bluuebunny/crossref_metadata_2025 huggingface dataset:
The Refined Calculation of the Band-gap Energy of Tetramethylammonium Pentaiodide
Authors: Kusabayashi Shigekazu , Mikawa Hiroshi , Konda Misako , Hayashi Masano
Published: July 2006

The band-gap energy has been calculated by a tight-binding approximation in a previous report. Although the value thus calculated coincided rather well with the experimental value, it might yet be possible that the band-gap energy will change appreciably when the interactions of all the energy levels are considered at one time. It was, therefore, calculated by the following method, which considers in principle all the level interactions. A repeating unit is composed of 30 atomic orbitals. Each atomic wave function makes three-dimensional Bloch functions. The crystal wave function is set up in the form of a linear combination of these 30 Bloch functions. The energy is then calculated by applying the variation principle and by using the Hückel approximation. The band-gap energy thus calculated is 1.20 eV. This value is near the experimental value, 1.36 eV.; it was also close to the previous result, 1.26 eV., thus confirming the previous calculations. The consideration of the band-widths and the density of the state may interpret the experimental results on the sign of the carrier. The results offer additional support for our previous conclusion regarding the conduction mechanism.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. X. Nitrates of α-Hydroxy-carboxylic Acids
Authors: Tsuzuki Yojiro , Tanabe Koko , Okamoto Kikuhiko , Fukubayashi Michiyo
Published: July 2006

The rotatory dispersion (RD) and ultraviolet absorption of some α-hydroxy-carboxylic acids and their nitrates have been measured and analyzed. A distinct relation has been found between the configuration and the sign of the Cotton effect; namely, nitrates of α-d-hydroxy-carboxylic acids (R-configuration) show positive Cotton effects, while those of α-l-hydroxy-carboxylie acids (S-configuration) show negative Cotton effects. Thus a rotatory contribution by the nitrates of the α-hydroxyl group has been suggested, though it is opposite in sign to the xanthates of the α-hydroxy-carboxylic acids.
A Thermodynamic Approach to Thixotropy
Authors: Sen\={o} Manabu
Published: July 2006

The thixotropic behavior is discussed on the basis of the thermodynamics of irreversible processes. The fundamental equations are given for the thixotropic fluids by accepting the concept that the internal structure of the system is destroyed by the applied forces, and the general phenomenological equations are written for all the processes occurring in this system. The process by which the thixotropic recovery takes place is non-stationary. A method of specifying this process is proposed by introducing the concept of a fictitious pressure tensor; the data on a rubber latex suspension given by Mooney is analyzed by this method.
The Application of the Molecular Orbital Theory to the Bond Scissiom of Aliphatic Amines
Authors: Hirota Kozo , Itoh Michiyasu
Published: July 2006

The relative scission-probabilities of C–C bonds of n-propyl, n-butyl and isobutyl amines being formed by electron impact (90 V.) were determined by the use of mass spectrometers of the usual type and of the high-resolution type. They were in good accordance with the theoretical values calculated by the LCBO-MO theory which had been proposed and found successful in explaining the mass spectra of n-paraffins and methyl alkyl ketones.
Organic Syntheses by Means of Noble Metal Compounds. XIV. The Carbonylation of Cyclooctadienes
Authors: Tsuji Jiro , Hosaka Shuntaro , Kiji Jitsuo , Susuki Tosaku
Published: July 2006

The 1,5-cyclooctadiene - palladium chloride complex and carbon monoxide react in ethanol to form ethyl 4-cyclooctenecarboxylate. The carbonylation of 1,5-cyclooctadiene catalyzed by palladium chloride has given ethyl 4-cyclooctenecarboxylate and cyclooctanedicarboxylate. It has been found that the monoester can be obtained selectively under certain conditions; the further carbonylation of the monoester gives the diester. Under the same reaction conditions, 1,3-cyclooctadiene gives ethyl 2-cyclooctenecarboxylate in a low yield. Metallic palladium has been found to be the true catalyst and the presence of hydrogen chloride has been found to be essential for the catalysis. It has also been found that the 1, 5-cyclooctadiene - palladium chloride complex can be formed from 1,5-cyclooctadiene, metallic palladium and hydrogen chloride by heating them in an autoclave under nitrogen. It seems likely that the catalytic carbonylation of 1,5-cyclooctadiene proceeds through the formation of the 1,5-cyclooctadiene - palladium chloride complex.
The Benzene-photosensitized Isomerization of Butene-2 and Pentene-2
Authors: Tanaka Masahiro , Kato Masaaki , Sato Shin
Published: July 2006

The benzene-photosensitized cis-trans isomerization of butene-2 has been reinvestigated, using 2537 Å as the light source. A comparative study with pentene-2 has also been carried out. In all experiments, pentene-2 behaved very similarly to butene-2. The quantum yield of the isomerization was estimated to be 0.27±0.03, irrespective of the olefin used. The following photostationary ratios of the cis to the trans isomer were obtained: 1.05±0.1 for butene-2, and 0.99±0.1 for pentene-2. The ratio of the initial rates of isomerization was, for both olefins, 1.15±0.15, in favor of the isomerization from the cis to the trans isomer. Both ratios are very close to unity; this finding is in agreement with our previous results (M. Tanaka, T. Terao and S. Sato, Bull. Chem. Soc. Japan,  38, 1645 (1965)).
On the Asymmetric Interaction of the Optical Antipodes with Amylose
Authors: Ohara Masaaki , Chen Chau-Yang , Kwan Takao
Published: July 2006

The asymmetric adsorption of d, l-mandelic acid and its homologues has been demonstrated on amylose by means of the column chromatographic and static techniques. The d-(−)-isomer of mandelic acid has been found to be adsorbed more weakly than the l-(+)-isomer; the separation factor of the two antipodes has been estimated to be 1.09 at 0°C. This value is greater than that on starch, suggesting that amylose may have a somewhat higher selectivity for the asymmetric adsorption of the optical antipodes than amylopectin. The anomalous interaction of d, l-atrolactic acid has been observed on the amylose much as in the case with starch reported previously.
Hydrothermal Synthesis of Fluor-Hydroxyl Muscovite
Authors: Noda Tokiti , Endo Yasuhiko , Ushio Masumi
Published: July 2006

Fluor-hydroxyl muscovite was synthesized from a mixture of gels and chemicals of the KAl3Si3O10Fx(OH)2−x composition, where x=0, 0.5, 1.0, 1.5 and 2.0, in the temperature range of 500–600°C under pressures ranging from 500 to 900 atm. The fluorine content of the synthetic muscovite increased with the increase in x, but the distribution coefficient of fluorine [(the fluorine content of the crystal)/(the fluorine concentration of the solution)] decreased with the increase in x, increased with the increase in the temperature of synthesis, and decreased with the increase in the pressure of synthesis. The synthetic fluor-hydroxyl muscovite crystallized mainly in 1M polymorph, and very little in 2M polymorph, at 500°C in 20 hr. The fraction of 2M muscovite increased with the increasing temperature of synthesis. The d005 and d060d lattice spacings of the mica were observed to decrease linearly with the increase in the fluorine content of the mica.
The Stability of Fused Rings in Metal Chelates. III. The Relative Stability of Copper(II) Complexes of Aldehyde- and Ketone-Schiff Bases
Authors: Nakao Yasuo , Sakurai Ken-ichi , Nakahara Akitsugu
Published: July 2006

The relationship between the structure of fused-ring systems and the relative stability of copper(II) Schiff base chelates has been discussed, on the basis of the properties of six copper(II) complexes, in connection with the transamination reaction. As the conclusion it has been suggested that the transamination reaction in fused-ring systems containing copper(II)-glyoxylate- or -pyruvate-Schiff bases may be expected only in such appropriately unstable systems as have two five-membered rings and that it is generally accompanied by a stabilization of the system. The preparation and properties of the two new copper(II) chelates, glyoxylidene-β-alaninatoaquo-copper(II) and pyruvidene-α-alaninatoaquocopper(II), have been described.
The Effect of Acetates on the Synthesis of Acetic Acid from Methanol and Carbon Monoxide in the Presence of Cobalt(II) Iodide as a Catalyst
Authors: Mizoroki Tsutomu , Nakayama Mikitake
Published: July 2006

In the synthesis of acetic acid from methanol and carbon monoxide in the presence of cobalt(II) iodide as a catalyst, the addition of an acetate has been shown to have a great influence upon the methanol conversion into total acetic acid. When the added amounts of potassium acetate are from one to two times as much as that of cobalt (II) ion, both methanol conversion and its reaction rate reach a maximum, and methanol is prevented from forming dimethyl ether. On the other hand, the reaction nearly stops when the amount of potassium acetate becomes more than four times as large. The variation in the absorption spectrum of cobalt (II) ion in course of the reaction shows that the increase in the added amount of an acetate is favorable for the formation of cobalt carbonyls and that most cobalt(II) ions are tetrahedral species of the [Co(AcO)4−n-In]2− type so long as the reaction is promoted with the catalyst. From these experimental results, the course of the reaction has been discussed.
The Reaction of Amino Alcohols with Acrylates
Authors: Ogata Naoya , Asahara Tomohiko
Published: July 2006

The addition reaction of amino alcohols with acrylates were studied. The addition takes place at the amino group of amino alcohol, producing N-(hydroxyalkyl)-β-alanine in a good yield. The reaction rate becomes slower as the ester group of acrylate becomes larger, and phenyl acrylate gives a polymer as soon as it is mixed with ethanolamine. The rates of the addition reaction with acrylate are in the following order: NH2CH2CH2OH>CH3NHCH2CH2OH>>RNH2>NH(CH2CH2OH)2.
Intramolecular Hydrogen Bonds. VII. Methyl Mandelates and Related Compounds
Authors: Mori Nobuo , Tanaka Yoshiteru , Tsuzuki Yojiro
Published: July 2006

The infrared OH spectra of an ArCH(OH)(CH2)nCOOMe series (n=0 and 1) in dilute carbon tetrachloride solutions have been measured at 25°C with a Perkin-Elmer 21 spectrometer. A comparison of the data with those of other related compounds shows that the OH group forms a hydrogen bond predominantly with the carbonyl-oxygen atom and also with the ether-oxygen atom and/or the π-electrons of the phenyl group, while, practically speaking, no free OH group is present. Further, the NMR chemical shifts of the methine- and the methyl-protons when n=0, as measured with a Varian A-60 spectrometer, have been correlated with the Hammett substituent constants; the shift of the methine-proton, when the ring-substituent is a halogen, does not fall on the correlation line, but falls on a separate line.
The Heats of Dilution of Atactic Polystyrene Solutions
Authors: Kagemoto Akihiro , Murakami Sachio , Fujishiro Ryoichi
Published: July 2006

The heats of dilution of atactic polystyrene (\barP=244)-various solvent systems have been measured by using a micro-twin-calorimeter at 25°C. Toluene, anisole, ethyl methyl ketone, dioxane and ethyl acetate were used as the solvents. For the analysis of the experimental data obtained by each dilution process, the simple Van Laar formula has been used, and the apparent enthalpy parameter between the polymer and the solvent has been derived. Since these interaction parameters seemed to depend on the concentration, we tried to analyze the experimental data with a modified Van Laar formula which contained interaction parameters depending on the concentration. The interaction parameters obtained by these analyses are considerably dependent on the concentration in good solvents, while those in poor solvents depend hardly at all on the concentration. This dependence of the interaction parameters on the concentration has been explained by using the dilute solution theory of polymer solutions proposed by Flory and Krigbaum (J. Chem. phys., 18, 1086 (1951)). The interaction parameters in the dilute region have been compared with those obtained by other methods, and the agreement between our values and those obtained by other methods has been found to be fairly good.
Ferrocene-containing Polymers. IX. Polycondensation of Ferrocene with Formaldehyde
Authors: Neuse Eberhard W , Quo Edward
Published: July 2006

The Lewis acid-catalyzed polycondensation of ferrocene with formaldehyde or its dimethyl-acetal gives rise to the formation of soluble, novolac-type polymers comprising ferrocenylene units interlinked by methylene bridges. In contrast to earlier work performed by other investigators in liquid hydrogen fluoride or sulfuric acid media, where only non-polymeric products were described, propagation is accomplished in the present case by condensing the reactants in a closed system in bulk at temperatures up to 170°C. The resulting polymers, with Mn values up to 4000 (unfractionated), are shown by elemental and spectroscopic analyses and viscometric data to be essentially identical with the previously reported polycondensation products of N, N-dimethyl-aminomethylferrocene with ferrocene. Infrared spectroscopy shows the intralinear substitution to be predominantly homoannular, which is expected as a result of the electronic effects exercised by the methylene substituent. Under appropriate conditions, additional methylene groups can be incorporated into the polymer, giving rise to double-bridged segments and inter-chain bridging. Strongly crosslinked polymers are obtained if excess aldehydic reactant is employed at temperatures in the 170–185°C range.
The Catalytic Dehyrochlorination of 1, 2-Dichloroethane on Active Carbon in the Presence of Some Hydrocarbons
Authors: Okamoto Kunio , Tanaka Noboru , Adachi Kiyoshi , Shingu Haruo
Published: July 2006

The catalytic pyrolysis of 1, 2-dichloroethane on active carbon, carried out at 300 and 400°C in the presence of toluene, benzene and n-hexane, resulted predominantly in ethylene instead of vinyl chloride, which is known in the literature as the major pyrolysis product of the titled compound; the pyrolysis rates were suppressed by these hydrocarbons. These results have been explained by assuming a radical-chain mechanism similar to that suggested for the “homogeneous” pyrolysis of this compound. The chain length derived from the proposed mechanism has been estimated to be 20 to 50.
Plastic Scintillators. II. The Synthesis of Some Distyrylbenzene Derivatives as Wavelength Shifters in Plastic Scintillators
Authors: Nakaya Tadao , Imoto Minoru
Published: July 2006

The synthesis and the absorption and fluorescence spectra of 2, 5-dimethoxy-1, 4-distyryl-benzene derivatives and the related compounds are reported on. Their absorption and their fluorescence spectra, are then discussed. According to the spectra, some of the compounds synthesized here are better wavelength shifters in plastic scintillators that the compounds described in the literature.
The Synthesis of Bicyclic Lactam Ether
Authors: Ogata Naoya , Tohoyama Shyunroku
Published: July 2006

The bicyclic lactam ether, 3-aza-10-oxabicyclic[4.3.1]decane-4-one has been attempted to synthesize by the Beckmann rearrangement of the oxime of 9-oxabicyclo[3.3.1]nonane-3-one; this rearrangement caused polymerization through the cleavage of the ether group in acidic media. Therefore, it may be presumed that the cationic polymerization of lactam ethers in the presence of Lewis acid proceeds through the opening of the ether linkage.
Methylene-hydantoin and Related Compounds. II. Poly-5-methylene-hydantoin and Poly-α-aminoacrylic Acid
Authors: Murahashi Shunsuke , Yuki Heimei , Kosai Koichi , Doura Fumihiro
Published: July 2006

5-Methylene-hydantoin was polymerized easily by free radical initiators, and showed a higher reactivity in copolymerization with styrene. From the copolymerization of styrene (M1) and 5-methylene-hydantoin (M2), the monomer reactivity ratios, r1 and r2, were found to be 0.03 and 24, while the Q and e values in Alfrey-Price’s Q-e scheme were found to be 21 and −0.23, respectively. As is shown by the large Q value, the high reactivity of 5-methylene-hydantoin is based on the high resonance stabilization of its radical, a stabilization which results from the conjugation system. This was also confirmed by a study of the ultraviolet spectrum. Poly-5-methylene-hydantoin showed electrolytic behavior in its solubility and solution viscosity. This property is due to the dissociation of NH at the 3 position of the hydantoin group. The polymers of 3-methyl-5-methylene-hydantoin and 3-phenyl-5-methylene-hydantoin were observed to show very weak acidities, resulting from the NH at the 1 position. Poly-α-aminoacrylic acid was obtained by the alkaline hydrolysis of poly-5-methylene-hydantoin. This polymer was soluble in water, and showed an unusual amphoteric behavior in solution viscosity.
The Behavior of Free Radicals Produced by Ultraviolet Irradiation in the Frozen Propargyl Alcohol-Hydrogen Peroxide System
Authors: Takeda Keiji , Yoshida Hiroshi , Hayashi Koichiro , Okamura Seizo
Published: July 2006

In order to assertain the polymerization mechanism in the solid state, a solid mixture of propargyl alcohol (monomer), hydrogen peroxide and water was irradiated at −196°C by an ultraviolet light. The structure of the free radicals so formed in the solid medium was then studied by the electron-spin-resonance method. The trapped free radical was a monomer radical, CH≡C–CHOH. This shows that the HO·radicals produced by the photolysis of hydrogen peroxide abstracted the methylenic hydrogen atoms from the alcohol. An examination of the kinetic behavior of free radicals revealed that HO· radicals migrated freely and reacted with monomers at −196°C. The reaction between the monomer radical and HO· radicals is more important than the recombination between monomer radicals.
Silent Discharge Reactions in Aqueous Solutions. III. Acidic Aqueous Solutions of Ferrous Sulfate and Ceric Sulfate in a Hydrogen Atmosphere
Authors: Yokohata Akira , Tsuda Satoru
Published: July 2006

A study has been made of silent discharge reactions in aqueous solutions of ferrous sulfate and ceric sulfate acidified with sulfuric acid in a hydrogen atmosphere. The present study has confirmed that silent discharge leads to the formation of hydrogen peroxide from water molecules in a dilute sulfuric acid solution, the oxidation of ferrous ions to ferric ions, and the reduction of ceric ions to cerous ions. The same reactions were previously studied in inert gases. A satisfactory interpretation can be made of their mechanisms by taking into consideration the action on the solvent of slow electrons produced in the gaseous phase. In a hydrogen atmosphere, the yields of the foregoing reactions were very small when compared with those in the case of inert gases; however, a good linear correlation was observed between the yield and the duration time of discharge. From these results it has been concluded that the yields can be well interpreted by taking into consideration the action of active species of hydrogen generated in the gaseous phase on the radicals formed from liquid water, besides the action of slow electrons; moreover, the action of active species on the solute cannot be serious. The absorbed dose in the solution was estimated to be approximately 1.9×107 r./hr. from the relation of the dissipated energy calculated electrically to the absorbed dose.
The Reaction of Oxygen Atoms with Dimethyl Ether
Authors: Takezaki Yoshimasa , Mori Sadayuki , Kawasaki Hironobu
Published: July 2006

The gas-phase reaction of dimethyl ether with oxygen atoms produced by the mercury photosensitized decomposition of nitrous oxide has been studied by means of quantitative determinations of the reaction products. Characteristic products are water, methanol, formaldehyde, carbon monoxide, methoxy ethanol and methyl formate. The possible mechanisms of the oxygen attack on the substrate have been considered, and the following steps postulated on the basis of the relative importance of these products and their time variations:

O+CH3OCH3 –\xrightarrowkE OH+CH3OCH2, OH+CH3OCH3 –→ H2O+CH3OCH2 and CH3OCH2+OH –→ CH3O+CH2OH.

The rate constant, kE, of the first step has been determined in the competitive reaction with n-butane as:

k E=6.3×1010exp(−4700/RT) 1. mol−1 sec−1·
The Quenching Action of Benzoic Acid and Methyl Benzoate on the Fluorescene of Naphthalene Derivatives. II
Authors: Miwa Takuji , Koizumi Masao
Published: July 2006

The quenching action of benzoic acid on the fluorescence of naphthalene derivatives, for instance, N, N-dimethyl-2-naphthylamine, is phenomenologically ascribed to its dimer. In order to examine its molecular mechanism, absorption and fluorescence spectra have been measured on solutions of N, N-dimethyl-2-naphthylamine with and without benzoic acid, using as a solvent cyclohexane to which various amounts of dioxane or ethyl ether has been added. The quenching action of benzoic acid has also been measured in similar solvents. A good parallelism has been found between the change in the absorption spectra of benzoic acid and the change in the quenching action of benzoic acid when both are examined as functions of the concentration of dioxane or ether. From this finding, and from the more precise analysis of the data described in a previous paper (This Bulletin, 38, 529 (1965)), it has been concluded that the quenching action of benzoic acid may be ascribed to the direct interaction between the fluorescer and the benzoic acid dimer. Further, similar quenching actions have been observed in o-, m- and p-toluic acids, and p-methoxy-bonzoic acid.
Theoretical Studies of the Use of the Double Extrapolation Method to Determine the Forward Scattering of Light by Spherical Colloidal Particles
Authors: Nakagaki Masayuki
Published: July 2006

An application of the double extrapolation method (the Zimm-plot method) for the reduced intensity of light scattered by colloidal dispersions, instead of polymer solutions, is discussed theoretically on the basis of the Mie theory. The correction factor, F, required to recalculate the experimental value of the molecular weight, MR, to the true value, M (M=FMR), is equal to unity in the case of the Rayleigh scattering (α→0) and the Rayleigh-Gans-Debye (R-G-D) scattering (|m–1|→0, where m is the relative refractive index of the sphere to the medium). Usually, however, the value of F is not equal to unity, but is found to be given by an empirical equation F=1–0.155Q+bQ1.5, where Q is a quantity proportional to the reduced specific scattering intensity at θ→0. For the determination of the radius of gyration from the “initial slope,” the R-G-D equation is applicable even in cases where |m–1| is not small. In order to determine the true molecular weight from the molecular weight, Mτ, obtained from the specific turbidity at the infinite dilution, the factor Φ is needed (M=ΦMτ). The factor Φ is considered to be a product; that is, Φ=F\varphi, where the factor \varphi seems to be independent of the m value. The empirical equation obtained was \varphi=1+0.537α2.08
On the Photochemical Behavior of Some Xanthenes and Xanthones and the Photochemical Formation of Dixanthenes, Mono-, and Dihydroxydixanthenes
Authors: Zanker V , Ehrhardt E
Published: July 2006

By ultraviolet spectrometric measurements we studied the photochemical behavior of xanthene, xanthone, 9, 9′-dihydroxydixanthene and dixanthene in aerated and deaerated ethanolic solutions in the range of concentration 5·10−3  m to 10−4  m by Osram-HBO 200- and Hanau TQ 81- lamps. We found: Xanthenes are photostable similar to monoacridans in the absence of oxygen; in the presence of oxygen photooxidation to the corresponding xanthones takes place. The xanthones are photochemically unstable; in oxygen free solvents containing H-atoms, like methanol, ethanol, benzene, cyclohexane, dioxane, they are reduced to xanthenes. In cyclohexane we found a soluble xanthene, 9-cyclohexylxanthydrol. In hexane there is formed a precipitate with a yield above 80%; this is the dimeric xanthene 9, 9′-dihydroxydixanthene. The photo-reaction presumably is going over a diradical, H-atom transfer from the solvent and formation of a xanthydrol monoradical in the primary step and dimerization to the 9, 9′-dihydroxydixanthene. Irradiation of solutions of xanthone and xanthene in benzene furnish 9-hydroxydixanthene. Solutions of equal molarity of xanthone and acridan yield under irradiation also a solid photoproduct; this is 9, 9′-diacridan. The first step of reaction is photoreduction, where xanthene tranfers a H-atom to xanthone and the hydroxyxanthyl radical dimerizes with the xanthyl radical or the acridanyl radical dimerizes with themselves and forms the diacridan.
Aminocyclitols. VIII. A Synthesis of Inosamines and Inosadiamines
Authors: Suami Tetsuo , Lichtenthaler Frieder W , Ogawa Seiichiro
Published: July 2006

muco-Inosamine-1, scyllo-inosamine, muco-inosadiamine-1,5 and myo-inosadiamine-1,2 have been synthesized from myo-inositol. Their structures have also been established by a study of the NMR spectra of their acetyl derivatives. When 1, 4, 5, 6-tetra-O-acetyl-3-O-mesyl-myo-inositol is treated with sodium azide in boiling aqueous 2-methoxyethanol, an azido derivative is obtained. The azido compound is hydrogenated in the presence of a catalyst and subsequently acetylated to give muco-inosamine-1. The stereochemical course of the reaction has been proposed to be an anchimeric reaction. When the analogous reaction is carried out with 2,3-di-O-mesyl-myo-inositol tetraacetate, myo-inosadiamine-1,2 or muco-inosadiamine-1,5 is obtained as the main product, depending on the solvent applied.
Methylene-hydantoin and Related Compounds. III. Synthesis of 5-Ethylidene-hydantoin: Attempts to Synthesize 5-Vinyl-hydantoin
Authors: Murahashi Shunsuke , Yuki Heimei , Kosai Koichi
Published: July 2006

A number of methods of preparation were studied in an attempt to synthesize 5-vinyl-hydantoin using acrolein as a starting material. There were three possible routes: 1) the thermal decomposition of 5-(9,10-dihydroanthracene-9,10-endo-α, β-ethyl)-hydantoin at 400°C; 2) that of 5-(2-acetoxyethyl)-hydantoin and 3) the elimination reaction of dimethyl 2-(5-hydantoin)-ethyl sulfonium iodide in dimethyl sulfoxide by potassium t-butoxide. However, all the reactions gave 5-ethylidene-hydantoin as the product instead of 5-vinyl-hydantoin. An extreme ease of isomerization from 5-vinyl-hydantoin to 5-ethylidene-hydantoin was caused by the highly stable structure of the latter compound. The strong resonance stabilization of 5-ethylidene-hydantoin was observed in the ultraviolet spectrum. 5-Methyl-5-vinyl-hydantoin, which has no migrating hydrogen, could not be obtained from the 5-methyl derivatives of the above compounds.
Studies on d-Glucosamine Derivatives. XII. The Synthesis of N-Acetyi-3-O- and -4-O-aminoacyl-d-glucosamines
Authors: Yoshimura Juji , Funabashi Masuo , Ishige Sadao , Sato Tetsuo
Published: July 2006

As a part of the investigation of the stabilities of the esters between N-acetyl-d-glucosamine and various amino acids, N-acetyl-3-O- and 4-O-aminoacyl-d-glucosamines were synthesized. Benzyl N-acetyl-4, 6-O-benzylidene-α- and -β-d-glucosaminide, and benzyl N-acetyl-3-O-benzyl-6-O-trityl-α- and -β-d-glucosaminide were condensed with N-benzyloxycarbonyl-amino acids by the dicyclohexylcarbodiimide method, followed by the step-by-step removal of the protecting groups. The α-Glycosidic benzyl group, however, could not be removed by the catalytic hydrogenolysis in the presence of oxalic acid, probably because of a steric hindrance.
The Reaction of 2-Cyclohexylimino-3-cyclohexyl-4, 5-diphenyl-4-oxazoline
Authors: Kumamoto Takanobu , Nagaoka Takenori , Mukaiyama Teruaki
Published: July 2006

The reaction of 2-cyclohexylimino-3-cyclohexyl-4, 5-diphenyl-4-oxazoline with isocyanate or isothiocyanate was studied. When the oxazoline was treated with isocyanate, an exchange reaction took place, thus forming new 2-imino-oxazoline and cyclohexyl isocyanate. Similarly, the reaction of the oxazoline with carbon disulfide resulted in the formation of 3-cyclohexyl-4, 5-diphenyl-4-oxazoline-2-thione and cyclohexyl isothiocyanate. Further, cyclohexyl isothiocyanate was obtained by the reaction of dicyclohexylcarbodiimide or cyclohexyl isocyanate with carbon disulfide.
Organic Sulfur Compound. X. The Mechanism of the Carboxylic Ester Formation from Carboxylic Sulfurous Anhydrides
Authors: Kobayashi Michio , Kiritani Reiko
Published: July 2006

Sodium benzoate-18O reacts with methyl chlorosulfite to give methyl benzoate-18O ina low yield; the excess 18O content has been found to be exactly one-half of that in the starting benzoic acid. Another reaction of the labeled benzoic acid with phenyl chlorosulfite gives phenyl benzoate-18O; its excess 18O atom% is also one-half of that of benzoic acid. Both reactions are considered to proceed by way of the intermediate formation of the benzoic sulfurous mixed anhydrides, the decomposition of which by acyl-oxygen splitting affords the carboxylic esters labeled only in the carbonyl group.
Kinetics of the Hydrogenation of Aniline in the Vapor Phase on a Cobalt-Alumina Catalyst
Authors: Hagiwara Hiroshi , Kojima Eiichi , Echigoya Etsuro
Published: July 2006

The kinetics of the catalytic hydrogenation of aniline with a cobalt-alumina catalyst in the temperature range from 160° to 210°C was studied by a differential flow reactor with a fixed bed. (1) The rate of reaction reaches a maximum in the 180–190°C range for the hydrogenation of aniline. From the thermodynamic calculations and the experimental results for a fluidized-bed reactor, the reverse reaction was found to be almost negligible below 200°C under the conditions of the reaction. This phenomenon was explained by the proposed kinetics of the reaction. (2) The initial rate of reaction without cyclohexylamine, and the rate when some cyclohexylamine was added to the reactants, were measured at atmospheric pressure over the following range of conditions of partial pressures; hydrogen 0.3–0.92 atm., aniline 0.05–0.2 atm., cyclohexylamine 0–0.24 atm. It was concluded that a plausible rate-controlling step was the surface reaction, i. e., the reaction between the adsorbed aniline and hydrogen on the surface of the catalyst. The equation for the vapor phase hydrogenation of aniline on a cobalt-alumina catalyst in the temperature range from 150°C to 210°C was determined to be:

r=k\fracKH3KAPH3PA(1+KHPH+KAPA+KCPC)4
The Energy of the Excimer Luminescence of Naphthalene under a Variety of Geometrical Configurations
Authors: Azumi Tohru , Azumi Hiroshi
Published: July 2006

A four-electron ASMO treatment of the interaction of two naphthalene molecules to yield excimers of D2h, C2, or S4 is developed, and the energies of these excimers are calculated as a function of the angle, α, between corresponding bonds of the two molecules. It is shown that excimers are stable at two configurations, α=0° and α=75°; that the excimer with α=0° does not emit because of the forbidden character of the transition, and that the excimer with α=75° emits and is considered to play a predominant role in the observed excimer fluorescence.
The Activation of Titanium Dioxide as a Decontaminant for Radioactive Contamination
Authors: Takami Toshiko , Sasaki Tsunetaka
Published: July 2006

The decontamination efficiencies of treated and untreated titanium dioxide pastes were measured using 60Co-contaminated surface of plastics, polyvinyl chloride. The titanium dioxides used were commercial titanium dioxide, hydrous titanium dioxide, titanium dioxide treated with sulfuric acid, and “Titanium Cake,” an intermediate product of the titanium dioxide industry. Among these titanium dioxide decontaminants, titanium dioxide treated with sulfuric acid proved most effective in decontamination, even in neutral conditions, if activated properly. The optimum condition of activation was the 50% sulfuric acid treatment of commercial titanium dioxide at 50°C for 6 hr.
Studies of Polybutenes. III. On the Molecular Motion Studied by Nuclear Magnetic Resonance
Authors: Kondo Shoichi , Ishii Fumiaki , Chokki Yasuo , Tanaka Koji , Takeda Masatami
Published: July 2006

The molecular motion of polybutenes of low molecular weights has been studied by observing the NMR line widths and spin-lattice relaxation times at temperatures in the range from −180 to 200°C. The temperature dependence of these values is similar to that of polyisobutylene of a higher molecular weight. The correlation time spectra calculated from the spin-lattice relaxation time and the spin-spin relaxation time shift in the shorter-time direction with the decrease in the molecular weight. The dependence of the correlation frequency upon the temperature is also discussed in terms of the W. L. F. equation.
The Solvent Effect on the Interaction between Perylene and Antimony Pentachloride
Authors: Kuroda Haruo , Sakurai Takako , Akamatu Hideo
Published: July 2006

The electronic spectrum of the mono-positive ions of perylene formed by the interaction of antimony pentachloride was examined in various solvents. The observed spectra may be classified into two types. The one is the spectrum observed when the solvent is of a high dielectric constant, a spectrum which almost coincides with the spectrum of perylene in sulfuric acid. The other is the spectrum observed for a solution in a solvent of a low dielectric constant, a spectrum consisting of broad absorption bands accompanied by an extra band at about 1200 mμ. The former type of spectrum may be attributed to the perylene ions in a free state stabilized by the solvation, and the latter to an associated state involving perylene and antimony pentachloride ions. It is suggested that, in the association of both kinds of ions, two or more perylene ions are in contact with each other, and that the interaction between them is responsible for the shift and broadening of the absorption bands of perylene ions, as well as for the appearance of the extra band.
The Isocyanurates. II. The Syntheses of Several Unsaturated Aliphatic Isocyanurates
Authors: Tanimoto Fumio , Tanaka Takatomi , Kitano Hisao , Fukui Kenichi
Published: July 2006

Triallyl, trimethallyl and tripropargyl isocyanurates were synthesized in good yields by the reaction of the corresponding halides with potassium cyanate in dimethylformamide or dimethyl sulfoxide. Allyl and ethyl isocyanates were easily trimerized in the presence of alkaline salts in dimethylformamide. Tris(1,3-pentadienyl) isocyanurate was synthesized by the trimerization of 1,3-pentadienyl isocyanate in a saturated solution of sodium benzoate in dimethylformamide. 1,3-Butadienylene-1,4-diisocyanate was also polymerized in the same solvent; it formed black solid mass, suggesting a polyisocyanurate structure of a low molecular weight.
The Oxygen Exchange Reaction of Phenol in Acidic Media
Authors: Oae Shigeru , Kiritani Reiko , Tagaki Waichiro
Published: July 2006

The acid-catalyzed oxygen exchange reaction to a number of phenolic compounds that is, phenol, o- m- and p-hydroxy phenols, α- and β-naphthols, o- m- and p-nitrophenols, o- m- and p-aminophenols, o- and p-bromophenols, 2, 4, 6-tribromophenol, o- m- and p-cresols and 2, 4, 6-trimethylphenol, plus quinone for comparison with 18O-enriched water was carried out under various conditions. A plot of the logkx⁄kh line against Hammett σ-constants in the substituted phenols gave a fairly good correlation line (ρ=0.47) except in the cases of p-bromophenol and p-aminophenol. The mechanism of these reactions has been discussed.
The Oxidation of Methyl Sorbate with Monoperphthalic Acid
Authors: Suhara Yasuo , Minami Toshikatsu
Published: July 2006

The products obtained by treating methyl sorbate with monoperphthalic acid under various conditions were studied by chemical and spectroscopic procedures. From the results of chemical tests and spectroscopic observations in the infrared and ultraviolet regions, it was inferred that the product in all cases is methyl trans-4, 5-epoxy-trans-2-hexenoate. This inference was confirmed by NMR spectroscopy.
Vinylacetic Acid Ester Formation in the Reaction of Crotonoyl Chloride with Alcohol in the Presence of t-Amine
Authors: Ozeki Toshitsugu , Kusaka Masakatsu
Published: July 2006

In the esterification of crotonoyl chloride, vinylacetic acid ester was obtained predominantly, with an unusual double bond shift from the α, β- to the β, γ-position in the presence of a strong basic amine. In the case of ethyl alcohol, for example, the yields of ethyl vinylacetate were as follows (%): triethylamine (96.1), tributylamine (86.1), N-ethyl morpholine (74.6), N,N-diethyl aniline (0.1) and pyridine (0.9). The rest were cis- and trans-crotomc acid esters.
The DTA of Polymer-Solvent Systems. The Solubility Curves of Isotactic Polypropylene-Decalin and Isotactic Polypropylene-Nitrobenzene Systems
Authors: Tamura Katsutoshi , Nakatsuka Kunio , Fujishiro Ryoichi
Published: July 2006

A DTA apparatus for a polymer solution has been constructed. The heating rate was adjusted to approximately 0.50 or 0.42°C/min., a favorable rate for a polymer solution. From the DTA curves obtained by the use of this apparatus, the temperatures of the end points of the melting or dissolution have been determined; their plots give the solubility curves. The solubility of the isotactic polypropylene in decalin system increases monotonously with the increase in the temperature, except for the abnormality in the region from 30 to 50 wt.% in polymer content. In the case of the isotactic polypropylene-nitrobenzene system, on the other hand, the melting curve has a horizontal part in the region with a polymer content of less than 50 wt.%; above this point lies the phase separation curve, which touches the melting curve at the point with a polymer content of approximately 50 wt.%. The double peaks which appear in the DTA curve of the melting of pure isotactic polypropylene, may be due to the paracrystalline smectic modification of isotactic polypropylene, as has been suggested by Natta (Makromol. Chem., 35, 93 (1960)). The heat of fusion for isotactic polypropylene has been estimated to be approximately 1000 cal./unit mol. by measuring the area under the melting peak of the DTA curve and the equation for the melting point depression.
The Cyclisation of Anthrimides to Carbazoles. III. The Structure of Indanthrene Gray A
Authors: Nair K S , Shah K H
Published: July 2006

The anthraquinonyl amino group of the 1, 2′-dianthrimide type, when included in the complex structure of vat dyes, does not cyclise to yield a carbazole structure, with alkali, under the conditions of isoviolanthrone formation; rather, it cleaves to yield an alizarin-type derivative under the conditions of violanthrone formation. The constitution assigned to Indanthrene Gray A (Colour Index No. 60020) has thus been confirmed.
A Phtometric Particle-size Analyzer with a Moving Light Flux
Authors: Kotera Yoshihide , Sato Kazuo , Miyayama Akihiro
Published: July 2006

A recording, photometric, particle-size analyzer has been developed which is useful in measuring the particle-size distributions of powdered materials in the subsieve range. Provision for continuously moving the optical system upwards allows for rapid analysis of the finer particles, while by moving the system downwards accurate analysis of the particles with a larger density is possible. It was ascertained that the movement of the optical system has no effect on the results obtained.
Internal Coordinate Green’s Function Analysis of Molecular Vibrations with Application to XY2Z Planar Molecules
Authors: Wolfram Thomas , DeWames Roger E
Published: July 2006

The Green’s function formalism for the analysis of molecular vibrations has been formulated for the internal or valence coordinate system. A general procedure for calculating isotopic frequencies and changes in force constants associated with the characterization of a perturbed molecule in terms of the unperturbed molecule is developed. It is shown that the internal molecular Green’s function can be constructed from the vibrational frequencies of the unperturbed molecule. Application is made to the XY2Z planar molecule. Exact formulae for the XY2Y(i) molecule are obtained. The shifts in the frequencies of an XY2Z planar molecule due to mass and bond length changes are obtained. It is shown that the A1 modes are unaffected by a change in the X–Z bond length while the B1 modes move to higher frequencies as the bond distance decreases. An explicit expression for the change in the valence bond bending force constant, fα, is obtained as an example of how force constant changes can be studied by means of the Green’s function procedure. Qualitative results for HBCl2 and HBBr2 are obtained which indicate that fα decreases in going from BCl3→ HBCl2.
Catalytic Activities of Metal Oxides in the Oxidation of Propylene
Authors: Takeuchi Toyosaburo , Honma Michiaki , Takeda Hideo
Published: July 2006

The catalytic oxidation of propylene by the flow method was carried out in order to investigate the correlation between the activity and the physical properties of the catalyst, using the oxides of zinc, copper, nickel, cobalt, iron, manganese, chromium, vanadium and titanium, all of which were supported with alumina. The analysis by means of gas chromatography indicated that the main products of the reaction were carbon dioxide and water. An abrupt increase in the rate of conversion against the temperature, denoted by CT, was irrespective of the amount of oxide and was characteristic of each oxide. The CT was expressed as a function of the % d character of the metal of the oxide, as well as a function of the heat of formation per gram-atom of oxygen in the oxide. The mechanism of the abrupt change in the rate of conversion was discussed in relation to the ability of oxygen to be removed from the oxide and the amount of propylene adsorbing on the oxide during the reaction.
Spectroscopic Studies of Dialkylaluminum Alkoxides and the Trialkyl-aluminum-Ether Complex. II. Assignments of Observed Frequencies
Authors: Tarao Ryokichi
Published: July 2006

The polarization data on the Raman lines of Al(CH3)3·(CH3)2O, [Al(CH3)2OCH3]3, [Al(C2H5)2OCH3]3, and [Al(C2H5)2OC2H5]2 have been obtained in the 3100–130 cm−1 region. Most of the infrared absorption bands and Raman lines of these four compounds in the skeletal vibration region (720–130 cm−1) have been tentatively assigned with the aid of these polarization data and on the assumption that the symmetries of these four compounds are as given in the previous paper. The Raman spectra of Al(CH3)3·(CD3)2O, [Al(CH3)2OCD3]3, and [Al(C2H5)2-OC2D5]2 have been measured in the 3100–130 cm−1 region. Most of the infrared absorption bands and Raman lines of Al(CH3)3·(CH3)2O, [Al(CH3)2OCH3]3, [Al(C2H5)2OCH3]3, and [Al(C2H5)2OC2H5]2 in the CH-stretching region (3100–2700 cm−1) have been assigned with the aid of the spectroscopic data of the above-mentioned partly-deuterated substances.
The Exchange Reaction of Oxygen Atoms between Oxygen and Carbon Dioxide on Metal Oxides of the Fourth Period of the Periodic System
Authors: Kiyoura Tadamitsu
Published: July 2006

The exchange reactions of oxygen atoms between oxygen and carbon dioxide on metal oxides were studied by the static batch method in the temperature range from 150 to 600°C. The order of the catalytic activity of the oxides in the reaction was found to be; (higher activity) Co3O4>MnO2>NiO>Fe2O3>Cr2O3>V2O5>TiO2. A very close similarity of the change in the reactivity of these oxides was found in the exchange between oxygen and oxides. There is an approximately linear relationship between the catalyst activity of the metal oxides and the heat of the formation of these oxides. At any temperature examined, carbon dioxide exchanged their oxygen atoms with those of oxide rapidly. The rate of isotopic exchange decreased in the following order on any oxide examined: CO2-Oxide>O2-Oxide>O2-CO2 on oxide. The exchange between oxygen and carbon dioxide was observed only when the exchange between oxygen and oxide took place. According to these results, it was concluded that the exchange between oxygen and carbon dioxide takes place through the exchange between these gases and oxygen atoms of oxide, and that the rate-determining step is the exchange with oxygen.
The Reactions of N-Phenyl Ethanolamine with Imido Phosphites, Amido Phosphites and Amino Phosphines
Authors: Mitsunobu Oyo , Ohashi Takashi , Kikuchi Motokazu , Mukaiyama Teruaki
Published: July 2006

Various symmetrical and unsymmetrical triesters of phosphorous acid have been obtained by the reactions of phosphazo compounds with alcohols or phenols. When a phosphazo compound, amido phosphites or amino phosphine is treated with 2 mol. of N-substituted ethanolamine, the corresponding bis(β-aminoethyl) phosphites or phosphonite is obtained. On the other hand, when the same reaction is carried out with 1 mol. of the ethanolamine, cyclic phosphorous compounds are obtained in fairly good yields. Further, it has been found that the treatment of bis(β-anilinoethyl)phenyl phosphonite with phenyl isocyanate gives 2-phenylimino-3-phenyl-1, 3-oxazolidine.
Effect of Temperature on the Molecular Structure of Iodine Observed by Gas Electron Diffraction
Authors: Ukaji Takeshi , Kuchitsu Kozo
Published: July 2006

The bond distance and its mean square amplitude for the iodine molecule were measured at 80°C, 300°C, and 500°C by gas electron diffraction. The observed temperature dependences of the above parameters were in good agreement with those calculated on the basis of an anharmonicoscillator model and experimental spectroscopic constants.
Dielectric Relaxation and Molecular Structure. II. Notes on Analysing Dielectric Data of Dilute Solutions
Authors: Higasi Keniti
Published: July 2006

Dielectric data from dilute solution studies consist of two slopes, a′ and a″, as defined by ε′=ε1′+a′c2 and ε″=a″c2. In this article it is shown that the Debye equations for dilute solutions can be described by the use of a′ and a″. These equations are obtained by replacing dielectric constant and loss, ε′ and ε″ in Debye’s equations for polar liquids by a′ and a″. As applications of these new equations based on a′ and a″ following topics are discussed: Symth’s a′, a″ plot in the complex plane; Scaife’s method of polarizability plot; the familiar loss tangent method originated by Debye for obtaining the relaxation time in solution; and Gopola Krishna’s new method for the same purpose.
The Simultaneous Extraction and Spectrophotometric Determination of Rhodium(III) with 2-Thenoyltrifluoroacetone
Authors: Rangnekar Asha V , Khopkar S M
Published: July 2006

A method has been described for the extractive spectrophotometric determination of rhodium (III) with 2-thenoyltrifluoroacetone (TTA) in an acetone-xylene mixture. The bright yellow rhodium(III)-TTA chelate solution in an acetone-xylene solvent mixture obeys Beer’s law over the concentration range of 1.95–19.5 μg. of rhodium per ml. Around pH 6.0 quantitative extraction is possible with 0.015 m TTA -acetone-xylene. The colour of the complex is quite stable up to 72 hr. Rhodium(III) can be extracted in the presence of a large number of ions.