for the range 12 to 300°K. Values of the heat capacity Cp°, entropy S°, enthalpy function (H°−H0°)/T, and Gibbs energy function −(G°−H0°)/T at 298.15°K are: 12.441, 26.785, 10.415, and 16.370 for CsBr and 12.571, 29.127, 10.788, and 18.339 for CsI, respectively, in cal·mol−1.°K−1.
An Internal-Monitor Method for the Activation Analysis of Silver in Palladium with Thermal Neutrons
Authors: Oka Yoshinaga , Kato Toyoaki , Tsai Hui-Tuh , Nomura Koichi
Published: July 2006

An internal-monitor method has been developed to eliminate many of the errors probable with activation analysis. This method involves the measurement of the composed radioactivity of the species to be analyzed and of an appropriate internal-monitor, and the estimation of the ratio of the induced activity of both the species. The present report will describe the principles and the applicability of the method to the determination of a trace amount of silver in palladium by means of thermal neutron irradiation. After the silver activity is chemically separated from the irradiated sample, the γ-ray spectrum corresponding to the mixture of 110mAg and 111Ag formed by the β− decay of 111Pd is measured. Synthetic mixtures of silver and palladium with known weight ratios have been prepared to check the accuracy of the method. A good proportionality has been obtained between the ratios of the 110mAg to 111Ag activities and the ratios of the concentrations. By using this relationship, silver analysis can easily be achieved. Contents of silver in a palladium sample down to about 1 ppm can be determined with a relative error of within ± 2%. By this method the errors which arise from neutron flux irregularities and self-shielding effects can be avoided, and no correction for chemical yield is necessary.
Electronic Absorption and Emission Spectra of 9, 10-Dichloroanthracene and 9, 10-Dibromoanthracene Crystals
Authors: Tanaka Jiro , Shibata Masao
Published: July 2006

The electronic absorption spectra of three crystalline modifications of anthracene derivatives have been measured; they are the α and β form of 9, 10-dichloroanthracene and 9, 10-dibromo-anthracene. The assignment has been presented for each absorption band. The charge transfer absorption which is regarded to the transition between two stacked molecules has been observed in the α-form of 9, 10-dichloroanthracene; also a Rydberg type transition which has an out of plane polarization is found in this crystal starting at 290 mμ. It is unusually broad and is regarded as a band to band transition. The emission band has been measured at different temperature; it is found that excimer type emission is most prominent in the β-form of 9, 10-dichloroanthracene, in which intermolecular approach in the excited state will occur with less difficulty. A criterion for strong, medium, and weak interactions in the excited state is presented by comparing the shift, and the shape of the emission band with the intermolecular vibrational spacing. These results show that the charge transfer interaction and excimer formation are greatly dependent on the relative orientation of molecules, the π-electron overlap, and the difficulty of intermolecular approach in the excited state, particularly with its correlation to the steric repulsion of the bulky substituent groups.
A Study on the Yield of (γ, p) Reactions with 20 MeV Bremsstrahlung
Authors: Oka Yoshinaga , Kato Toyoaki , Nomura Koichi , Saito Tatsuya , Tsai Hui-Tuh
Published: July 2006

The yields of the (γ, p) reactions on 13 elements up to an atomic number of 80, irradiated with 20 MeV bremsstrahlung, have been given through the γ-ray spectrometric measurements of the resultant activities. The yield values, as measured in absolute disintegration rates at the end of irradiation per mole per roentgen, have been plotted against atomic number of the target nuclides. The shape of the yield curve thus obtained is similar to that of the curve for the photo-proton yield as a function of atomic number. The yield values are 105 order of magnitude in the lower-Z region, and drop rapidly with increasing atomic number up to a Z of 50. For barium and mercury targets, a yield value of 2.2×104 was obtained. Neutron excess nuclides were found to be restrictive to the (γ, p) processes. The present results permit a study of general behavior of the (γ,p) reaction yields as well as of the applicabilities of the resultant activities to photoactivation analyses for many elements distributed throughout the periodic table.
Dimerization of Acrylonitrile by Ruthenium Chloride
Authors: Misono Akira , Uchida Yasuzo , Hidai Masanobu , Shinohara Hiroyuki , Watanabe Yoshihisa
Published: July 2006

The end-to-end dimerization of acrylonitrile was effected with a ruthenium trichloride trihydrate catalyst under a hydrogen atmosphere, thus obtaining a mixture of cis- and trans-1, 4-dicyano-1-butene as the main products. Under nitrogen, however, only very small amounts of these products were formed. The reaction occurred at temperatures of 120–200°C under moderate hydrogen pressures in alcoholic media such as ethanol. The effects of various salts or electron-donating compounds on the catalysis were examined.
Synthesis of Trimethylhydroquinone from p-Xylene
Authors: Sato Kikumasa , Fujima Yoshito , Yamada Arihiro
Published: July 2006

The synthesis of trimethylhydroquinone from p-xylene was carried out via two routes; one includes the formylation of p-xylene, followed by nitration, and the other, the chloromethylation of nitro-p-xylene. The oxidation of the trimethylanilines, VI and IX, prepared from 2,5-dimethyl-6-nitrobenzaldehyde and 2,5-dimethyl-3-chloromethylnitrobenzene and their subsequent reduction gave trimethylhydroquinone (TMH) in appreciable yields.
Studies of Aminosugars. XVIII. Syntheses of Amino Derivatives of Schardinger α-Dextrin and Raffinose
Authors: Umezawa Sumio , Tatsuta Kuniaki
Published: July 2006

In continuing our study of the relationship between structural and biochemical characteristics of aminoglycosides, amino-deoxy derivatives of polysaccharides have been synthesized. The six primary hydroxyl groups of Schardinger α-dextrin and the three primary hydroxyl groups of raffinose have successfully been replaced by amino groups respectively, to give hexa-(6-amino-6-deoxy)-cyclohexaglucan (α-1,4) (IV) and 1″,6,6″-triamino-1″,6,6″-trideoxyraffinose (X). Their structures were confirmed by their NMR and IR spectra and by the studies of their chemical reactions. It has been found that hexa-(6-amino-6-deoxy)-cyclohexaglucan (α-1,4) showed significant antitumor activity.
Studies of the ζ-Potential of Natural and Synthetic Fibers in Dye Solutions. XVIII. ζ-Potential and Surface Dyeability of Heat-Set Nylon 6 Fiber in an Acid Dye Solution
Authors: Suzawa Toshiro , Saito Tomoyuki
Published: July 2006

In order to ascertain the relation between the change in the fibrous fine structure and the dyeability of nylon 6 fiber caused by its heat-setting, the ζ-potential, the surface dye adsorption, and the total dye adsorption of the heat-set nylon 6 fiber in an acidic solution (pH 3.0) of acid dye—Orange II were determined. The crystallinity and the birefringence of the fiber increase in the order of the untreated, the wet-heat-treated, and the dry-heat-treated fiber. The isoelectric points of the untreated, the wet-heat-treated, and the dry-heat-treated fiber are pH 5.4, pH 4.6, and pH 2.8 respectively. With the increase in the dye concentration, the sign of the ζ-potential of the untreated and the wet-heat-treated fiber in a dye solution change from positive to negative because of the electrostatic bonds between the NH3+ of the fiber and the dye anion, RSO3−, while the ζ-potential of the dry-heat-treated fiber increases its negative value because of the van der Waals’ forces between the fiber and the dye. The surface dye adsorption, as calculated from the difference between the surface charge density, Δσ, of the system with dye and that without dye, increases in any case as the dye concentration increases. The total dye adsorption increases as the dye concentration increases and attained the plateau regions at higher dye concentrations. The surface dye adsorptions become smaller in the order of the untreated, the dry-heat-treated, and the wet-heat-treated fiber. The total dye adsorptions become smaller in the order of the wet-heat-treated, the untreated, and the dry-heat-treated fiber. The differences in behavior among the fibers may be attributed to the adsorption of the dye to the loosely-packed portions in the amorphous region of the wet-heat-treated fiber, in addition to the differences in crystallinity and birefringence among the fibers. Moreover, the surface areas covered by adsorbed dye molecules, which were calculated from the reciprocal of the slope of the surface dye adsorption vs. the total dye adsorption curve of each fiber, were 1.8, 4.0, and 0.6×106cm2/g fiber in the order of the untreated, the wet-heat-treated, and the dry-heattreated fiber.
Studies of Poly-2-vinylpyridine. V. Temperature Dependence of the Intrinsic Viscosity and Osmotic Pressure of an Ethanol Solution
Authors: Arichi Shizuo
Published: July 2006

The viscosity of a series of 10 fractions of poly-2-vinylpyridine and the osmotic pressure of a fraction of the same polymer in ethanol were measured at several temperature. The temperature coefficients of the intrinsic viscosities of all the fractions measured were found to be completely negative. The Mark-Houwink equations for molecular-weight-homogeneous samples were obtained in ethanol at 10, 25, 40, and 65°C. The Flory constant, K=[η]θ⁄M1⁄2, obtained by the method of Fixman was found to be 13.0×10−4 at 25°C; this value is considerably larger than those estimated from the intrinsic viscosity data of this polymer in non-acidic solvents. The K value lowered to an ordinary level when it contained 2.7 n of dry ammonia in ethanol at 25°C. The values of the thermodynamic interaction parameters for dilution, ψ1 and θ, were obtained from the viscosity data; the former was negative, but nearly zero (−0.02), while the latter was unusually large (397°C). The excess molar entropy of dilution obtained from the measurements of the temperature dependence of the osmotic pressure was found to be negative, but almost zero, which was in accordance with the value of ψ1 described above; the excess molar heat of dilution obtained in the same way was found to be completely negative. Thus, the exhothermic interaction and negative excess entropy for dilution in this system were studied somewhat quantitatively.
Determination of the Self-diffusion Coefficient of Nickel Atoms in Nickel Sulfide
Authors: Fueki Kazuo , Oguri Yasuo , Mukaibo Takashi
Published: July 2006

The self-diffusion coefficient of ions or atoms in such crystals as halides, oxides and sulfides can be determined from the rate of the diffusion-controlled solid-state reaction as well as by the tracer method. In the present study, the self-diffusion coefficient of nickel atoms in nickel sulfide was determined from the rates of the sulfidation and desulfidation of nickel sulfide in H2S-H2gas mixtures. The results agreed well with the data obtained by the previous investigators employing the tracer technique.
Extraction-Photometric Determination of Osmium with Thenoyltrifluoroacetone
Authors: Rangnekar Asha V , Khopkar S M
Published: July 2006

The study of the liquid-liquid extraction of some platinum group elements (A. V. Rangnekar and S. M. Khopkar, Bull. Chem. Soc. Japan, 38, 1696 (1965); 39, 2169 (1966)), with fluorinated β-diketones showed that, osmium reduced to trivalent state with hydroxylamine hydrochloride forms a red chelate with 2-thenoyltrifluoroacetone, TTA. The chelate is readily extracted in benzene giving strong absorbance at around 440 mμ.
The Coprecipitation and Spectrophotometric Determination of Iron as 8-Hydroxyquinolinate
Authors: Shigematsu Tsunenobu , Matsui Masakazu , Munakata Megumu , Sumida Takayuki
Published: July 2006

The coprecipitation and spectrophotometric method, which is likened to the solvent extraction and spectrophotometric method, was applied to the following system for the first time; ferric ion was coprecipitated as 8-hydroxyquinolinate with an organic coprecipitant, and was determined spectrophotometrically after the precipitate was dissolved with an organic solvent. The effect of the ligand concentration on the pH vs. absorbance curve in the present method was apparently similar to that for solvent extraction. A nearly constant absorbance was obtained above pH 4 at a ligand concentration of 4×10−3  m. Over 100 mg of o-phenylphenol, an almost quantitative coprceipitation was obtained, though the absorbance decreased gradually as the coprecipitant was increased. The effect of diverse ions was also examined. Titanium(IV), vanadium(V) and molybdenum(VI) interfered considerably, while others have little effect on the absorbance. The method was applied to the determination of trace amounts of iron in natural waters and reagent grade sodium chloride.
Synthesis of Pyridoxine. II. The Preparation of Pyrrole Derivatives
Authors: Murakami Masuo , Takahashi Kozo , Matsumoto Jun , Tamazawa Kazuharu , Murase Kiyoshi , Iwamoto Hidenori , Iwanami Masaru
Published: July 2006

A new method for the synthesis of 2-acetyl-3, 4-diethoxycarbonylpyrrole and its derivatives by the Diels-Alder reaction is described, and the reaction mechanism of their formation is discussed.
Thermal Transformation of Alkali Salts of Aromatic Carboxylic Acids. V. Reaction of Potassium and Sodium Salts of Naphthoic Acids
Authors: Dozen Yasuhiko
Published: July 2006

The cadmium fluoride-catalyzed thermal transformation of potassium and sodium salts of naphtoic acids has been investigated. At the initial reaction stage both potassium and sodium α-naphthoate gave naphthalene and naphthalene-1, 2- and 1, 3-dicarboxylates, which were converted to naphthalene-2, 3- and 2, 6-dicarboxylates. The products composition, however, differed between potassium and sodium salts. Potassium β-naphthoate gave naphthalene and naphthalene 1, 2- and 2, 3-dicarboxylates, which were then further converted to naphthalene-2, 6-dicarboxylate. On the other hand, sodium β-naphthoate gave naphthalene and naphthalene-1, 2- and 2, 3-dicarboxylates. In the presence of potassium cyanate, potassium α- and β-naphthoates gave a high yield of naphthalene-2, 6-dicarboxylate. The mechanism of the reaction was discussed.
Organic Catalysts. IV. The Role of the Iron as an Oxidation Catalyst in Copper-Iron-Polyphthalocyanine
Authors: Inoue Hiroo , Kida Yasuji , Imoto Eiji
Published: July 2006

The role of the iron in copper-iron-polyphthalocyanine in the catalytic action in the oxidation of acetaldehyde ethylene acetal and cyclohexene was investigated on the basis of the inhibition of the reaction by the treatment of copper-iron-polyphthalocyanine with iron-binding agents and oxidizing agents. The catalytic action of copper-iron-polyphthalocyanine decreased or disappeared upon the addition of 2-phenylimidazole and pyridine to the reaction system, and upon the treatment with bromine or concentrated hydrochloric acid in the presence of air. However, the reduction of the oxidized copper-iron-polyphthalocyanine with ascorbic acid or sodium thiosulfate recovered the catalytic activity. Furthermore, the catalytic activities of iron-metal-polyphthalocyanines (metal; V, Cr, Mn, Co, Ni, Cu and Zn) and copper-metal-polyphthalocyanines (metal; V, Cr, Co, Ni and Zn) in the oxidation of acetaldehyde ethylene acetal were investigated. The former groups showed the catalytic actions, but no catalytic actions were observed in the latter groups. The catalytic activities of iron-metal-polyphthalocyanines increased with a decrease in the activation energy of the electrical conductivity of the polymer. From these results, it was presumed that the Fe(II) ions located in the conjugated system act as active sites for the activation of oxygen and for the decomposition of peroxide.
Organic Catalysts. V. Specific Catalytic Properties of Copper-Iron-Polyphthalocyanine in the Oxidation of Aldehydes
Authors: Inoue Hiroo , Kida Yasuji , Imoto Eiji
Published: July 2006

Copper-iron-polyphthalocyanine showed a specific catalysis for the oxidations of the substituted benzaldehydes and the saturated aldehydes with oxygen. The catalytic activity of copper-iron-polyphthalocyanine was solvent-dependent: tetrahydrofuran, ethanol, acetonitrile, ethyl acetate and anisole inhibited the oxidation of benzaldehyde by copper-iron-polyphthalocyanine and oxygen, while benzene and acetone resulted in catalytic oxidation. Benzaldehyde and the saturated aliphatic aldehydes in benzene were oxidized catalytically with copper-iron-polyphthalocyanine and oxygen to afford the corresponding peroxy acids and acids in quantitative yields. Furthermore, oxygen was absorbed with no induction period; the rate of oxygen absorption was in the range of 8–13 ml/min. On the other hand, the unsaturated aliphatic aldehydes, cinnamaldehyde and acrolein, were oxidized with a very slow rate of oxygen absorption in spite of the existence of copper-iron-polyphthalocyanine in the reaction system. p-Methylbenzaldehyde and p-chlorobenzaldehyde were oxidized by copper-iron-polyphthalocyanine and oxygen in Induction periods of about 8 and 15 min respectively, thus affording the corresponding peroxy acids and acids. However, no oxidations of p-nitrobenzaldehyde, p-hydroxycarbonylbenzaldehyde, p- and m-hydroxybenzaldehyde, p- and m-methoxybenzaldehyde and p-dimethylaminobenzaldehyde with copper-iron-polyphthalocyanine and oxygen were observed.
A Study on Mixed Vanadium Catalysts for the Ammoxidation of Xylene
Authors: Ito Masatomo , Tanaka Hazime , Matsumoto Akira
Published: July 2006

The phase composition and the physicochemical properties of an antimony-vanadium catalyst and a chromium-vanadium catalyst for the ammoxidation of xylene were studied by X-ray diffraction method, differential thermal analysis, infrared absorption analysis and ESR measurement. An antimony-vanadium catalyst consisted essentially of SbVO4 which contained no double covalent bond V=O, while a chromium-vanadium catalyst consisted essentially of a chemical compound which was different from CrVO4. SbVO4 and CrVO4 were hard to be reduced with ammonia at 400°C, while a chemical compound in the chromium-vanadium system was reducible. The activity and the selectivity of reaction were affected by the nature and the distribution of metal ions and oxygen ion on surface.
A Measure of the Electron-donating Power and Electron-accepting Power of Liquid Organic Compounds
Authors: Kagiya Tsutomu , Sumida Yūzō , Inoue Tokuji
Published: July 2006

A quantitative study has been made of the measurement of the electron-donating nature and the electron-accepting nature of various liquid organic compounds. The position of the O–D or C=O absorption band of a liquid compound which contained a small quantity of methanol-d or of acetophenone was measured by means of an infrared spectrophotometer. The relative magnitude of the electron-donating nature or of the electron-accepting nature of the compound was compared by a measurement of the perturbation which it produced on the O–D vibrational band of methanol-d or on the C=O vibrational band of acetophenone. The electron-donating power or the electron-accepting power of a compound is defined as the relative difference (counted as wave numbers) of the O–D or the C=O absorption band observed in the compound from that in benzene. From the results, it was found that, in a homologous series, the electron-donating power decreased with an increase in the ionization potential in the gaseous phase, or with an increase in the pKb value in the liquid phase, and that it increased linearly with the co-ordination power to diethyl zinc. It was also found that the electron-accepting power increased with an increase in the electron affinity in the gaseous phase and decreased with an increase in the pKa value in the liquid phase. Moreover, the various liquid organic compounds, classified into four typical groups, were considered on the basis of their electron-donating and electron-accepting power.
A Definition of Selectivity of Nucleophilic Solvation in a Binary Solution
Authors: Kagiya Tsutomu , Sumida Yūzō , Inoue Tokuji
Published: July 2006

This is the third paper of a series in which the behavior of nucleophilic solvation is investigated by a measurement of the position and the area of the O–D vibrational band of methanol-d. In a binary solution which consisted of two components remarkably different in electron-donating power, the relation between the mol fraction (n1) of the S1 component and the area fraction (n1) of S1 was not a straight line, but a concave or convex curve. This fact suggests that a component co-ordinates selectively to a deuterium atom in a methanol-d molecule. The following definition of the selectivity of nucleophilic solvation to methanol-d as a cation model of the S2 component to the S1 component is proposed:

(Remark: Graphics omitted.)

The selectivity of the S2 solvent to the S1 solvent was considered in detail in connection with the equilibrium constant of the nucleophilic solvation to methanol-d of the solvent; the selectivity was also found to be defined as the ratio of the equilibrium constants of the solvents used. Since there was a correlation between the equilibrium constants and the electron-donating powers, it was concluded that the selectivity of an S2 solvent to a standard solvent, S1 could be quantitatively estimated by measuring only the position of the O–D vibrational band of methanol-d in each solvent.
Electron Spin Resonance Study on Ultraviolet Light Irradiated Benzene Adsorbed on Silica Gel and Alumina
Authors: Tanei Tadayoshi
Published: July 2006

Benzene adsorbed on silica gel was irradiated at 77°K with ultraviolet light. Three kinds of samples, with different degree of adsorption, were examined. ESR spectra were strongly dependent on the amount of benzene adsorbed and three different spectra were observed; (1) six-line spectrum with a splitting value of 6 gauss, assigned to phenyl radical, (2) seven-line spectrum with a splitting value of 4.5 gauss, assigned to benzene cation radical, and (3) apparent nine-line spectrum with 2.4 gauss splitting due to benzene dimer cation radical. Upon raising temperature, benzene cation radical was found to transform into benzene dimer cation radical. In UV-irradiated benzene-alumina system, cyclohexadienyl radicals were observed in addition to the ion radicals. It is suggested that the above reaction may be occurred by two photon absorption process involving the excitation of triplet benzene.
Synthesis of Chelating Agents. V. 1,2,3-Triaminopropanehexaacetic Acid and Its Acid Dissociation Scheme
Authors: Miyazaki Mitsumasa , Moriguchi Yoshiki , Ueno Keihei
Published: July 2006

1,2,3-Triaminopropane-N,N,N′,N′,N″,N″-hexaacetic acid (TAPHA) was synthesized by the carboxymethylation of 1,2,3-triaminopropane. The acid dissociation scheme of the ligand was studied by means of potentiometric titration, infrared absorption spectroscopy and proton nuclear magnetic resonance spectroscopy. It is found that TAPHA exists as a zwitter ion in aqueous solution, in which protons attach to each nitrogen atom of 1- and 3-carbon, and that the dissociations of first four and the last two steps correspond to the dissociations of carboxylic protons and ammonium protons, respectively. The stepwise proton dissociation constants of the ligand is determined as pK1≈2, pK2=2.43, pK3=3.52, pK4=4.30, pK5=8.26 and pK6=9.88 (μ=0.1, 25°C).
The Mössbauer Spectra of Various Natural Minerals
Authors: Takashima Yoshimasa , Ohashi Shigeru
Published: July 2006

The Mössbauer spectra have been measured for sixteen samples of natural minerals, including siderite, vivianite, garnets, olivines, pyroxenes, and other silicate minerals, The spectra were analyzed for the isomer shifts and quadrupole splittings, and the information thus obtained was correlated with the oxidation states of irons and the crystal structure of minerals. The relative abundances of the various sites present in a given mineral were also estimated by measuring the relative intensities of the absorption peaks in the resolved spectrum of the mineral. All the basic Mössbauer spectral patterns observed for the natural minerals are presented in graphic form.
Kinetic Study of the Gas-phase Oxidation of Propylene in a Propylene-excess Atmosphere under Pressure
Authors: Masai Mitsuo , Echigoya Etsuro , Morikawa Kiyoshi
Published: July 2006

Reaction-rate equations are derived for oxygen, acetaldehyde, propylene oxide, carbon monoxide, and ethylene on the basis of a plausible reaction scheme. These rate equations are shown to fit the experimental results obtained using a flow-type reactor. It seems most reasonable to conclude that the above reaction mechanism is correct. The type of flow of the reactant gas through the reactor used in this work can be practically regarded as a plug flow from the measurements of the resisdence time distribution using the pulse-tracer method.
The Chemiluminescence of Indole Derivatives. III. On the Mechanism of the Chemiluminescence of 2,3-Dimethylindole and 5-Substituted- 2,3-dimethylindoles in the Dimethyl Sulfoxide - Alkali System
Authors: Sugiyama Noboru , Akutagawa Masamoto , Yamamoto Hiroshi
Published: July 2006

A bright green light is observed on the treatment of a solution of 2,3-dimethylindole (I) and its hydroperoxide (II) in dimethyl sulfoxide (DMSO) with alkali (potassium t-butoxide or granular potassium hydroxide) under streams of oxygen and hydrogen respectively. The change in their ultraviolet and fluorescent spectra with the time and the chemiluminescent spectra is measured. The compound II is concluded to be the reaction intermediate of I; it decomposes to yield an excited singlet state of an o-acetamidoacetophenone anion (III*), a light emitting species in this reaction. The investigation, then extended to four 5-substituted-2,3-dimethylindoles, revealed that three of them displayed chemiluminescence through the same mechanism as in the case of I.
The Mechanism of the Alkaline Fusion of Halodiphenyl Sulfone and Halobenzenesulfinic Acids
Authors: Furukawa Naomichi , Oae Shigeru
Published: July 2006

The alkaline fusion of 2-chlorophenyl phenyl sulfone afforded phenol, benzene and chlorobenzene. The initial step of the reaction appears to be the aromatic SN2-type replacement of chlorine to form 2-hydroxyphenyl phenyl sulfone upon which the hydroxide ion further attacks both phenyl carbon-1 and the sulfur atom of the sulfone group to form the final products. The 14C tracer experiment indicates that the preference of the nucleophilic-attacking site of the hydroxide ion appears to vary with the reaction temperature. A similar alkaline fusion of 2-bromo-4-tolyl phenyl sulfone gave not only benzene, bromotoluene, and phenol, but also o- and m-cresol, indicating that the reaction proceeds through a somewhat different path. Meanwhile, the alkaline fusion of 2-chlorobenzenesulfinic acid appears to proceed through the o-sulfinic benzyne formation; thus 2-bromo-4-tolylsulfinic acid gave equal amounts of o- and m-cresols.
Studies on Isothiazoles. IV. A New Synthetic Route to 4-Cyanoisothiazoles
Authors: Naito Takayuki , Nakagawa Susumu , Okumura Jun , Takahashi Kiyoshi , Masuko Kenji , Narita Yukio
Published: July 2006

4-Cyanoisothiazoles have been prepared by a novel procedure which comprises the reacreaction of β-cyano enamines with thionyl chloride or sulfur monochloride. The reaction proceeds favorably in nonpolar solvents or in the absence of solvent. However, the cyclization did not occur in dimethylformamide and instead an amidine derivative was isolated. The preparations of the corresponding isothiazole-4-carboxylic acids are also described briefly.
Solvent Effect under High Pressure. II
Authors: Kondo Yasuhiko , Uchida Miyoji , Tokura Niichiro
Published: July 2006

The activation volume of the reaction of triethylamine with ethyl iodide has been measured in four solvents. A linear relationship has been observed between the values of ΔV0\eweq for the Menschutkin reaction in various solvents and the products of the compressibility and the molar volume of the pure solvent, as has been suggested in a previous paper. From the slope of the plots of (−ΔV0\eweq) vs. KV°, the product of the solvation number and the average pressure within the solvation shell of an activated complex has been calculated to be 2.6×103 (kg·cm−2) according to a model proposed by the authors. An abnormal acceleration due to pressure has been observed for the reaction of triethylamine with ethyl iodide in p-xylene and dioxane at 30°C. This acceleration effects has been attributed to the partial freezing of the solvent under high pressure.
The Crystal Structure of (−)D-Tris(trimethylenediamine)cobalt(III) Bromide Monohydrate
Authors: Nomura Teruo , Marumo Fumiyuki , Saito Yoshihiko
Published: July 2006

The structure of (−)D-[Co(tn)3]Br3·H2O (tn: H2N–CH2-CH2-CH2-NH2) has been solved by the heavy atom method and refined to R=0.11 by least-squares analysis based on 1845 threedimensional data. The substance crystallizes in the monoclinic space group P21 with unit cell dimensions: a=16.274, b=9.863, c=9.489 Å, β=126.4° and Z=2. The complex ion in the structure has approximately a three-fold axis of rotation. The three six-membered Co-tn rings are nearly identical and take chair form. The chelate ring is rather flattened out, owing to the strong H-H repulsion. The absolute configuration of (−)D-[Co(tn)3]3+ has been found to be the same as that of (+)D-[Co(en)3]3+.
The Insertion Reaction of Propylene into Metal-Ethyl Bonds in the Ziegler-Natta Catalyst
Authors: Takegami Yoshinobu , Suzuki Toshimitsu , Okazaki Takuya
Published: July 2006

The insertion reaction of propylene into metal-ethyl bonds in TiCl4-AlEt3, TiCl3-AlEt3, TiCl3-AlEt2Cl, and TiCl3-ZnEt2 catalyst systems was studied. The insertion products were converted to the corresponding hydrocarbons by methanolysis, and then analysed by gas-liquid chromatography. From these hydrocarbons, the following three metal alkyls were considered to be formed in the reaction system;

(Remark: Graphics omitted.)

These metal alkyls were formed in the solid phase of the catalyst at first and were then transferred to the liquid phase of the catalyst. The amount of the metal alkyls formed in the reaction system was dependent on the catalytic system used. The active polymerization system TiCl3-AlEt3 gave a very small amount of metal alkyls, but the less active TiCl3-ZnEt2 and -AlEt2Cl systems gave a much greater quantity of the metal alkyls, (I) and (III). In the case of the TiCl4-AlEt3 system, metal alkyl formation was much affected by the Al/Ti molar ratio and the reaction time. Finally, it was concluded that the metal alkyls formed in the system were connected to the polymerization of propylene.
The Ionic Telomerization of Diene Compounds. IV. The Cationic Telomerization of Butadiene with Its Hydrobromides
Authors: Asahara Teruzo , Kise Hideo
Published: July 2006

The cationic telomerization of butadiene with its hydrobromides (1-bromo-2-butene and 3-bromo-1-butene) in the presence of metal halide was investigated. It was found that the molecular weights of the telomers depend on the conversion of the telomerization, initial bromide/ butadiene ratio and the solvent used. When halogenated hydrocarbons were used as solvents, telomers with high molecular weights and low unsaturations were obtained. On the other hand, the telomerizations in ether solvents gave telomers with low molecular weights, which contained appreciable amounts of the simple adducts of butadiene and bromobutene. The infrared spectra of the telomers suggested that the addition of butadiene occurred mainly at 1,4-position. On the basis of the analyses of the telomers, the reactivities of the carbonium ion to the basic species which were present in the reaction system were estimated.
Deuteron Magnetic Resonance Study in Co(ND3)6Cl3
Authors: Ito Takeshi , Chiba Takehiko
Published: July 2006

Deuteron quadrupole coupling tensors in Co(ND3)6Cl3 were determined at various temperatures. The observed quadrupole coupling shows that Co(ND3)63+ ions execute a rapid isotropic reorientation at high temperatures (above 320°K for one of the sites (the 4f sites) and above 190°K for another (the 2e sites), while at low temperatures (below 190°K for the 4f sites, and 170°K for the 2e sites), only a C3 axis reorientation of the ligand ND3 groups is present. The deuteron resonance spectra clearly show that Co(ND3)63+ ions in the 4f sites begin to reorient about one of the three C4 axes at intermediate temperatures (about 240°K). On the basis of the orientation of quadrupole tensors, probable orientations of Co(ND3)63+ ions in the 4f sites in the crystal are proposed. Additional measurements of the proton resonance on a single crystal of Co(NH3)6Cl3support the results obtained from the deuteron resonance. To obtain the reorientation rates and the activation energies of these reorientational motions, the deuteron resonance line width at the 4f sites is measured at various temperatures and at various crystal orientations. From the temperature dependence of the line width, the presence of two cations with slightly different rates at the 4f sites is suggested. However, because of the limits set by the various experimental conditions, reliable values of the reorientation rates and activation energies could not be obtained.
Oxygen Exchange Reaction of Sulfoxides in Dinitrogen Tetroxide
Authors: Kunieda Norio , Sakai Kazuo , Oae Shigeru
Published: July 2006

Sulfoxides are known to undergo concurrent oxygen exchange and racemization reactions with various reagents (Bull. Chem. Soc. Japan, 41, 1025 (1968)). Especially well studied are the oxygen exchange reactions in acid media. We have found a similar concurrent oxygen exchange and racemization reaction of sulfoxides with liquid dinitrogen tetroxide. The pseudo first order reaction rates of both oxygen exchange and racemization reactions have been determined using both optically active and 18O-labeled sulfoxides. The kex⁄krac value was found to be unity, and the polar effect of substituents on the rates of oxygen exchange of substituted diphenyl sulfoxides was found to be considerably large, and correlated with σ+ values with ρ=−1.30. From these results a plausible mechanism for this reaction has been discussed.
Photochemistry of β-Acylacrylic Acids and Their Esters
Authors: Sugiyama Noboru , Kataoka Hiroshi , Kashima Choji , Yamada Kazutoshi
Published: July 2006

The irradiation of methyl trans-β-acetylacrylate (I-A) in methanol or acetone or without any solvent gave the cis-isomer (I-B). On the contrary, the irradiation of the free acid of I-A, trans-β-acetylacrylic acid (II-A), in methanol or without any solvent gave the angelica lactone, 5-methyl-5-hydroxy-2-oxo-2,5-dihydrofuran (II-C). The irradiation of trans-β-pivaloylacrylic acid (III-A) in methanol also afforded the angelica lactone, 5-t-butyl-5-hydroxy-2-oxo-2,5-dihydrofuran (III-C). The reaction route from a cis-isomer to an angelica lactone was explained in terms of the inductive effect.
The α Effect. Aminolysis on a Saturated Carbon Atom
Authors: Oae Shigeru , Kadoma Yoshihito , Yano Yumihiko
Published: July 2006

The rates of aminolyses of methyl, isopropyl, allyl and benzyl iodides have been determined in acetonitrile. Bases used were hydrazine, morpholine, imidazole and piperidine. The rates of all the aminolysis reactions can be correlated nicely with the basicities. Hydrazine also did not show any positive deviation from the Brφnsted plots. This fact suggests that the α-effect is not operative in these displacement reactions on the saturated carbon atom.
Amino-quinoid Polymeric System. The Preparation of a Polyester Containing 2,5-Diamino-p-benzoquinone Nuclei and Its Crosslinking
Authors: Kumanotani Ju , Sugita Kazuyuki , Kazama Seiji , Yoshikawa Toshio
Published: July 2006

A polyester containing 2,5-diamino-p-benzoquinone nuclei was prepared by the polycondensation of 2,5-bis(ω-carboxyl-pentylamino)-p-benzoquinone with polyethylene glycol 400 at 160°C, 170°C and 180°C. At 160°C the esterification was brought about easily without gelation, giving an amino-quinoid polyester (prepolymer), but above 170°C an unexpected gelation was observed. The amino-quinone nuclei incorporated in the polyester thus prepared were confirmed by NMR spectroscopy. To make clear the influence of the amino-quinone nuclei upon the gelation, the thermal reactions of the model compounds, the above amino-quinoid dibasic acid, and its ethyl ester were investigated by means of IR spectroscopy and chemical analysis. It was concluded that the hydrogen atoms in the amino-groups of the quinone move to the oxygen atoms and that the resulting hydroxy groups combine with each other to form an ether bond as a result of dehydration. When the prepolymer prepared at 160°C was heated at 170°C for 4 hr with p-toluenesulfonic acid (5% by weight) or at 180°C for 8 hr without the acid catalyst, there was obtained an infusible and insoluble film which made crosslinkage as shown in the above mechanism.
Electroless Nickel Plating from Acid-acetate Baths Containing Hypophosphite as a Reducing Agent
Authors: Ogawa Kin’ya
Published: July 2006

The properties of acid-acetate baths containing hypophosphite as a reducing agent were studied in an attempt to obtain an electroless nickel deposit; further, the protective property of such deposits with phosphorus contents of 4 to 13% was investigated. The hypophosphite utilization efficiency for the deposition of electroless nickel was found to be 0.33; the deposition rate indicates a first-order dependence on hypophosphite, but it is independent of nickel concentration, within the limits specified in the range of suitable conditions. The phosphorus content of the deposits increases with a decrease in the pH value of the bath and with an increase in the initial concentration of hypophosphite, but it is independent of that of nickel. An electoless nickel with a high phosphorus content affords more protection against metallic bases.
Effect of Additives in the Radiolysis of Gaseous Ammonia at High Densities
Authors: Nishikawa Masaru , Kuroda Kazufumi , Matsuura Niro
Published: July 2006

The effect of additives and density on the radiolysis of ammonia at 140°C was studied over the density range 0.07 to 0.13 g/cc. The observation of a sharp decrease of G values in the radiolysis of pure ammonia at d∼0.1 g/cc confirmed the result reported by Toi et al. (Radiation Res., 17, 399 (1962)). The yield of hydrogen in the presence of ∼1.5 mol% C3H6 was practically independent of density at G=0.65 over the density range studied. G(H2) in the presence of C3H8, estimated by extrapolation to zero propane concentration, was also constant at G\simeq5.7 at d\simeq0.07 and 0.13 g/cc. These observations were discussed in relation to the mechanism for depression of G values in the radiolysis of pure ammonia at higher densities.
Thermodynamic Properties and Phase Transitions of Thallous Cyanide Crystal
Authors: Matsuo Takasuke , Sugisaki Masayasu , Suga Hiroshi , Seki Syûzô
Published: July 2006

The heat capacities of TlCN crystal were measured from 15 to 300°K with an adiabatic calorimeter. Three regions of anomalously high heat capacity were discovered. Thermodynamic functions of the crystal were calculated by the graphical integration of the heat capacity data. 205Tl nuclear magnetic resonance was observed as functions of temperature and applied static magnetic field. Their second moment values could be interpreted in terms of the anisotropic chemical shift tensor.
Absorption Spectra and Circular Dichroisms of Metal Complexes. III. trans-Dihalogeno-bis-l-propylenediamine Complexes of Cobalt(III), Rhodium(III), Palladium(IV) and Platinum(IV)
Authors: Ito Haruko , Fujita Junnosuke , Saito Kazuo
Published: July 2006

Absorption (AB) and circular dichroism (CD) spectra of trans-[MX2(l-pn)2]n+ (where M=RhIII, PdIV- and PtIV-, and X=Cl− and Br−) have been discussed by comparing them with those of cobalt (III) complexes which had been studied extensively. A positive CD peak was observed at around the so called Ia band region of all the complexes studied except for trans-[PtBr2(l-pn)2]2+. A negative CD peak of this complex ion at 26000 cm−1 was assigned to be a split component of the Ia band. The AB peaks at 38000, 28600 and 31100 cm−1 for trans-[PtCl2(l-pn)2]2+, trans-[PdCl2(l-pn)2]2+ and trans-[PtBr2(l-pn)2]2+ respectively were assigned to pπ→dz2 charge transfer transition. An ion association band was observed for trans-[PtBr2(l-pn)2]Br2 in 1n hydrobromic acid.