bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthetic Studies of the Derivatives of Nitroacetic Acid. III. The Synthesis of Isoxazole-3,5-dicarboxylic Acids from Schiff Bases and Nitroacetic Ester
Authors: Umezawa Sumio , Zen Shonosuke
Published: July 2006

1) Schiff bases react with ethyl nitroacetate in the presence of n-butylamine or benzylamine to give 4-substituted isoxazole-3,5-dicarboxylic amides. This is a new synthesis of isoxazole derivatives.

2) Twenty kinds of 4-substituted isoxazole-3,5-dicarboxylic amides, including aliphatic, aromatic and heterocyclic derivatives, have been prepared.

3) Seven of the above-mentioned amides have been hydrolyzed to give the corresponding 4-substituted isoxazole-3,5-dicarboxylic acids.

4) Some Schiff bases have been described.
X-Ray Diffraction Studies of the Molecular Complexes of Tetracycline Salts
Authors: Inouye Shigeharu , Iitaka Yoichi
Published: July 2006

An examination of the salt-complexes of tetracycline and oxytetracycline by the X-ray powder method has shown the presence of at least four different kinds of crystal structures, i.e., the dα, dβ, hγ, and hδ forms. Among them, the dα form has been studied in detail by the use of single crystals. The monoclinic unit cell dimensions of the dα crystals do not vary much either with a salt anion or with a complexing agent, and the intensities of the various reflections so far examined are very similar. On the basis of these findings, it is suggested that the crystal structures of the dα-type salt-complexes consist of an almost identical framework of tetracycline or oxytetracycline molecules which encloses spaces capable of containing complexing agents of various types. The orthorhombic dβ form is a polymorphic modification of the dα form, probably arising from submicroscopically polysynthetic twinning of the latter.
The Luminescence Spectra of Triply-ionized Dysprosium and Terbium in Alkaline Earth Fluorides
Authors: Iwase Eiichi , Nishiyama Seijiro
Published: July 2006

(i) The luminescence spectra of dysprosium-(III) and terbium(III) ions have been measured in the cubic field (Oh5) of calcium fluoride, strontium fluoride and barium fluoride under excitation by cathode-ray-bombardment.

(ii) The displacement of the luminescence bands of dysprosium (III) ion has been studied with relation to the matrices mentioned above, a blue shift being observed, with 25 and 22 bands as the matrix was changed in successive sequences of calcium fluoride to strontium fluoride and strontium fluoride to barium fluoride respectively. Similarly, this was the case with 35 bands of the terbium (III) luminescence when, the matrix was changed from calcium fluoride to strontium fluoride, and with 33 bands for that from strontium fluoride to barium fluoride.

(iii) The magnitude of the relative crystalfield splittings Δν of the luminescence bands of dysprosium (III) and terbium(III) ions was reported in relation to the increasing strength of the crystal field, i.e., in the sequence of matrices barium fluoride, strontium fluoride and calcium fluoride. For the dysprosium (III) luminescence, the crystalfield splittings observed in the 6F11/2→6H11/2, 6F11/2→6H13/2 and 6F11/2→6H15/2 transitions had a tendency to increase in the matrix-sequence barium fluoride, strontium fluoride and calcium fluoride. In the case of the terbium (III) luminescence, variations similar to that found in the dysprosium (III) luminescence took place in the crystalfield splittings of the 5D4→7F3, 5D4→7F4, 5D4→7F5, 5D3→7F2, 5D3→7F3 and 5D3→7F5, transitions, while the reverse was the case with the 5D4→7F6 and 5D3→7F4 transitions.

(iv) It was found that the band appearing at 18480cm−1 in the luminescence spectrum of the terbium(III) ion embedded in barium fluoride splits into its respective two components when the terbium ion was embedded in matrices of strontium fluoride and calcium fluoride with a more intense crystalfield strength. The magnitudes of these splittings, 30 and 50cm−1 as observed in strontium fluoride and calcium fluoride respectively, are presumably proportional to the differences between the crystalfield strength for barium fluoride, strontium fluoride and calcium fluoride.
Electronic Properties of Quaterrylene, C40H20
Authors: Maruyama Yusei , Inokuchi Hiroo , Harada Yoshiya
Published: July 2006

Quaterrylene (C40H20) is a dark green-coloured aromatic hydrocarbon and is extraordinarily stable, as it can be heated to over 500°C without decomposition. The semiconduction of the aromatic hydrocarbon possesses a substantial anisotropy by a factor of 107∼108; the resistivity in the direction parallel to the b axis is 106Ωcm. (for a single crystal) or 105Ωcm. (for a surface-type cell) and that perpendicular to the b axis is 1013Ωcm. However, their energy gaps are around 0.6 eV.

From its pulsed photoconduction of the thin film, a drift mobility has been estimated in the order 10−3 cm2/V. sec. However, the rectifying effect of the photoconduction can scarcely be recognized; that is to say, it seems that the mobilities of the holes and electrons in crystal are almost the same.

Further, its photovoltage between aluminium and quaterrylene has a value of 0.1∼0.3 V., while the ionization potential of the hydrocarbon is 4.9 eV. judging from the threshold value of the spectral response of the photoelectric emission.

From these results, a energy level diagram has been introduced for the system of the aromatic hydrocarbon-aluminium contact when a band-type model is employed as the organic semiconductor.
Studies of the Photochemical Reactions. V. The Synthesis of Dimethyldioxanylcarbinol and Dimethyl-α-tetrahydrofurylcarbinol
Authors: Shima Kensuke , Tsutsumi Shigeru
Published: July 2006

The photochemical reaction of acetone in dioxane or tetrahydrofuran has been studied, and two new compounds, dimethyldioxanyl-carbinol (III) and dimethyl-α-tetrahydrofuryl-carbinol (IV), were easily produced by this photoreaction.
Thermal and Radiation Oxidations of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. III. The Effect of Copper Ions
Authors: Hotta Hiroshi , Suzuki Nobutake , Terakawa Akira
Published: July 2006

The yield of phenol increases abruptly above 170°C in the cupric sulfate solutions. When the solutions contain copper metal pieces, phenol is produced, even below 160°C, regardless of irradiation or non-irradiation. On the other hand, scarcely any phenol is produced in the cupric-ferric sulfate solution, even at 180°C. These facts are to be attributed to the fast rate of cuprous oxidation by oxygen.
The Absorption Spectra of Cobalt(III) Complexes. IV. The Preparation and the Absorption Spectra of Monohalogenomonoamine-bis (ethylenediamine)-cobalt(III) Complexes
Authors: Yasui Takaji , Shimura Yoichi
Published: July 2006

The four iodo-amine complexes and some chloro- and bromo-amine complexes belonging to [CoX(NH2-R)en2]X2 type have been newly synthesized to complete the series.

From the measurements of the near-infrared, visible and ultraviolet absorption spectra, the geometrical structures of the complexes have been determined. The ammine complexes, [CoX(NH3)en2]X2, exist in both the cis- and the trans-forms, but the organic amine complexes, [CoX(NH2-R)en2]X2, exist only in the cis-form.

The weak splitting of the A band has been observed for the first time in the bromo-amine complexes.
The Viscometric Properties of Polyesters. I. A Comparison between Crystalline and Amorphous Polyesters
Authors: Nakatsuka Ryuzo
Published: July 2006

From the study of the viscosity of aliphatic long-chain polyesters over a wide range of temperatures, the following results have been obtained :

(1) Among aliphatic long-chain polyesters with ether bonds in the main chains, several crystalline polyesters have been obtained.

(2) Accordingly, it has been possible to compare the temperature dependence of the viscosity of the amorphous and the crystalline polyesters with similar chemical structures.

(3) When the temperature is raised, every apparent activation energy for viscous flow (E\eweq) approaches a fixed value, independently of the chemical structure of the polyester.

(4) However, the viscous flow state of the amorphous polyester changes discontinuously in connection with the chemical structure near the melting point of the corresponding crystalline polyester.

(5) In the “transition area” for viscous flow, the viscosity and the apparent activation energy (E\eweq) are, respectively, about 10 poises and 11 kcal./mol.
Studies of the Synthetic Inorganic Ion Exchanger. III. The Separation of the Fission Product by Means of a Stannic Phosphate Cation Exchanger
Authors: Inoue Yasushi
Published: July 2006

The mutual separation of various nuclides contained in fission product has been carried out with a stannic phosphate cation exchanger. Various concentrations of nitric acid and ammonium chloride solutions have been used as eluants, and the separation has been performed on hydrogen- and ammonium-form exchangers.

The separations of 89Sr–137Cs, 89Sr–144Ce, 137Cs–144Ce and 90Sr–90Y were easy and complete except for that of 137Cs–144Ce on a hydrogen form exchanger. 95Zr and 95Nb were almost completely adsorbed on the exchanger over a wide range of acidity and salt concentration; therefore, they were not eluted at all. As the behavior of 106Ru is complex and its separation from other nuclides is impossible, it is necessary to separate the ruthenium from the fission product in advance by a method other than that of ion exchange.

With reference to the above results, the total analysis of the fission product on an ammonium form exchanger has been carried out. It is almost complete except for the contamination of rare earth in the cesium fraction.
Cadmium Sulfodichlorohydroxydimethylfuchsondicarboxylate Chelate—A Spectrophotometric Study
Authors: Sangal Satendra P , Dey Arun K
Published: July 2006

Sulfodichlorohydroxydimethylfuchsondicar-boxylate forms a 1:2 violet colored chelate (λmax 540 mμ) with cadmium(II). The chelate is stable between pH 9.5 and 11.5. The values of stability constant as determined by two different methods are 9.1 and 9.0, at 25°C.
Behavior of Chromotropic Acid as a Colloidal Electrolyte in Aqueous Solution
Authors: Sangal Satendra P
Published: July 2006

The nature of chromotropic acid as a colloidal electrolyte has been established from electrical conductance studies. The curve obtained by plotting the square root of concentration and molar conductance of the reagent solution is not linear and resembles that of a colloidal electrolyte. The temperature coefficient per degree centigrade per hundred units of conductance at 35°C is between 1.5 and 1.7. The temperature of zero conductance, determined by extrapolation, is −20.0°C.
The Preparation of Dimer Aldehydes and Dimer Alcohols in an Oxo Reactor. I. Modifiers Effective in Producing Dimer Aldehydes and the Hydrogenation of the Aldehydes with Synthesis Gas
Authors: Uchida Hiroshi , Matsuda Akio
Published: July 2006

Among the modifiers which have been tested, magnesium compounds are the most effective in producing a great amount of dimer aldehydes in the course of the propylene hydroformylation. The addition does not result in any reduction of the hydroformylation rate at 150°C. A certain amount of C-4 aldehydes had already been dimerized in the presence of dicobalt octacarbonyl alone, but the amount of dimerized aldehydes is greatly increased by the further addition of magnesium compounds, the total amount exceeding the sum of the amounts obtainable in the presence of either one of them. Moreover, the addition of an organic base further increases the yield of dimer aldehydes to some extent.

When starting with the raw material also containing iron pentacarbonyl, the hydrogenation of the aldehydes with the synthesis gas can be accomplished by the simple elevation of the temperature to 200°C. In the hydrogenation stage, iron pentacarbonyl does not behave as the catalyst for itself, but it contributes to the hydrogenation by suppressing, at that high temperature, the decomposition of the dicobalt octacarbonyl that is the real catalyst.
Kinetics of the Catalytic Hydrogen Peroxide Oxidation of Thiodiglycol in Aqueous Solutions
Authors: Ogata Yoshiro , Sawaki Yasuhiko
Published: July 2006

The catalytic activities of some inorganic compounds for the hydrogen peroxide oxidation of thiodiglycol (TDG) have been examined in aqueous media at 25°C and at pH 4.7. It has been found that the order of catalytic activities was: Na2MoO4, Na2WO4>>H2SeO3>NH4VO3, Na2TeO4, UO2(OAc)2, Cu(OAc)2. The rates of oxidation using all these catalysts, except sodium molybdate, may be expressed as v=k2[H2O2] [TDG].

The kinetics of this reaction has been studied in detail, especially with the sodium molybdate (SM) catalyst, by means of iodometry. The oxidation in the range [H2O2]>2[SM] follows the pseudo-first-order kinetics : v=k1c[SM] [TDG]. The rate at pH below 2 is several times faster than that at pH 3∼6, the energies of the activation at pH’s below 2 and at 3∼6 being 9.21 and 11.2 kcal. mol−1 respectively. The oxidation in the range of [H2O2]<2[SM] follows the second-order kinetics : v=k2′[Active oxygen] [TDG]. The values of k2′ were identical with the second-order rate constants obtained in the oxidation of thiodiglycol by yellow sodium peroxymolybdate. It is probable that dihydroperoxymolybdate, HMoO6−, produced rapidly from Na2MoO4 and hydrogen peroxide, oxidizes thiodiglycol The increase in the rate with a decreasing pH may be due to the transformation of HMoO6− to more active H2MoO6, since the Na2MO4-hydrogen peroxide system gave two different ultraviolet absorption maxima corresponding to HMoO6− and H2MoO6 at pH 4.7 and 0.8 respectively.
Polymerization and Polymers of Itaconic Acid Derivatives. V. The Copolymerization Reactivity of Itaconic Acid in an Aqueous Solution
Authors: Nagai Susumu
Published: July 2006

The copolymerization of itaconic acid with acrylonitrile has been carried out in aqueous solutions of three different pH values. From the composition data obtained, the monomer reactivity ratios and the Q-e values have been calculated. The results indicate that itaconic acid, when ionized to the second-step dissociated form, is able to copolymerize with other monomers, while it is almost completely unable to homopolymerize.
The Chemical Compositions of Crystals and Glasses of the NaPO3–Na2SiO3 and NaPO3–SiO2 Systems
Authors: Ohashi Shigeru , Oshima Fumio
Published: July 2006

Crystals and glasses of the NaPO3–Na2SiO3 and NaPO3-SiO2 systems with various P/Si ratios have been prepared from sodium metaphosphate, silicon dioxide, and sodium carbonate. The samples with P/Si ratios in the range from 0.05 to 4.00 have been obtained as crystalline substances containing amorphous substances, while those with P/Si ratios in the range from 6.00 to 200 have been obtained as glassy substances. By the X-ray diffractometry and the paper chromatography, it has been revealed that the crystals of neither system contains any P–O–Si linkages. By the paper chromatography and the pH-titration method, it has been disclosed that the glassy substances of either system with P/Si ratios higher than 6 are hydrolyzed to give mixtures of polyphosphates when dissolved in water. The lower the P/Si ratio, the more shorter chain polyphosphates are formed. The variation in the average chain length of the polyphosphates with the P/Si ratio indicates that these glassy substances are condensed phosphate-silicates containing P–O–Si linkages. Three structural types of P–O–Si linkages have been proposed for the condensed phosphate-silicates.
Formaldehyde Resins. LXVII. On the Reaction Order of Sodium Hydroxide and on the Salt-effect of Sodium Bromide in the Base-catalyzed Reaction of Benzamide with Formaldehyde
Authors: Imoto Minoru , Ninagawa Akira
Published: July 2006

A kinetic study of the reaction of benzamide with formaldehyde in the presence of sodium hydroxide has been made. The following results have been obtained: (1) A linear relationship is obtained between the concentration of sodium hydroxide and the critical bending concentration of formaldehyde where the reaction-order changes from one to zero. (2) The pH value is constant throughout the reaction. (3) The rate of the reaction decreases upon the addition of sodium bromide. However, the decrease reaches a miuimum at a definite concentration of sodium bromide. After this point, the salt has no effect on the rate. (4) The activation energy has been computed as 8.25 kcal./mol. The findings (1) and (3) have been explained by the solvated cage theory.
The Colorimetric Determination of Traces of Selenium with Dithizone
Authors: Mabuchi Hisao , Nakahara Hiromichi
Published: July 2006

A colorimetric method of determining traces of selenium with dithizone has been studied. Selenium is extracted from a 6 N hydrochloric acid solution with a carbon tetrachloride solution of dithizone almost quantitatively, and the dithizone complex of selenium in carbon tetrachloride has a maximum absorption at the wavelength of 420mμ. One p.p.m. of selenium can be determined spectrophotometrically, by measuring the extinction at 420 mμ in the mono-color method and at 410 mμ in the mixed-color method.

The errors of these two methods are estimated to be within 3%. Copper(II) and mercury (II) were found to be interfering metals. However, they are easily removed by a preliminary extraction. Finally, attention should be paid to the fact that the color of the dithizone complex of seleium is apt to fade away rapidly when it is left in contact with a 6n hydrochloric acid solution for some time.
Charge Mobility in Pyrene Crystals
Authors: Ohki Kenji , Inokuchi Hiroo , Maruyama Yusei
Published: July 2006

To estimate the charge mobility in a direction perpendicular to the ab plane in the sixteen atoms of the aromatic hydrocarbon crystal, pyrene, the overlap integrals between two molecules have been calculated. On the basis of these results, the hole mobility (μh) has been found to be twice that of the electron mobility (μe). However, judging from the transient photocurrent of the pyrene crystal, μe (∼3 cm2/V. sec.) was considerably larger than μh (1.2cm2/V. sec). This discrepancy may be eliminated by the introduction of a more accurate theoretical treatment.
The Absorption Spectra of Oil-soluble Dyes Solubilized by a Polysoap and a Monosoap
Authors: Tokiwa Fumikatsu
Published: July 2006

The absorption spectra of several oil-soluble dyes, 1-benzeneazo-2-naphthol and three 1-nitrobenzeneazo-2-naphthols, have been measured in aqueous solutions of polysoap and monosoap and in hydrocarbons. The spectra of the above dyes in monosoap solutions are similar to those in hydrocarbons, while the spectra of dyes with a nitro group in polysoap solutions, especially the spectrum of p-nitro-BAN, are different. The differences in the solubilization behavior of the dyes in polysoap and in monosoap solutions and the ways in which the dyes are solubilized have been discussed. It has also been proposed that the loci of the solubilization in the polysoap molecule are not only the dense hydrocarbon region in the interior but also the polar region near the polymer backbone. In this case, the nitro group of the dye molecule seems to play an important role in the solubilization.
Amperometric Determinations of Metals with Chloramine T
Authors: Deshmukh G S , Eshwar M C
Published: July 2006

An indirect procedure for the determination of V5+, Ce4+ and Cr6+ is given. Three re-ductants, viz., ascorbic acid, arsenous oxide and hydrazine have been employed for reduction of each oxidant. Iodine monochloride has been used as catalyst in the reduction of V5+ and Ce4+ by arsenous oxide. Reduction of Ce4+ with hydrazine presented certain difficulties and is not pursued at the present stage. The excess reductant in each case is determined amperometrically with chloramine T at the rotating platinum wire micro-electrode, and an impressed potential of +0.3 volt vs. S.C.E. The titrations are performed at a pH of 4.3∼4.9, using citrate-citric acid buffer. For titration of excess arsenous oxide and N2H4·H2SO4, 0.25 ml. of iodine monochloride (0.005 m) has been employed as catalyst. The procedure, which is rapid and accurate, has been employed for determination of amounts up to 1.05 mg. vanadium, 5 mg. cerium and 0.86 mg. chromium.
The Electronic Spectra and Electronic Structures of Amino-substituted Benzenes
Authors: Mataga Noboru
Published: July 2006

The electronic spectra and electronic structures of amino substituted benzenes have been studied by the semiempirical MO method, with the explicit inclusion of the electron repulsion.

According to the calculated results, we can interpret the difference between the spectra of various poly-substituted aminobenzenes; also, the calculated excitation energies and oscillator strengths are in satisfactory agreement with the observed values.

The relation between the present calculation and the simple Hückel MO calculation has been analyzed. Moreover, several interesting relations between the Hückel MO quantities of substituted benzenes and naphthalenes have been demonstrated and discussed.

The calculated π-moment of aniline in the ground state is in satisfactory agreement with the experimental value. Furthermore, the π-moment of aniline in the lowest excited singlet state has been calculated and compared with the experimental value obtained from the measurement of the solvent shifts of the absorption and fluorescence spectra.
The Photoreduction of Acridine in Deaerated and Aerated Alcohol Solutions. II.
Authors: Niizuma Shigeya , Koizumi Masao
Published: July 2006

The photoreduction of acridine in methanol and isopropanol has been studied and the following results obtained :

1) The quantum yield for the photoreduction in the dagassed solution is, for methanol, 0.13 and, for isopropanol, 0.09. The photoreduction can take place even in an air-saturated solution with quantum yields of 0.032 for methanol) and of 0.032 (for isopropanol).

2) In case of a degassed solution, the product is acridan for both isopropanol and methanol, while in an aerated solution the product is acridan in the case of methanol and mainly diacridan in the case of isopropanol.

3) When the concentration of oxygen is of the order of that of acridine, the reaction proceeds at first at a rate equal to that of an air-saturated solution and then, from the point at which the oxygen is exhausted, the rate increases up to the value of a degassed solution.

4) The ratio of the quantities of oxygen and of acridine consumed before the break is, for methanol, about 3 and, for isopropanol, 5.3.

5) By the sensitizing action of acridine, acridan is oxidized to acridine in the presence of aldehyde (or acetone) and a small quantity of oxygen.

6) On the basis of the scheme proposed in the preceding paper and from the reaction product, some tentative discussion of the scheme has been undertaken. It seems plausible that, in the case of ethanol and methanol, AH· + RH· → AH2 + R occurs, while in the case of isopropanol, AH· + AH· → AH2 + A and RH· + RH· → take place (for a degassed solution).
The Preparation of Strictly Halide Complexes of Copper(II) and Their EPR Spectra
Authors: Mori Masayasu , Fujiwara Shizuo
Published: July 2006

Some copper complexes which have only chloride ions in the coordination spheres have been prepared and their EPR spectra examined at the microwave frequency of the X-band. Most of these compounds gave single EPR lines with half-widths ranging from 110 to 220 oe; this seems to indicate the existence of superexchange interaction. Only the yellow plates of dimelammonium hexachlorocuprate-(II) showed the fine structure of an anisotropic g-tensor, from which fact the g-components were evaluated as g||=2.32 and g⊥=2.08 for this compound. The dark green color of diethylenetriammonium chlorocuprate(I, II) is probably due to the interaction of Cu+ and Cu2+ in the crystal lattices. Brown chlorocuprates with a chlorine to copper ratio of 3 : 1 are probably coordination polymers ; the EPR lines of these compounds are so broad as to cover thousands of oersteds.
Photoconductive Polymer: Its Preparation and Photoconductive Behavior
Authors: Morimoto Kazuhisa , Hayashi Yoshiki , Inami Akira
Published: July 2006

A photoconductive polymer, poly[1, 3-diphenyl-5-(4-vinylphenyl)-2-pyrazoline], has been synthesized from polystyrene via polyvinyl-acetophenone and polyvinylbenzalacetophenone. Under carefully controlled preparative conditions, a high degree of substitution has been obtained without its being insoluble. The photoconductive behavior of the polymer has been measured using a sandwich-type cell. The current obeyed Ohm’s law, and the value of Ip/Id was 34 or 147 depending on whether the illuminated electrode was positive or negative respectively.
The Electrical Conduction of the p-Phenylenediamine Iodine Complex
Authors: Nishizaki Shun-ichiro , Kusakawa Hideaki
Published: July 2006

In the case of a complex of p-phenylenediamine with iodine, a nonstoichiometrical composition has been established; the minimum values for both the magnitude and the temperature dependence of resistivity exist on the complex the coordination number of which is around 0.8. On the other hand, the maximum value of the apparent density appears in the vicinity of 1.0.

In comparison with the complex of p-phenylenediamine-iodine and that of p-phenylenediamine-chloranil, even though the redox potential of chloranil is larger than that of iodine, the resistivity and the activation energy of the p-phenylenediamine-iodine system are smaller than those of the chloranil complex.
A Spectrophotometric Study of the Metal Chelates of Resacetophenone Oxime. III. Nickel Chelate
Authors: Bhatki K S , Rane A T , Kabadi M B
Published: July 2006

RAPOX (resacetophenone oxime) in certain water-immiscible organic solvents is found to extract nickel from an aqueous medium as a nickel RAPOXimate complex. Cyclohexanone was found to be the best solvent for this purpose. The brilliant green-coloured solution of the complex in cyclohexanone gave a maximum absorption at 600 mμ on a Beckman spectrophotometer DU. The coloured solution obeyed Beer’s law in the lowest range—six parts per million. The extraction of this complex was quantitative in the pH range from 8 to 11.

The composition of the complex as determined by Job’s method and the slope ratio method in a two-phase system was 1 : 2 (nickel to RAPOX). The back extraction study for the metal from the complex in the organic solvent was carried out and quantitative results obtained using an aqueous solution with a pH value below four.
The Menschutkin Reaction in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Kondo Yasuhiko
Published: July 2006

1) The Menschutkin reaction (reaction of methyl, ethyl or isopropyl iodide with pyridine, dimethylaniline or dimethyl-o-toluidine) has been carried out in liquid sulfur dioxide. The reaction rate has been compared with those in other commonly used solvents.

2) The reaction rate in liquid sulfur dioxide is the slowest, whereas the previously performed reactions such as the Beckmann rearrangement and the cationic polymerization in this solvent were the fastest among the solvents ordinarily used.

3) The reason for such a discrepancy has been discussed. Importance of the Bare (or unsolvated) ion or species in an ionic reaction is presented.
The Surface Activities of Bivalent Metal Alkyl Sulfates. I. On the Micelles of Some Metal Alkyl Sulfates
Authors: Satake Iwao , Iwamatsu Ichiro , Hosokawa Shizuko , Matuura Ryohei
Published: July 2006

Dodecyl sulfates of bivalent nickel, cobalt, copper and magnesium were synthesized, and studies were carried out on the CMC values of these detergents, the effects of the added electrolytes on these CMC values, on micellar molecular weights, and on micellar charges. The CMC values of the detergents were independent of the kind of metal, and the CMC value of 1.2×10−3 mol./l. was obtained. The micellar aggregation numbers of bivalent metal dodecyl sulfates were of the order of 100, which is about twice that of sodium dodecyl sulfate. The dissociation degrees of the micelles were also evaluated from the conductivity data. The α values obtained were 0.66 for cobalt, 0.60 for copper and 0.42 for magnesium. The dissociation degree of the copper dodecyl sulfate micelle was also estimated to be 0.52 from the depression of the CMC value by the added electrolyte; this figure is approximately the same as the value of 0.60 obtained from the conductivity data. These results suggest that the fundamental factor responsible for determining the surface activities of bivalent metal dodecyl sulfates is the valency of the gegenion and that the kind of metal has little or no detectable effect on them.
Asymmetric Hydrogenation with Modified Raney Nickel. I. Studies on Modified Hydrogenation Catalyst. II
Authors: Izumi Yoshiharu , Imaida Masami , Fukawa Hideaki , Akabori Shiro
Published: July 2006

1. Raney nickel catalyst treated with optically active glutamic acid has the property of catalyzing the hydrogenation of carbonyl compounds asymmetrically with high reproducibility and efficiency.

2. Excellent results were obtained in the hydrogenation of methyl acetoacetate to optically active methyl 2-hydroxybutyrate in the presence of Raney nickel catalyst treated with l- or d-glutamic acid.

3. The capacity for asymmetric hydrogenation was strongly dependent upon the pH of the modifying solution. The highest capacity was obtained when modifying solutions were adjusted to pH 4.8∼5.5.

4. With elevation of the temperature of the modifying process, the asymmetric capacity of the catalyst decreased markedly, nearly disappearing at 60°C, and yielding products with reverse optical rotation above 80°C.

5. The asymmetric capacity was independent of the concentration of the modifying solution within the range of 6 to 0.0625%.

6. Hydrogenation in the presence of catalyst modified with d-glutamic acid yielded a product with reverse optical rotation to that obtained when l-glutamic acid was used.

7. Asymmetric yield of the reducing product of methyl acetoacetate by the catalyst treated with Glu was varied with the relative amount of the substrate and the catalyst.
The Polarographic Reduction and Electronic Structures of Organic Halides
Authors: Fukui Kenichi , Morokuma Keiji , Kato Hiroshi , Yonezawa Teijiro
Published: July 2006

The polarographic reduction potential of haloalkanes is connected with the energy of their lowest unoccupied σ level. Moreover, the reduction products are well explained in terms of the anti-bonding nature of the carbon halogen bond of the level. The polarographic reduction potential of conjugated halides is also correlated to their lowest unoccupied σ, not π, level. It has also been suggested that, in conjugated halides, the lowest unoccupied σ level might be lower than the lowest unoccupied π level and that the π→σ* transition might be observed.

Most of the calculations have been carried out on the KDC-I digital computer of Kyoto University.
The Interpretation of Absorption Spectra of Condensed Polycyclic Aromatic Hydrocarbons by Using a Simple Resonance Theory. I. The Resonance Structure of the Excited State in Correlation with Platt’s Theory
Authors: Handa Takashi
Published: July 2006

The chemical resonance structures of the excited states are assumed to correspond to the type of polarization in each state. This theory can explain the absorption energies as the difference in the empirical resonance energies between the ground and excited states by an application of Carter’s empirical equations. Imaginary charges are introduced to estimate the number of resonance structures, thus eliminating the influence of cross-linking atoms; the meaning of the resonance hybride corresponding to each levels is easily interpreted in correlation with Platt’s theory. As a result,, the individual excited state can be represented as a chemical resonance hybride consisting of a group of simple polarized structures; this theory may be said to be adequate from the view-point of absorption energies and of absorption intensities in relation to the direction of electric dipoles.
The Electrical Properties of Microcrystalline Selenium. I. Chlorine-doped Selenium
Authors: Araki Tsuneo
Published: July 2006

1. The resistivity of microcrystalline selenium doped with chlorine was changed by heat treatment. The results were in fairly good accord with the measurements obtained by Schweickert. Selenium doped with chlorine had the same characteristics as that doped with iodine or bromine.

2. The results of microscopic observation showed that the grain size became smaller with the higher chlorine concentration. This tendency was similar to that found in iodineor bromine-doped selenium.

3. The resistivity variation with temperatures below room temperature was affected by the heat treatment of the specimen. The effect was greater for the specimen free from chlorine.

4. Carrier concentrations were obtained from the measurement of capacity and also from the thermoelectric power. These two methods gave results which were in agreement with each other. The concentrations were shown to be increased at low temperatures.
A Study of the Properties of Mixed Solutions of Sodium Dodecyl Sulfate and Dodecyl Alcohol
Authors: Tokiwa Furnikatsu
Published: July 2006

Measurements have been made of the electrical conductivity and the viscosity of mixed solutions of sodium dodecyl sulfate (SDS) and dodecyl alcohol (DA). The addition of DA caused a lowering of the conductance, a phenomenon probably related to the formation of a complex composed of SDS and DA, but it did not essentially alter the form of the Λ−\sqrtc curves up to 0.3 mol. fraction of DA in SDS-DA. The Λ−\sqrtc curves of the mixed solution exhibit a break point which corresponds to a critical concentration of SDS, up to a 0.3 mol. fraction of DA in SDS-DA; the break point becomes obscure when the amount of DA present is larger than this value. The effect of the amount of DA on the critical concentration was not very large in this experiment.

The variation of the conductance and viscosity with the temperature was measured on the solution of SDS with varying concentrations of DA. For the solution of SDS without DA, the product of the conductance and the viscosity is almost independent of the temperature, while for the mixed solutions the product is dependent on the temperature, especially in the case of the mixed solution containing a considerable amount of DA.
Sterically-hindered Organosilicon Compounds Containing Cyclohexyl Groups. II. Hydrogenation of Phenylsilicon Compounds
Authors: Takakusa Michio
Published: July 2006

Tricyclohexylbutylsilane, tetracyclohexylsilane and tricyclohexylphenylsilane were prepared by hydrogenation of triphenylbutylsilane and phenyltricyclohexylsilane and partial hydrogenation of tetraphenylsilane, respectively. Preparation of tricyclohexylisopropylsilane and tricyclohexyl-t-butylsilane was unsuccessful due to failure of obtaining corresponding triphenyl derivatives. An attempt to obtain tricyclohexylcyclohexoxysilane by hydrogenating triphenylphenoxysilane was also unsuccessful. In preparation of highlysubstituted cyclohexylsilicon compounds, the steric factor is of less importance in the hydrogenation process, while it is very much enhanced in reactions with organolithium compounds.
Decomposition of Peroxybenzoic Acid in Solution. VI. Theoretical Consideration of the Induced Decomposition of Peroxides by Radicals
Authors: Tokumaru Katsumi , Simamura Osamu
Published: July 2006

On the basis of observations on the induced decomposition of peroxides by radicals, it has been suggested that the interaction of the charge-transfer type, involving the highest occupied molecular orbital in an attacking radical and the 2pσu antibonding orbital around the oxygen to oxygen bond in a molecule of peroxide, contributes to a lowering of the activation energy of reaction. Possible extension of this idea to elucidation of the reactions of peroxides with other reagents has been pointed out.
Studies of Ion Exchange Membranes. XVI. The Preparation of Ion Exchange Membranes by the “Paste Method”
Authors: Mizutani Yukio , Yamane Reiichi , Ihara Hirofumi , Motomura Hiroji
Published: July 2006

A method for the preparation of ion exchange membranes, called the “paste method”, has been proposed. The pastes prepared from styrene-divinylbenzene-dioctyl phthalate-poly-(vinyl chloride) powder-benzoyl peroxide or from 2-methyl-5-vinylpyridine-styrene-divinylbenzene-dioctyl phthalate-poly(vinyl chloride) powder-benzoyl peroxide were coated on rein forcing materials of Teviron fabric and were treated in a hot press to prepare the base membranes, to which the ion exchange groups were then introduced. The ion exchange membranesthus prepared were excellent in electrochemical, mechanical and dimensional properties as well as in appearance.
The A. C. Polarography of Thiamine O-Monophosphate
Authors: Okamoto Koichi
Published: July 2006

A. C. polarographic studies of TMP, as well as a discussion of the polarographic behavior of TMP compared with that of B1 reported on in a previous paper, were carried out.

TMP showed well-defined peak currents of almost the same Es values as the second peak current of B1 in the region of pH values <10, and obscure second waves were also observed at pH values between 1.75 and 3.00. The relation of the is of the first wave of TMP to the pH value was also similar to the second wave of B1. The wave corresponding to the first wave of B1, however, was not recognized for TMP under any of the conditions studied.

The nature of the first wave of TMP was determined to be that of the diffusion currents, not of the adsorption, kinetic, etc.

The number of electrons discharged could be ascertained by the millicoulometric technique as 9 at pH values <3 and 8 at a pH value of 4. The electrode reaction, therefore, of TMP was considered to be the same as that of B1.

Some explanation of the relation of is to the pH value was attempted by reference to the pK values of TMP obtained from its experimental potentiometric titration curve.
The A. C. Polarography of S-Benzoylthiamine O-Monophosphate
Authors: Okamoto Koichi
Published: July 2006

The polarographic behavior of BTMP was studied using the a. c. polarographic method.

The two peak currents of BTMP in a wide pH value range could be observed definitely. Especially, the observation on the second wave, which was not clearly observed by the d. c. method, could be made.

The variations of the two peak current with the change in pH value were not similar to that of the diffusion currents in that the d. c. first wave height gave the largest value at about the pH value of 5, while the a. c. first wave height was largest at the pH value of 2 and then decreased with the increase in pH value.

The second a. c. wave height showed a maximum value at the pH values between 4 and 5, a minimum at a pH value of about 3, and increased at pH values <3.

The two a. c. waves were recognized to be of the diffusion current, not adsorption or kinetic waves.

The approximation of the diffusion coefficient of BTMP was carried out using the d. c. reduction wave of S-p-nitrobenzoylthiamine O-monophosphate (NBTMP) to give D=522×10−6 cm2 sec−1.

The estimation of the electron number, n, at various pH values on the d. c. first wave of BTMP was made using the value of D, so that it was found that 3 or 4 electrons were discharged in the reduction of BTMP in the acidic solutions.

The calculation of the transfer coefficient, α, and the rate constant, kG, for the first a. c. wave was undertaken by Matsuda’s method, giving, α=0.916, kG=5.75×10−4 cm. sec−1 at a pH value of 1.00, and α=0.430, kG=5.02×10−4 cm. sec−1 at a pH value of 5.5, etc.

The reaction processes of BTMP were estimated again according to the results obtained in this work. For the first wave two splitting mechanisms of the S-acyl bond which produced benzyl alcohol and benzpinacol consuming 4 and 3 electrons respectively, were considered. For the second wave, as no definite discussion could be undertaken on account of the illdefined form of the d. c. wave, it can only be suggested that it is the reduction of the reduction products, TMP. Some of the differences between the second wave of BTMP and the first wave of TMP observed in their pH value −is curves can be explained by the difference in the wave heights of the thiazol type and of the thiol type of TMP and also by the rather slow rate of the thiazol-ring formation of the latter.
Kinetics of the Acid-Catalyzed Decomposition of Trimeric Acetone Peroxide
Authors: Furuya Yoshiaki , Ogata Yoshiro
Published: July 2006

It was confirmed by the iodometry and gas chromatography that one mole of TAPO in acetic acid was decomposed to three moles of acetone and peroxyacetic acid in the presence of sulfuric acid. The rate of the reaction satisfied the first-order equation with a short induction period. The plot of logk vs. Ho gave a straight line with a slope of −1.12. When the concentration of TAPO was high, the amount of peroxyacetic acid was not quantitative, probably because of the transformation of peroxyacetic acid into acetyl peroxide.
The Crystal Structures of Metal 8-Hydroxyquinolinate. I. Copper 8-Hydroxyquinolinate
Authors: Kanamaru Fumikazu , Ogawa Kazuhide , Nitta Isamu
Published: July 2006

The crystal structure of anhydrous copper 8-hydroxyquinolinate has been determined by the two-dimensional Fourier method. It is monoclinic and has been shown to belong to the B21/a space group, with eight molecules in a cell of the dimensions: a=23.66, b=8.72, c=15.30Å and β=117.5. A copper atom is surrounded by four atoms with Cu–N distances of 1.92 and 1.90Å, and Cu–O distances of 2.01 and 2.07Å. Two nitrogen and two oxygen atoms form a square and are coplanar with the copper atom. The closest approach of adjacent chelate molecules occurs along the b axis and in the [101] direction, where the interplanar distances are 3.36, 3.47, and 3.32Å. These chelate molecules are grouped in pairs around the symmetry center at the point of origin with a Cu–Cu bond of 3.45Å. The perpendicular distances between successive dimeric molecules given above are almost the same within the range of experimental error. A π-bond overlapping of molecules is considered to be a part of the binding forces between such layers. The metal-metal bond is presumably the same as that in nickel dimethylglyoxime.
The Normal Vibrations of trans-trans Diacetamide
Authors: Uno Toyozo , Machida Katsunosuke
Published: July 2006

A normal coordinate analysis of the in-plane vibrations of diacetamide and of diacetamide-d taking the trans-trans configuration has been undertaken. The calculated frequencies agree well with the observed frequencies for the crystals in form B. The Urey-Bradley force field has been adopted, and the force constants obtained have been interpreted in terms of the difference in resonance structures between amides and imides. It has been shown that the vibrational modes of the characteristic imide frequencies are closely related to the behavior of the corresponding characteristic bands upon the change in the alkyl frameworks attached to the imide group.
The Wetting of Paraffin by Aqueous Solutions of Sodium Decyl, Dodecyl and Tetradecyl Sulfates
Authors: Tsunoda Teruo , Sasaki Tsunetaka
Published: July 2006

The wettability of the paraffin by aqueous solutions of sodium decyl, dodecyl and tetradecyl sulfate have been studied. A slight but distinct discontinuity of the slope in the curve of the cosine of the receding contact angle vs. the surface tension of the solution was observed for the solution of sodium decyl, dodecyl and tetradecyl sulfate. The discontinuity of the slope appeared at the surface tension of about 40 dyn./cm. It was found that the wetting isotherm which had been proposed by the present author, and which had been found valid for the wetting of paraffin by the aqueous solution of fatty alcohol homologues, was also valid for this experiment in the dilute aqueous solution of sodium alkyl sulfates. The adsorption energy was 588.9 cal./mol. CH2 and 534.7 cal./ mol. for the paraffin/solution and air/solution interfaces respectively.
σ Electronic Structures and Some Physicochemical Properties of Halogenated-conjugated Hydrocarbons
Authors: Morokuma Keiji , Fukui Kenichi , Yonezawa Teijiro , Kato Hiroshi
Published: July 2006

The simple LCAO MO method previously developed by the present authors has been adopted to the calculation of the σ electronic structures—σ molecular orbitals, their energies, separate and total σ electron densities, etc.— of conjugated halides. The general results of the computation—the so-called inductive effects along σ bonds, the unoccupied levels with the very low energy which is characteristic to halides, and so forth—have been described. Sigma dipole moments and the coupling constants in PQR have been calculated with the σ electron densities obtained and discussed in comparison with the experimental values.
Redox Reaction of Tetrahydrofuran Hydroperoxide
Authors: Murai Shinji , Sonoda Noboru , Tsutsumi Shigeru
Published: July 2006

1) Reaction of tetrahydrofuran hydroperoxide with ferrous sulfate produced hexane-1, 6-diol-diformate (13.8%), which was formed by the dimerization of 3-formoxypropyl radical generated from 2-tetrahydrofuranoxy radical, and γ-butyrolactone (31.4%) and 4-hydroxybutanal (trace).

2) In the presence of metal halide, the dimerization of the 3-formoxypropyl radical did not occur and halogenation of the 3-formoxypropyl radical was observed. For example, when tetrahydrofuran hydroperoxide was reacted with cuprous chloride and cupric chloride, 3-formoxypropyl chloride was obtained in a yield of 42.3%.

3) It is worth nothing that under suitable experimental condition the chloro compound was obtained in a good yield.

4) Probable reaction process was discussed.
The Electronic Structures and Antioxidizing Activities of Substituted Phenols
Authors: Morokuma Keiji , Kato Hiroshi , Fukui Kenichi
Published: July 2006

We have tested several models and their molecular orbital indexes of the rate-determining step of antioxidization by substituted phenols. Some molecular complex models have been found to be rational, though the problem of which of them is actually the true mechanism of the chain-breaking inhibition of autooxidation cannot yet be settled. Another possibility, that the earlier stage of the hydrogen abstraction reaction may be the rate-determining step, cannot yet be abandoned.

The numerical calculations have been carried out on the KDC-I digital computer of Kyoto University.
The Diffusion of Barium in a Rutile Single Crystal
Authors: Nakayama Takashi , Sasaki Tsunetaka
Published: July 2006

1) Microscopic and radiotracer studies have been made upon the diffusion of barium into a rutile single crystal.

2) In the microscopic observation, the diffusion layer of barium oxide in the rutile single crystal was confirmed to liquefy above 1300°C due to the formation of a eutectic mixture between both constituents. Below 1300°C solid phase diffusion prevails, and the diffusion layer consists of polycrystalline of a random orientation.

3) The diffusion coefficients of barium oxide in a rutile single crystal were measured by means of the radiotracer method using 133Ba. The diffusion coefficients obtained were 3.5×10−14∼2.4×10−13cm2/sec. in the range of 1100∼1200°C and 1.1×10−12 cm2/sec. at 1300°C. Between 1100°C and 1200°C, small differences seemed to be observed for the values obtained according to the direction of the diffusion in the crystal, but this is not conclusive. The large value of the diffusion coefficient at 1300°C was considered to be due to the liquefaction of the diffusion layer. The energy of activation was calculated to be 43 kcal./mol. (parallel to the c-axis) and 59 kcal./mol. (perpendicular to the c-axis).