bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fractures in Thin-sectioned Corundum Crystals
Authors: Yamaguchi Goro , Kubo Yasushi , Ogawa Hiroshi 
Published: July 2006

Abstract
The fracture properties of corundum crystals have been examined on various artificial corundums, such as electrically-fused corundum, Verneuil-flame-fused corundum and hydro-thermally-synthetised corundum. The specimens were ground to a tihckness of less than 5/100 mm. The microscope generated in the grinding process were observed by means of a polarizing microscope. The orientation of the c-axis (C) and the crack normal to the section normal (T) was measured using a universal stage. The direction of the crack has a close relation to the crystal orientation of the thin section. Frequent irregular cracks intercrossing one another occur in crystals ground with T∧G angles from 0° to 50°. Cleavage cracks along the {10\={1}1} plane take place prominently in the range of T∧C angles from 50°to 80°. Rare irregular cracks streaming in one direction take place in the range of T∧C angles from 80° to 90°. The heat treatment in air of titania-containing corundum decreases the number of cracks in the crystal. The results have been interpreted on the basis of the cohesion strength theory of M. D. Shappel (Am. Mineralogist, 21, 75 (1936)). In order to explain the limited range of the ocurrence of cleavage cracks, a model has been proposed in which the shearing along the cleavage plane takes place prior to the crack nucleation in the corundum crystal.
Kinetic Studies of Solvolysis. XII. The Question of a Single Mechanism for the “Borderline” SN Reactions—The Solvolysis of Optically Active α-Phenylethyl Chloride in Aqueous Ethanol
Authors: Okamoto Kunio , Uchida Nobuko , Saitô Seiki , Shingu Haruo 
Published: July 2006

Abstract
Competitive solvolysis has been conducted in binary solvents of water and ethanol on optically active α-phenylethyl chloride at 40.0°C. The extents of inversion (α%) for solvolysis products, i. e., α-phenylethyl alcohol and α-phenylethyl ethyl ether, have been calculated from the optical rotations of these products isolated after ten half-lives, and the values of α% have been plotted Vs. the volume percentage of water. In the region of 90% aqueous ethanol, the two α% lines for the alcohol and the ether intersect with each other. This intersection of the two lines conflicts with any single mechanism for the borderline SN reactions, whereas the dual mechanism can explain this phenomenon without any difficulty. In the region of a 100% water-solvent (a typical medium for the SN1 solvolysis), the two lines do not converge to the same α% value. On the basis of these findings, a general mechanism of racemization for the SN1 solvolysis has also been discussed.
The Volatile Constituents of Some Plants of the Compositae Family
Authors: Tsubaki Naoko , Nishimura Kiichi , Hirose Yoshio 
Published: July 2006

Abstract
Full analyses of the essential oils obtained from Yomena (Aster indicus L.), Yomogi (Artemisia princepts Pamp.) and Hog weed (Ambrosia elatior L.) were carried out. Each essential oil was separated by fractional distillation under reduced pressure, and the fractions thus obtained were identified.
The Reactions of cis, trans, trans-1, 5, 9-Cyclododecatriene. IV. Selective Reactions with cis-Addition Reagents
Authors: Ohno Masaji , Okamoto Masaru , Torimitsu Seiichi 
Published: July 2006

Abstract
The addition reactions of cis, trans, trans-1, 5, 9-cyclododecatriene with cis-addition reagents, such as osmium tetroxide, potassium permanganate, diimide, and nitrosyl chloride, have been investigated. It has been shown that the first attack of each reagent preferentially takes place at one of the trans double bonds. The reactions with osmium tetroxide and potassium permanganate at room temperature afforded cis-5, trans-9-cyclododecadiene-trans-1, 2-diol in 89 and 59% yields respectively. The glycol was then further oxidized with osmium tetroxide into cis-y-9-cyclo-dodecene-1, 2, 5, 6-tetrol in a 60% yield. The reduction of the cyclotriene with diimide, generated in situ by the oxidation of hydrazine, afforded cis-cyclododecene in 60—82% yields. The addition of nitrosyl chloride in the presence of hydrochloric acid afforded 2-chlorocyclodode-cadienone oxime in a quantitative yield; this was then reduced into cyclododecanone oxime, obtained in a quantitative yield, by catalytic reduction with palladium-charcoal.
Asymmetric Hydrogenation with Modified Raney Nickel. VI
Authors: Izumi Yoshiharu , Tatsumi Susumu , Imaida Masami , Fukuda Yoshio , Akabori Shiro 
Published: July 2006

Abstract
The asymmetric hydrogenation catalyst has been prepared by the modification of Raney nickel with solutions of (−)-2-methyltartaric acid (A), (+)-2-methyltartaric acid (B) and (+)-2,3-dimethyltartaric acid, and its asymmetric hydrogenation activity has been measured by the hydrogenation of methyl acetoacetate to optically active methyl 3-hydroxybutyrate. The asymmetric activity of the catalyst is much influenced by the pH and the temperature of the modifying solution. Generally, (+)-2-methyltartaric acid (B) and (+)-2,3-dimethyltartaric acid have a high asymmetric activity in reaction to Raney nickel. The highest asymmetric activity has been obtained by modification with (+)-2-methyltartaric acid (B) and with it the specific rotation of the hydrogenation product has been found to be [α]D20 +11.72° (without a solvent) under the optimum conditions. This value means that the product is 78% composed of the dextro- and 22% of the levorotatory form. On the other hand, the asymmetric activity of the catalyst modified with (−)-2-methyltartaric acid (A) is very low and quite different from that of the catalyst modified with (+)-2-methyltartaric acid (B). It has been supposed that this difference depends on the stereoisomerism of the threo-erythro form of the 2-methyltartaric acid molecule.
The Transfer of the Oxygen Atom of Water in an Aqueous Solution of Iron and Copper Sulfates
Authors: Suzuki Nobutake , Hotta Hiroshi , Hashimoto Hitoshi 
Published: July 2006

Abstract
When an oxygen-18 enriched aqueous solution of ferrous, ferric and cupric sulfates was heated between 130 and 200°C, the oxygen-18 content decreased in the order of FeII&gt;FeIII&gt;CuII in water; and it increased in the sulfate group and in the molecular oxygen of the gaseous phase. A transfer of oxygen from water to the sulfate group was also observed, even in a nitrogen atmosphere. The oxygen transfer was promoted in all the cases in the presence of molecular oxygen, and it increased further in the presence of benzene. Since the exchange reaction of oxygen does not occur between water and sulfate ions, the above facts may be attributed to the reactions between water and the thermal decomposition products of the sulfate group, and between water and the hydrogen peroxide produced. The peroxy species, produced by the oxidation of the decomposition products, are more reactive in such a transfer of oxygen, since the reaction is promoted in the presence of oxygen. The peroxides in the autoxidation of benzene seem also to be reactive in it.
Silent Discharge Reactions in Aqueous Solutions. I. An Acidic Aqueous Solution of Ferrous Sulfate in Atmospheres of Helium and Argon
Authors: Yokohata Akira , Tsuda Satoru 
Published: July 2006

Abstract
In an atmosphere of helium or argon, the silent discharge reactions of aqueous solutions have been investigated from the point of view of radiation chemistry. A discharge tube with two coaxial glass tubes was used. In a dilute oxygen-free aqueous solution of sulfuric acid, hydrogen peroxide appeared as a result of discharge. Also, the oxidation of ferrous ions to ferric ions has been found. It has been confirmed, first, that neither the effect of metastable excited states of helium and argon nor that of luminescence is serious, and, second, that the reaction may well be interpreted by taking into consideration the actions of slow electrons generated in the gas phase on the liquid water. The yield of hydrogen atoms plus hydroxyl radicals has been estimated from the yields of hydrogen peroxide and ferric ions. The ratios of the yield of hydrogen peroxide to that of radicals show that the silent discharge reaction corresponds to the reaction by ionizing radiation of high LET, the value of which apparently equals 3eV./Å in helium and 8 eV./Å in argon. The G(Fe3+) value and the absorbed dose (E) estimated were, respectively, as follows: In helium: G(Fe3+)=4.6, E=3.8×106 r./hr.; in argon: G(Fe3+)=4.3, E=7.2×106 r./hr.
The Absorption Spectra of Dyes. X. Note on the Configuration of the Component Molecules in the Complex State
Authors: Hoshi Toshihiko , Tanizaki Yoshié 
Published: July 2006

Abstract
The configuration of the component molecules in the complex formed between Chryophenine G (G) and the direct dyes (P),such as Chlorazol Sky Blue FF, has been discussed qualitatively with respect to the relation between the steric structure of the individual P molecules and the enthalpy or the entropy changes in the complex formations. the electrons to be transferred from the partner (P) to the G molecule are the π electrons of the functional (hydroxy) groups and are those of the inner-side groups when the respective coupling components of the dye have more than one functional group. The large the charge density of such an effective functional group becomes, the more the enthalpy change (−ΔH) is increased. It may be said with certainty that there must exist a certain configuration of the component molecules peculiar to the complex formation. Such a configuration may be seen for the configuration of G and ND (NW-acid←dianisidine→NW-acid). For other combinations of which the partner of G is more deformed in free than ND state, the shifts of equilibrium to the configuration for the complex state are almost due to an entropy change (−ΔS) which increases in proportion to the magnitude of the deformation.
An MO-Theoretical Illumination for the Principle of Stereoselection
Authors: Fukui Kenichi 
Published: July 2006

Abstract
The principle of the stereoselection in organic chemistry has been discussed from the point of view of the molecular orbital theory. The stereoselectivity in the stereospecific ring-closure of conjugated polyenes and the stereospecific ring-cleavage of unsaturated carbon cycles, trans-1,2-noncycloadditions, cis-1,2-additions and cis-1,3-dipolar additions have been accounted for with a qualitative generalization. In many cases the symmetry relationship of certain particular molecular orbitals (“frontier orbitals”) plays a conspicuously significant role in the steric control of stereochemical processes. This may be put in contrast with the role of the frontier electron density in the orientation process in organic reactions.
Syntheses of dl-Tetrahydroanhydrodesoxyaucubigenin and Related Compounds
Authors: Kurosawa Kazu , Obara Heitaro , Uda Hisashi 
Published: July 2006

Abstract
The racemic tetrahydroanhydrodesoxyaucubigenin, one of the derivatives from a glycoside, aucubin, has been synthesized using cis-cis-2-(2′-hydroxyethyl)-5-methoxycarbonylcyclopentane-carboxylic acid δ-lactone as an intermediate. 6,7-Dimethoxycarbonyl-2-oxa-bicyclo[3.3.0]-octane has also been synthesized, and the mechanism of the base-catalyzed rearrangement of the naturally-derived tetrahydroanhydroaucubigenin p-toluenesulfonate has been elucidated.
Vinylpolymerisation. CXXIX. Pfropfung von Methylmethacrylat auf Naturkautschuk in Abwesenheit von Initiatoren
Authors: Kondo Mitsuru , Yamada Kuniyoshi , Takemoto Kiichi , Imoto Minoru 
Published: July 2006

Abstract
The graft polymerization of methyl methacrylate on natural rubber was studied in an aqueous suspension at 90°C, in the absence of initiators. It was found that methyl methacrylate could be grafted fairly smoothly on uncured natural rubber crepe and latex, both of which had previously been extracted with acetone.
The Ring-opening Polymerization of Ethylene-methylphosphite
Authors: Shimidzu Takeo , Hakozaki Tomio , Kagiya Tsutomu , Fukui Kenichi 
Published: July 2006

Abstract
Several Lewis acids have been found to be effective catalysts for the polymerization of ethylene-methylphosphite, giving a solid polymer with a poly(ethylene-methylphosphonate) structure. The use of Al(C2H5)3 gave a wax-like polymer with the structure of poly(ethylene-methoxy-phosphinate), while Na and Li in liquid NH3 at −78°C produced a jelly-like polymer partly composed of poly(ethylene-methylphosphite).
Phosphorylation via the Oxidation of Phosphite. II. The Preparation of the Diesters of Phosphorous Acid by the Reaction of Alcohols with Ethyl N-Phenylimino Phosphite and Acids
Authors: Mukaiyama Teruaki , Osaka Kazutoshi 
Published: July 2006

Abstract
The diesters of phosphorous acid were prepared in good yields by the reaction of primary or secondary alcohols, such as methanol, ethanol, and s-butanol, or of phenols, such as phenol, p-chlo-rophenol and p-cresol, with ethyl N-phenylimino phosphite and p-toluenesulfonic acid monohy-drate. Similarly, when carboxylic acids, such as acetic acid, benzoic acid, p-chlorobenzoic acid and trichloroacetic acid, were used in place of the acid monohydrate in the above experiment, the diesters of phosphorous acid were also obtained. Ethyl N-n-propylimino or ethyl N-isopropylimino phosphite could be successfully used in place of ethyl N-phenylimino phosphite in the above experiments. Further, various derivatives of methylphosphinic acid, such as ethyl dicyanomethyl-, ethyl cyanocarboethoxymethyl- and ethyl dicarboethoxymethylphosphinate, were obtained by the reaction of ethyl N-phenylimino phosphite, p-toluenesulfonic acid monohydrate and active methylene compounds, such as malononitrile, ethyl cyanoacetate and diethyl malonate.
The Determination of Micro Amounts of Polythionates. IV. A Photometric Method for the Determination of Tetrathionate by Decomposition with Sodium Sulfite
Authors: Iwasaki Iwaji , Suzuki Shigeru 
Published: July 2006

Abstract
A new photometric method for the determination of tetrathionate by means of its decomposition with sulfite has been developed. It is based on the formation of thiosulfate equivalent to the tetrathionate, and on the photometric determination of thiosulfate by measuring its decoloration of an iodine solution. 5×10−6–1×10−3 m (1 mg./l.–0.2 g./l.) of tetrathionate can be determined easily and rapidly within a range of error of ±2×10−6–2×10−5 m (0.4 mg./l.–4 mg./l.) by using 20 ml. of a sample. The tetrathionate solution is decomposed with sodium sulfite in a slightly alkaline medium. After the completion of the decomposition reaction, a formaldehyde solution is added to mask the interference of the excess sulfite remaining and this solution is acidified with acetic acid. Then the standard iodine solution is added. The absorbancy of the solution is measured at the wavelength of 372 or 440 mμ 20 min. after the addition of an iodine solution. By this method tetrathionate can be determined, even when it is coexistent with thiosulfate and sulfite in up to similar amounts. Many substances, such as aluminum, calcium, cadmium, magnesium, zinc, silicate, nitrate, sulfate, phosphate, chloride and fluoride, do not interfere, but iron(II, III), manganese(II), copper(II) and sulfide do interfere.
Copper(II) Halide Complexes with Substituted Pyridine N-Oxides
Authors: Muto Yoneichiro , Jonassen Hans B 
Published: July 2006

Abstract
Pyridine N-oxide copper(II) chloride, the structure of which has recently been elucidated by X-ray analysis [J. C. Morrow and H. L. Schäfer, private communication], has a subnormal magnetic moment (0.85 b.m. [J. V.Quagliano, J. Fujita, G. Franz, D. J. Phillips, J. A. Walmsley and S. Y. Tyree (J. Am. Chem. Soc., 83, 3770 (1961)]). It consists of a binuclear molecule [Cu(C5H5NO)Cl2]2 in which copper atoms are bridged in pairs by two oxygen atoms. In this work, copper(II) complexes with the empirical formulae of CuX2L, CuX2L2 and CuX2LY (X=Cl, Br;L=pyridine N-oxide, 3-picoline N-oxide, 4-picoline N-oxide, 4-chloropyridine N-oxide, 2,4-lutidine N-oxide, 2,4,6-collidine N-oxide, 4-nitroquinoline N-oxide; Y=N,N′-dimethylformamide, dimethylsulfoxide) have been prepared, and magnetic and spectral studies of these complexes have been made. The room-temperature magnetic susceptibilities of CuX2L complexes have been found to be correlated with the pKa (acid-dissociation constant) values of the attached N-oxides. The absorption band in the 735–900 mμ region (the so-called copper band) in the solid-state reflectance spectra of CuX2L complexes has been found to shift towards a lower frequency as the ligand field strength decreases, and a good parallelism between the frequencies and the magnetic moments has been observed. The effect of the attached ligand on the magnetic interaction has been discussed in terms of the electronic effect of the substituent on the pyridine ring. The infrared spectral data on the N–O stretching frequency indicate the absence of Cu–O–Cu linkage in the CuX2L2 complexes with normal magnetic moments.
Calculation of the Three π–π* Absorptions of Conjugated Systems by Hückel MO Method
Authors: Nishimoto Kichisuke 
Published: July 2006

Abstract
Correlation relations between the Hückel molecular orbital energies and the absorption wavelengths of the 1La, 1Lb, and 1Bb species of an alternant hydrocarbon are presented. After a small modification, the present relations are applied fairly well to the calculations of the electronic spectra of α-substituted hydrocarbon and N-heterobenzenes. This shows us that the nature of the electronic spectra of these compounds are very similar with those of parent hydrocarbon. On the other band, the calculation for β-substituted derivatives does not give good results, although the agreement between the calculated and observed values is semi-quantitatively satisfactory. This should be attributed to the complicated configuration interaction scheme between the lower excited configurations of the molecule.
The Oxidation of Acetylacetone in the Presence of Cobaltous Ions
Authors: Koga Tadashi , Hara Tadashi 
Published: July 2006

Abstract
Concerning the oxidation of toluene and p-xylene with atmospheric oxygen at 90°C in glacial acetic acid in the presence of cobaltous acetate and acetylacetone (HAAH), it was found that the reaction proceeds smoothly only at the mole ratio of [HAAH]/[Co2+]=2. When the absorption rate of oxygen was then measured for acetic acid solutions containing cobaltous ions and HAAH, the following results were obtained:
at [HAAH]⁄[Co2+]≤3, −d[O2]⁄dt=Ka[HAAH]1⁄2[Co2+]−1⁄3
at [HAAH]⁄[Co2+]≥4, −d[O2]⁄dt=Kb[HAAH][Co2+]1⁄4
These rates agree well with those derived by means of elementary equations in the radical chain reactions. It was further supposed, on the basis of the elementary equations, that active intermediates, such as Co3+, [Co3+(AAH−)2]+, and some radicals, were produced smoothly at the mole ratio of [HAAH]/[Co2+]=2. However, ketones, such as acetonylacetone and ethyl acetoacetate, were still active even at the mole ratio of [ketone]/[Co2+]=3. This seems to stem from the differences in complex stabilities between cobalt and HAAH or other ketones.
The NMR Analysis of the Water of Crystallization in Beryl
Authors: Sugitani Yoshinori , Nagashima Kozo , Fujiwara Shizuo 
Published: July 2006

Abstract
The existence of two types of protons in beryl was proved by the proton magnetic resonance technique; one is as a molecular form of water in the channel of the crystal, while the other is as a hydroxyl-ion replacing O2− ion of the crystal lattice. The proton-proton line of the water was found to be parallel to the c-axis of the crystal.
Colloid Chemical Studies of Phase Diagrams of Binary Polyoxyethylene Nonylphenyl Ether - Water Systems
Authors: Kenjo Kazutoshi 
Published: July 2006

Abstract
Colloid chemical studies of the phase diagrams of binary systems of aqueous polyoxyethylene nonylphenyl ethers with different degrees of the polymerization of ethylene oxide, n, have been undertaken. The phase diagrams obtained have been divided into the heterogeneous region 1, existing in the range of temperature higher than cloud points; the homogeneous phase region II; the heterogeneous region III, existing below the II region; and the solid phase region IV. The II region contains a gel-like hardening region. The III region has been further divided into two sub-regions, on the higher and lower concentration sides; these subregions contain one hardening region each. The molecular and micellar structure models of these hardening regions have been presented. An unusual zone has been found in the phase diagram of the system for n=7.5 its state has also been discussed. Further, the mechanisms of the phase separation and phase inversion have been proposed, and three different types distinguished for the phase separation at the cloud point. A functional relationship has been found between the cloud point, the water content of an aqueous solution at the cloud point (the water affinity), and the n value. A linear relation has also been found between the solidification points of 100% surfactants and the ethylene oxide contents of the surfactants.
Catalytic Asymmetric Benzaldehyde Cyanohydrin Synthesis with Synthetic Optically Active Polymer. III. N-Substituted Poly-(s)-isobutylethylenimine
Authors: Tsuboyama Sei 
Published: July 2006

Abstract
Asymmetric syntheses of benzaldehyde cyanohydrin in the presence of polymers of N-methyl-,N-ethyl- and N-benzyl-(s)-2-isobutylethylenimine as catalysts have been studied. The selectivity of these polymers was poor (optical yield of (−)-isomer obtained; 0–1%) compared with that of a non-N-substituted polymer (20%). It seems that the large difference in the optical yield can be ascribed to their conformation. As to the polymer being capable of promoting the reaction asymmetrically, it is assumed that the isobutyl group and a helical form are the responsible factors. On the basis of these findings, a model for the addition step has been suggested in order to explain the observed result.
Studies of the Solution Properties of Co-polymer. I. Styrenepolysulfone
Authors: End\={o} Ry\={u}ichi , Manag\={o} Tomoyuki , Takeda Masatami 
Published: July 2006

Abstract
Styrenepolysulfone was polymerized and then, for its fractionation, tetrahydrofuran and methanol were used as solvent and precipitant respectively. The viscosities and osmotic pressures of fractions of this co-polymer were examined in tetrahydrofuran. The relation between the intrinsic viscosity and the molecular weight, [η]=0.389×10−4\barMn0.78, was thus obtained. The unperturbed molecular dimension was calculated by the Fixman-Stockmayer method. The results were then compared with the calculated end-to-end distance of the hypothetical freely-rotating chain. The steric parameter, σ=1.53, was also obtained and compared with that of polystyrene.
Dipole Moment and Molecular Structure of Copolymers. III. Dipole Moment of p-Methoxystyrene-Styrene Copolymers and p-Chlorostyrene-Styrene Copolymers
Authors: Kotera Akira , Suzuki Keizo , Matsumura Kimiyoshi , Shima Mikiko , Joko Etsuro 
Published: July 2006

Abstract
The p-methoxystyrene monomer has been synthesized from anisole through p-methoxyacetophenone and p-methoxyphenyl methyl carbinol. Then copolymers of p-methoxystyrene and styrene have been prepared. The dielectric properties of the copolymers in a benzene solution have been measured, and it has been found that the value of the dipole moment, μ, of the p-methoxystyrene monomer unit in the copolymers increases with an increase in the styrene content, e. g., from 1.21 D (for poly-p-methoxystyrene) to 1.32 D (for the copolymer in which the mole fraction of p-methoxystyrene is 0.175) at 20°C. The variation in the value of μ has been discussed in view of the detailed arrangement of polar monomer units. The theory concenring the relation between the dielectric polarization and the detailed structure of the copolymer molecule developed in the preceding paper, Part I, has been applied to the experimental results. In addition, a similar analysis has been made for the dielectric polarizations of the p-chlorostyrene-styrene copolymers which had been measured previously by one of the authors.