bluuebunny/crossref_metadata_2025 huggingface dataset:
The Electron Paramagnetic Resonance Absorption of Chromium Ions Dispersed on Silica-alumina. II. The Variation in the Spectrum under Several Chemical Treatments
Authors: Matsumoto Akira , Tanaka Hazime , Goto Nobuhisa
Published: July 2006

The dispersed state of chromium and the effect of heat treatment have been compared in Part I in chromium dispersed on different supporting materials. The behavior of the EPR absorption of the same materials in the reaction of several chemical reagents have been observed in the present work. The catalytic activities of these samples in the polymerization of ethylene and in the decomposition of hydrogen peroxide have also been measured.

The γ-absorption sites of the samples had different stabilities. In the sample with a silica gel base, this absorption disappeared quite easily in a reductive atmosphere, but that of the sample with a silica : alumina 1 : 1 base was stable in the same atmosphere. The former showed the greatest initial reaction rate in the polymerization of ethylene at 1 atm., while the latter had no catalytic activity in the polymerization, even at 40 kg./cm2. The sample with a gamma-alumina base showed an intermediate character in many respects. The activity in the decomposition of hydrogen peroxide generally corresponded to the oxidation number of the samples, even after reduction with cyclo-hexane, but in the case of the silica gel base different behavior was observed.

Taking the present and the preceding results into account, the character of this type of catalyst has been discussed. Its nature must essentially be due to the cluster-form dispersion of chromia; the addition of alumina to the supporting material gives an effect of stabilization to the active site, which extends the life of the catalyst, though an excess in the addition results in an inactive material. The 3d3 state of the chromium ions is inactive in the polymerization of ethylene, probably because of the lack of a beneficial adsorptive property to the monomer. The ease in the transfer among d0, d1 and d2 states of chromium ions may decide the activity, while the transfer into the d3 state may decide tha life of the catalyst. Water accelerates the latter and deactivates the catalyst.
Chemical Effects Associated with the β-Decay Process. II. A Kinetic Study of the Chemical Behavior of 144Pr in the EDTA Complex System
Authors: Shiokawa Takanobu , Omori Takashi
Published: July 2006

The substitution reaction of 144Ce(III) ions with the 144Pr(III)-EDTA complex in an aqueous solution at 25°C has been investigated; the rate-determining step has been found to be the acid-catalyzed dissociation of the Pr(III)-EDTA complex.

On the basis of the above substitution mechanism, the chemical behavior of the 144Pr atoms produced by the β−-decay of 144Ce has been satisfactorily explained in terms of a model which involves the formation of an intermediate complex. The kinetic treatment leads to the conclusion that the intermediate, produced as a results of an increase in the nuclear charge by the β−-decay of the complexed 144Ce, is available for attack by hydroxide ions and protonated EDTA anions and, consequently, produces free 144Pr(III) ions.
The Electrodeposition of Ruthenium from a Ruthenium(III) and Ruthenium(IV) Solution and a Fission Products Solution
Authors: Kobayashi Yoshii , Yamatera Hideo , Okuno Hisateru
Published: July 2006

The electrodeposition of ruthenium from ruthenium chloride and ruthenium nitrosyl chloride solution has been studied and has been applied to the separation of the radioactive ruthenium contained in fission products. When the amount of the ruthenium deposited in a given time was plotted against the cathode potential, the curves for 1×10−7m solutions of chloride and nitrosyl chloride showed a maximum. The decrease in the electrodeposition at lower cathode potentials may be due to the anodic oxidation of ruthenium as well as to the evolution of hydrogen gas at the cathode. The rate of electrodeposition was found to depend on the material used as the cathode, and to be increased by an increase in the temperature and by the addition of the carrier platinum or ruthenium. A complete separation of radio-ruthenium from fission products resulted when electrolysis was carried out with a 0.1 m hydrochloric acid solution of fission products containing carrier ruthenium under the appopriate conditions mentioned in the text. The ruthenium electrodeposited on the platinum electrode was completely recovered into the solution by anodic oxidation.
The Zeeman Effect of Nuclear Quadrupole Resonance Spectrum in α-BHC Crystal
Authors: Soda Gen , Toyama Masaharu , Morino Yonezo
Published: July 2006

The Zeeman effect of the nuclear quadrupole resonance has been studied on the 35Cl-nuclei in the racemic α-BHC single crystal at room temperature. The directions of the principal x-, y- and z-axes of the field-gradient tensor at each nucleus have been determined through two runs of measurements of the no-splitting loci of each absorption line. The asymmetry parameters of the field-gradient tensor have also been determined. The C–Cl bonds have been found to be considerably distorted from the directions to be expected from the tetra-hedral bond angles for each carbon atom. The distortion takes place in such a way that the skeleton of each molecule approachs a planar configuration. Since the principal axes show a tendency to satisfy the two-fold symmetry, the distorting force has been attributed mainly to the intramolecular forces, and only partly to the intermolecular forces. The previous assignment of the six absorption lines to the six chlorine atoms in the molecule has thus been confirmed.
Traube’s Rule for Soluble Monolayers of Homologous Strong Electrolytes
Authors: Tamaki Kunio
Published: July 2006

By using the free energy of the adsorption of the CH2 or the CF2 group from water to the surface, W, and the surface potential of Gouy’s theory, Traube’s factor, K, that is, the ratio of the respective concentrations, Cn and Cn+1, required to effect the equal lowering of surface or interfacial tension for successive homologous strong electrolytes with n and n+1 CH2 or CF2 groups, has been derived as;

K=Cn⁄Cn+1=exp(−W⁄2RT)

where R is the gas constant and T, the absolute temperature. This equation has been shown to be applicable also in obtaining a very good approximation for homologous sodium alkyl sulfates or perfluoro acids.
A Study of Zinc Oxide-Chromium Oxide Catalysts. VI. The Changes Brought about by Heat Treatment in the Activity for Methanol Synthesis and in the Structure of the Raw Catalysts
Authors: Uchida Hiroshi , Oba Masaaki , Araki Michio
Published: July 2006

The activity for methanol synthesis has been determined for two series of catalysts prepared from zinc oxide and chromic acid with and without subsequent heat treatment in the air. Also, the correlations between catalytic activity and other catalyst properties have been studied. Each catalyst series has consisted of four catalysts, three of them prepared from slurries of zinc oxide powder in aqueous chromic acid, and the other prepared directly from zinc oxide powder. The chromium/zinc ratios in the catalysts made from the slurries are 0.1, 0.5, and 1.0. The catalysts of one series have been heated in the air at 400°C after their preparation (the “heated series”).

In both series, the activity and the specific activity have been found to be influenced by the chromium/zinc ratio. The catalysts not heated in the air after their preparation (the “unheated series”) show higher activities than the corresponding catalysts of the heated series, though the former catalysts have much smaller surface areas.

The results of electron microscopic examination show that the two series of catalysts, after having been used for methanol synthesis, are structually different. The structural difference has been ascribed to the difference in the way of the decomposition of the layer-structure of zinc hydroxychromate. In the case of the unheated series, the layer-structure is decomposed into crystallites of zinc oxide and zinc chromite by reduction in the synthesis gas, whereas in the case of the heated series the layer-structure is decomposed by heat treatment in the air.

X-Ray diffraction data show that, in all cases, the lattice constant for the zinc oxide in catalysts is normal, whereas the lattice constant for the zinc chromite is larger than the normal value.

The average particle diameter as calculated from the surface area and density of catalysts does not agree with the size as estimated by electron microscopic observations.

The difference in specific activity between the two series may be due to the difference in the degree of the mutual penetration of zinc oxide and zinc chromite crystallites rather than to the variation in the zinc chromite lattice constant.

In addition, the effects upon the activity and upon the catalyst structure of catalyst treatment inhydrogen at 500°C after methanol synthesis have been discussed.
Studies on Reactions of Polypropylene. V. On the Thermal Degradation Accelerated by Vinyl Polymers
Authors: Mizutani Yukio , Matsuoka Seishiro , Yamamoto Keiichi
Published: July 2006

The thermal degradation of polypropylene in the presence of such vinyl polymers as polystyrene, polymethyl methacrylate, the 2-methyl-5-vinylpyridine-styrene copolymer, and the acrylonitrilestyrene copolymer has been studied at 280–345°C by the use of glass ampoules and an extruder.

1) The vinyl polymers added were effective as accelerators for the thermal degradation of polypropylene. The activation energies for the scission reaction of the polypropylene chain were 57.2 and 58.4 kcal./mol. for the two polypropylene samples, and 46.8, 43.5, 46.9 and 38.6 kcal./mol. for polypropylenes containing 3% polystyrene, 3% polymethyl methacrylate, 4.7% the acrylonitrilestyrene copolymer, and 3% the 2-methyl-5-vinylpyridine-styrene copolymer respectively.

2) The reaction time needed for the modification of polypropylene to an appropriate intrinsic viscosity by the use of an extruder is shorter than that in glass ampoules.

3) Graft or block polymers have been detected in the residue after the acetone-extraction of the extruded polypropylene. They could be used in the modification of the polypropylene dyeability.

4) It has been concluded that the simple process of the thermal degradation of polypropylene accelerated by vinyl polymers can be used for the modification of polypropylene with a very high molecular weight and, simultaneously, for the preparation of graft or block polymers.
Studies of the Decomposition Products of Ethereal Blue Perchromate by Ion-exchange Resins. II. The Open Bottle Decomposition Product
Authors: Rajput B S , Rai R C
Published: July 2006

The composition of the open bottle decomposition product has been studied and a chemical formula Cr2(CrO4)3 has been assigned to it. It has been shown that the formation of this product can be explained successfully if we accept the formula suggested by Rai for the ethereal blue perchromate.
The Copolymerization of Cyclic Olefins with Maleic Anhydride
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Yasufuku Katsutoshi
Published: July 2006

The relative reactivities of cyclo-butene, -pentene, -hexene, -heptene, -octene(cis), cis- and trans-butene-2 have been compared in the copolymerization with MAn. The reactivity showed a minimum at cyclohexene, with the higher members having slightly higher reactivities and the lower members having markedly higher reativites than cyclohexene. cis-Butene-2 was found to be twice as reactive as the trans-isomer. These facts have been explained by a combination of the effects of the strain energy of olefins and of steric hindrance.

The kinetics of the copolymerization of cyclopentene and MAn was studied at 60°C in benzene,, the overall rate being expressed by:

Rp=k[I]0.7[M1]1.5 when [M1]=[M2]

k=5.83×1012e−24.2kcal⁄RT
Studies of Peptide Antibiotics. III. Cyclo-(l-valyl-l-ornithyl-l-leucyl-d-phenylalanylglycyl)2
Authors: Aoyagi Haruhiko , Kato Tetsuo , Ohno Motonori , Kondo Michio , Waki Michinori , Makisumi Satoru , Izumiya Nobuo
Published: July 2006

A cyclic decapeptide, cyclo-(l-valyl-l-ornithyl-l-leucyl-d-phenylalanylglycyl)2, has been synthesized in an attempt to obtain information about the relation of the structure to the antibacterial activity of gramicidin S.

The synthesis of the cyclic decapeptide was achieved in two ways. The condensation of p-methoxybenzyloxycarbonyl-l-valyl-δ-benzyloxycarbonyl-l-ornithyl-l-leucyl-d-phenylalanylglycine azide with l-valyl-δ-benzyloxycarbonyl-l-ornithyl l-leucyl-d-phenylalanylglycine afforded the corresponding N-blocked decapeptide, which was converted to the p-nitrpohenyl ester by the action of di-p-nitrophenyl sulfite. After the p-methoxybenzyloxycarbonyl group had been removed with trifluoroacetic acid, the decapeptide p-nitrophenyl ester was transformed to the cyclic benzyloxycarbonyl-substituted decapeptide by treatment with pyridine. On the other hand, this compound was also obtained by a dimerization reaction of l-valyl-δ-benzyloxycarbonyl-l-ornithyl-l-leucyl-d-phenylalanylglycine p-nitrophenyl ester. In the latter case, however, the yield was poor. The cyclic benzyloxycarbonyl-substituted decapeptide was hydrogenated in the presence of palladium black to give the desired cyclic decapeptide dihydrochloride.

The effects of the synthesized cyclic decapeptide on bacterial growth have also been examined. It was observed that the compound was about ten times as active as gramicidin S against B. subtilis in a synthetic medium; however, it showed silghtly less activity than gramicidin S in a bouillon agar medium.
The Metal-catalyzed Autoxidation of Tetralin. V. The Effect of Fatty Acid Solvents
Authors: Kamiya Yoshio
Published: July 2006

The rate of the cobalt-catalyzed decomposition of tetralin hydroperoxide in fatty acid solvents was first order with respect to hydroperoxide and second order with respect to the cobalt, and it was inversely proportional to the square of the acid concentration; i.e., -dROOH/dt=″(Co)2·(ROOH)/(Acid)2. The rate constant, k″, was found to be almost constant, regardless of the molecular weight of the acid. The values of k3⁄k61⁄2 obtained from the limiting rate of the oxidation showed an excellent linear correlation against the dielectric function of (D−1)/(2D+1). The rate of the oxidation of tetralin calculated by -dO2/dt=k3(k1′⁄2k6)1⁄2(RH)(Co)−k1′(Co)2/2 showed an excellent agreement with the value observed at cobalt concentrations lower than 3×104 mol./l. Strong organic acids such as chloroacetic acids deactivated the cobalt catalyst, and oxalic acid, which has shown the strongest deactivating effect of all the acids tested, deactivated equimolar cobalt salt.
The Cross-linking Reaction of the Poly butadiene Binder for Composite Propellants
Authors: Yamazaki Kiroku , Tokui Harusuke
Published: July 2006

The cross-linking reactions of carboxy-terminated polybutadiene with tris[1-(2-methyl)aziridinyl] phosphine oxide have been studied in order to obtain an excellent fuel binder of good mechanical properties as well as good combustion characteristics.

The tensile strength and elongation at the break point, as shown by the elastomer studied, were about 10–15 kg./cm.2 and 250–500% respectively. For high tensile modulus of the elastomer, an 100–200% excess of the cross-linking agent over the equivalent ratio was required.

The reaction temperature for cross-linking was lowered to the 50–70°C range by the addition of a suitable accelerator.

The stress-strain curve of the elastomer closely fit the equation for the rubber elasticity theory, and these stress-strain data was in accordance with the measured swelling data.
The Radiation-induced cis-trans Isomerization of 2-Butenes by Hydrogen Sulfide
Authors: Sugimoto Ken’ichi , Ando Wataru , Oae Shigeru
Published: July 2006

Radiation-induced free radical isomerizationsxs of 2-butenes with hydrogen sulfide at room temperature gave identical mixtures of about 72% trans- and 28% cis-butenes. The G-value of the isomerization is 20 to 50 times larger than that of the formation of the addition product. With gamma irradiation, 2-butenes in the presence of hydrogen sulfide were rapidly isomerized, even with a very small radiation dose. This ready isomerization indicates the ease of the reversibility of the first step of the sulfhydryl-radical addition reactions.
A Deuteron Magnetic Resonance Study of Urea-d4
Authors: Chiba Takehiko
Published: July 2006

A deuteron magnetic resonance study has been made on a single crystal of urea-d4. At room temperature deuteron quadrupole coupling corresponding to a stationary molecule is obtained. The eqQ and η values determined are: eqQ⁄h=210.8±1.0 kc./sec. and η=0.139±0.010 for D1, and eqQ⁄h=210.7±1.0 kc./sec. and η=0.146±0.010 for D2 at room temperature, and eqQ⁄h=206.3±1.2 kc./sec., η=0.138±0.010 for D2 at 117°C. In both cases the maximum field gradient component and the N–H direction are in good agreement.

The onset of reorientational motion about the C=O bond of a whole molecule has been concluded from the line-width change at high temperatures. Above 110°C the effect on the line-width of the reorientation about C–N bond has also been observed. The barrier heights for these motions are estimated to be 11±2 kcal./mol. for the reorientation about the C=O bond and 15±3 kcal./mol. for that about the C–N bond. The temperature dependence of the quadrupole splitting and that of the dipole coupling between 14N and D have been observed and dicussed in relation to the motion of the urea molecule.
The Structure and Stereochemistry of Four New Sesquiterpenes Isolated from the Wood Oil of “Kaya” (Torreya nucifera)
Authors: Sakai Tsutomu , Nishimura Kiichi , Hirose Yoshio
Published: July 2006

Four new sesquiterpenes, nuciferal (II), nuciferol (III), torreyal (IV) and neotorreyol (V), together with dendrolasin and o-methoxycinnamic aldehyde, have been isolated from the neutral volatile wood oil of Kaya (Torreya nucifera Sieb. et Zucc.) by adsorption chromatography on silica gel.

The structures and stereochemistry of these new compounds have been confirmed by infrared, ultraviolet, NMR and MS spectrometry, as well as by chemical methods.
Equilibrium Study of Propylenediaminetetraacetato Complexes of Some Divalent Metal Ions
Authors: Tanaka Nobuyuki , Ogino Hiroshi
Published: July 2006

The relative stability constants of propylenediaminetetraacetato complexes (KM′M=KMY⁄KM′Y) of six metal ions were determined at 25°C and ionic strength 0.2 by the polarographic method reported previously. The values obtained are KCoCu=3.7×102, KNiCu=1.66, KZnCu=3.2×102, KCdCu=1.61×102 and KPbCu=8.8 and are Quite similar to the corresponding values of the ethylene-diaminetetraacetato complexes respectively.
Vibration-Rotation Spectra, the Coriolis Coupling Constants and the Intramolecular Force Field of Symmetric Top Molecules. I. The E-type Fundamental Bands of Methyl and Methyl-d3 Halides
Authors: Morino Yonezo , Nakamura Junko
Published: July 2006

The infrared spectra of CH3X and CD3X (X=Cl, Br and I) have been observed with a high-resolution instrument in the region 500–3300 cm−1. The rotational fine structures of all the E-type fundamental bands have been resolved and analyzed, giving the Coriolis coupling constants, the rotational constants and the frequencies of the band origins. The uncertainties of the observed molecular constants have been discussed. On the basis of the observed data for the rotational constants and their changes by the excitation of vibration, the structures of methyl halide molecules have been determined.
Adsorption of Trimethylamine, Ammonia and Pyrrole on Amorphous Silica-alumina
Authors: Tezuka Yosisato , Takeuchi Toyosaburo
Published: July 2006

The adsorptions of trimethylamine, pyrrole and ammonia on pure silica, alumina and three silica-aluminas with (2%, 13% and 26% of alumina) have been studied. Isosteric heats have been obtained from adsorption isotherms at 100 and 120°C. A conspicuous rise, followed by a gradual fall, was observed at an early stage of the heat curve obtained from the isotherm on silica-alumina, but not from those on silica and alumina. At the peak of the curve, the amount of the adsorption of trimethylamine agreed with that of pyrrole, both of which, again, agreed with the amount of the acid point as measured by the titration using n-butylamine. The amount of ammonia was twice as large as that of the acid point. The acid points of silica-alumina are assumed to exist in clusters on the surface. The rise of heat is due to the mutual interaction of the adsorbed molecules, the peak indicating the completion of the monolayer on such acid domains.
On Glumamycin, a New Antibiotic. V. The Steric Configuration of α,β-Diaminobutyric Acid
Authors: Fujino Masahiko , Inoue Michitaka , Ueyanagi Jisaburo , Miyake Akira
Published: July 2006

Glumamycin has been treated with nitrous acid to convert the free amino group into hydroxyl, and the resulting deamino-glumamycin has been hydrolyzed with hydrochloric acid. A mixture of threonine and allothreonine has then been isolated from this hydro-lysate. The DNP derivative of the product shows an optical rotation [M]D24=−294°±14 (c 0.48, 4% sodium bicarbonate). This fact shows that the above product is a mixture of d-threonine and d-allothreonine.

Further, as the α, β-diaminobutyric acid obtained from the hydrolysate of deaminoglumamycin and that obtained from the hydrolysate of glumamycin have the same optical rotation, it may be concluded that the two moles of α, β-diaminobutyric acid in glumamycin have the same steric configuration.

On the other hand, the product obtained by the oxidation of α, β-diaminobutyric acid with hydrogen peroxide is in agreement with d-alanine. Thus, it has been found that the α- and β-carbons of α, β-diaminobutyric acid belong to the d series and that, consequently, α, β-diaminobutyric acid takes the d-erythroconflguration.
The Extractional Behavior of Cerium with Acetylacetone
Authors: \={O}ki Sh\={o}hachir\={o}
Published: July 2006

The extraction behavior of tracer amounts of cerium-144 with acetylacetone has been studied. The distribution ratio of acetylacetone between benzene and a 0.1 m sodium perchlorate solution is constant in the pH range 1.5–7, and the distribution coefficients have been determined to be 5.5, 5.4, and 5.3 at 10, 25, and 40°C respectively. The distribution ratio of cerium has been shown to be proportional to the fourth power of the concentration of the acetylacetonate ions and to the square of that of acetylacetone in the organic phase. From these results, it has been concluded that cerium exists as a tetravalent ion in the system and that the chemical form of cerium extracted in the organic phase is CeA4·2HA. Two molecules of acetylacetone are assumed to combine with CeA4 forming hydrogen bonds.
Sulfoxides. V. The Ionization of Sulfoxides in Sulfuric Acid
Authors: Oae Shigeru , Kitao Teijiro , Kitaoka Yoshinori
Published: July 2006

Contrary to the earlier claim that diphenyl sulfoxide ionizes in nearly 100% sulfuric acid to give a “diphenyl sulfidonium” ion, which can then return to the original sulfoxide when quenched with water, the 18O tracer experiment and a new set of cryoscopic determinations of a few sulfoxides have revealed that the dissociation of the sulfoxide takes place in a concentrated sulfuric acid in the following manner:

(Remark: Graphics omitted.)
Particle-size Determination of Suspensions or Emulsions by Viscometry
Authors: Matsumoto Sachio
Published: July 2006

An apparatus for sedimentation analysis by the viscometric method, making possible the measurement of viscosity change with time at a fixed position in the bulk due to the sedimentation or ascension of dispersed particles, has be constructed. The new method has been examined with both a potato-starch-granule suspension and oil-in-water emulsions.
Quinoxaline Derivatives. V. Some Reactions of 2-Cyano-3-hydroxyquinoxaline 1-Oxide
Authors: Ahmad Yusuf , Habib M S , Iqbal M , Ziauddin
Published: July 2006

2-Cyano-3-hydroxyquinoxaline 1-oxide (Ia), and its 7-chloro- or 7-ethoxy-derivatives (Ib, c), on treatment with aniline, are deoxygenated, with a simultaneous displacement of the nitrile group, resulting in the formation of 2-anilino-quinoxalines (IIa, e and f). Ia undergoes similar transformations with N-methylaniline and cyclohexylamine.

The N-oxide (Ia), on being heated with fuming hydrobromic acid, yields 6-bromo-2,3-dihydroxyquinoxaline (IVa), the mechanism of formation of which has been outlined.
Electronic Spectra of 1,4,9,10-Anthradiquinone and Its Complexes with Aromatics
Authors: Kuboyama Akira , Wada K\={o}ichi
Published: July 2006

The electronic spectrum of 1,4,9,10-an-thradiquinone, and the charge transfer absorption bands of molecular complexes between 1,4,9,10-anthradiquinone and aromatic compounds in solutions, have been studied. The weak absorption band near 600 mμ (εmax∼20) of 1,4,9,10-anthradiquinone has been assigned to an n→π* band. The charge transfer absorption bands of the molecular complexes are found at nearly the same positions as those of the corresponding chloranil complexes. From this fact it has been conluded that the electron affinity of 1,4,9,10-anthradiquinone is nearly the same as that of chloranil.
Monolayer Studies of the Interactions between Histidyl Polypeptides and Metal Ions. II. The Effects of Copper, Zinc, Cobalt and Calcium Ions on the Monolayer Properties of Poly-1-benzyl-l-histidine
Authors: Yamashita Takuya , Isemura Toshizo
Published: July 2006

The effects of metal ions on the monolayer properties of poly-1-benzyl-l-histidine, a model substance of the histidyl residue in protein, have been investigated at the air/water interface when the subphase pH is varied, and at the oil/water interface at pH 5.6.

At the air/water interface, it was found from the measurements of the surface viscosity that the cupric ion interacts especially strongly with the monolayer of poly-1-benzyl-l-histidine over a wide pH range and that the interaction of the calcium ion is quite weak. The decreasing order of metal-monolayer interactions is Cu2+, Zn2+, Co2+, Ca2+. The surface pressure-area isotherms suggest that the cobalt ion forms a somewhat looser cross-linked structure in the monolayer than does the zinc ion because of its weaker interaction.

At the oil/water interface, the film expands remarkably because of the release of van der Waals force between side chains. No appreciable effects on the interfacial pressure-area relation were observed with the zinc and cobaltous ions, because the accessibility of these ions to the interacting sites of side chains would have been restricted by the oil. The cupric ion had a considerable effect here as well as at the air/water interface.
A Microcell for Differential Thermal Analysis
Authors: Tanaka Satohiro
Published: July 2006

Microcells to carry out differential thermal analysis using a small amount of a sample have been described. The features of these cells are that they are small and light in weight, and are supported only by a thermocouple, not coming in contact with the wall of the metal block. The effects have been described of the variation in heating rate and in sample amount. The peak areas of the benzoic acid melting curve are proportional to the sample amount. The melting temperature can be measured with a precision of ±1°C if the heating rate is less than 2°C/min. The improvement of the quality of the microcell has also been considered.
The Mechanism of the Electrical Conduction in Solid Acetamide
Authors: Hirano Koichi
Published: July 2006

1) Conductivity measurements of solid acetamide have been carried out over the temperature range of 60–90°C and the specific conductivity, κ=1.7exp−{34×103⁄RT} Ω−1. cm−1, has been determined.

2) The mechanism of conduction has been discussed in terms of the proton transfer, and the value of the potential barrier between two positions of equilibrium in the NH…O hydrogen bonds has been estimated.
Synthetic Studies starting from β-Cyanopropionaldehyde. II. The Syntheses of Aliphatic Aldehydes and ω-Aldehydic Acids
Authors: Motoki Shinichi , Satsumabayashi Sadayoshi , Kusano Hajime
Published: July 2006

Electrolysis of the ethylene acetal of β-formylpropionic acid with butyric acid gave caproaldehyde ethylene acetal as a result of crossed coupling. Crossed electrolysis with monoesters of succinic, adipic and sebacic acid were then studied. The expected products, adipinaldehydic, suberinal dehydic and ω-formylundecylic acid, were obtained as their ethylene acetal ester respectively. As ω-aldehydic acids are usually inaccessible compounds, these electrolytic reactions may provide a new convenient synthetic route.

Furthermore, it has been found that the tetramer of β-formylpropionic acid underwent the normal electrolytic reaction in the presence of fatty acids and the corresponding aliphatic aldehydes were obtained in relatively good yields.
Reaction of Bis(acetylacetonato)copper(II) with Bromine
Authors: Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

In the reaction of bis(acetylacetonato)-copper(II) with bromine the chelate ring is broken and 3-bromoacetylacetone and copper-(I) or copper(II) bromide are formed depending on the mole ratio of the reactants.

Bis(3-bromoacetylacetonato)copper(II) also reacts with bromine in a similar fashion resulting in 3, 3-dibromoacetylacetone and copper(I) or copper(II) bromide. The possibility of the copper(II) ion functioning as a catalyst in the second step of the bromination of acetylace-tone is suggested.
The Molecular Structure and Force Constants of Boron Trifluoride and Boron Trichloride
Authors: Konaka Shigehiro , Murata Yoshitada , Kuchitsu Kozo , Morino Yonezo
Published: July 2006

The interatomic distances and the mean amplitudes of BF3 and BCl3 have been determined, by the sector-microphotometer method of gas electron diffraction, to be: rg(B—F)=1.3156±0.0044 Å, rg(F···F)=2.2733±0.0041 Å, l(B—F)=0.0398±0.0029 Å, and l(F···F)=0.0541±0.0020 Å for BF3 and rg(B—Cl)=1.7421±0.0044 Å, rg(Cl···Cl)=3.0134±0.0060 Å, l(B—Cl)=0.0505±0.0023 Å, and l(Cl···Cl)=0.0700±0.0023 Å for BCl3. The force constants have also been determined from the mean amplitudes. Their values are in good agreement with those obtained by the isotopic shifts and by the Urey-Bradley force field. The complex scattering factors for B, F, and Cl have been calculated from the Hartree-Fock potential, and it has been shown that the background intensity and the mean amplitudes of BF3 and BCl3 are much better accounted for by these scattering factors than by those calculated from the Thomas-Fermi potential.
The Homogeneous Hydrogenation of Acetylenes by Dicyclopentadienyltitaniumdicarbonyl
Authors: Sonogashira Kenkichi , Hagihara Nobue
Published: July 2006

The homogeneous hydrogenation of acetylenes and olefins in the presence of dicyclopentadienyltitaniumdicarbonyl (I) was studied. The results of the hydrogenation varied with the acetylene substituent. The relative activating effects of the substituents on the hydrogenation of such acetylenes as RC≡CH and R′C≡CR′ are as follows: R: Ph>t-butyl>n-alkyl, R′ : Ph>n-alkyl. The order is the reverse of that observed with the usual metal catalysts of the VIII group. In order to elucidate the mechanism of hydrogenation, the reaction of the dicarbonyl (I) with various acetylenes was studied, and the structures of the products were discussed.
Syntheses of Organic Phosphates. I. Pyridylmethyl Phosphates
Authors: Murakami Yukito , Takagi Makoto , Nishi Hiroshi
Published: July 2006

The reaction of pyrophosphoric acid with 2-, 3- and 4-pyridylmethanols resulted in the formation of the corresponding pyridylmethyl phosphates. The separation of each ester from the corresponding phosphorylation mixture was performed by passing the mixture through a column of Dowex 50W-X8 [H+] resin. The 2-, 3-, and 4-isomers were recrystallized from ethanol-water as white crystals with melting points of 182—182.5°C (part, decomp.), 194.5—195.5°C (part, decopm.), and 201.5—202.5°C (decomp.) respectively. An attempt to separate each of these esters from an artificial mixture of them consisting of an equal amount of each was performed by using an ion-exchange resin, Dowex 50W-X8 [H+]. The acid dissociation constants were determined by a potentiometric method at 25.0°C and μ=0.10 m (KNO3); this gave three pK’s for each phosphate, PKH3A, PKH2A, and PKHA: 2-pyridylmethyl phosphate, 1.8, 4.42, 6.29; 3-pyridylmethyl phosphate, 1.9, 4.86, 6.23; 4-pyridylmethyl phosphate, 1.7, 5.14, 6.25. Of these pK’s, PKHA refers to the dissociation of a pyridinium proton, while the other pK’s refer to those of phosphate protons.
The Intermolecular Hydrogen Bonding between Methanol and Triethylamine in Various States
Authors: Hirano Etsuko , Kozima Kunio
Published: July 2006

The intermolecular hydrogen bond energy between methanol and triethylamine was determined by infrared studies in the vapor state and in solutions. It was also found that, with an increase in the dielectric constant, ε, of the solvents, the free O–H stretching band of methanol shifts to a lower frequency, the molar absorptivity of this band increases, and the hydrogen bond energy of this system decreases. As is well known, the hydrogen-bonded system is mainly stabilized by the contribution of two resonating structures, the non-bonded structure and the charge-transfer structure. It seems probable that the weight of the latter for a relatively weak hydrogen-bonded complex is small. Therefore, if the energies for both resonating structures are assumed to be mainly determined by the electrostatic interaction, the hydrogen bond energy may be expected to be reciprocal to the dielectric constant of the environment. This is actually true within the limits of experimental error in a few solutions. It was also found, however, that the relation cannot be extrapolated to the case of ε=1, i. e., to the case of vapor.
The Direct Iodination of Polyalkylbenzenes Bearing Bulky Groups
Authors: Suzuki Hitomi , Nakamura Kiyomi , Goto Ryozo
Published: July 2006

The following polyalkylbenzenes bearing bulky groups have been subjected to direct iodination using iodine and periodic acid, and the corresponding mono-iodinated products have been obtained in fairly high yields: 4-t-butyl-1, 2-dimethylbenzene, 5-t-butyl-1, 3-dimethylbenzene, 5-t-butyl-1, 2, 3-trimethylbenzene, 1, 2, 4, 5-tetraisopropylbenzene and p-di-t-butylbenzene. The polyiodination of polymethylbenzenes has also proceeded smoothly, giving polyiodo compounds in high yields. A comparison of various direct methods has proved the above reagent to be the best iodinating agent for a variety of polyalkylbenzenes.
The Electron Spin Resonance of γ-Irradiated Sodium Polyphosphate. I. The Glass and the Single Crystal
Authors: Miura Masaji , Hasegawa Akinori , Fukui Tokinori
Published: July 2006

Under irradiation with γ-rays at room temperature, the glass of sodium polyphosphate or its single crystal doped with sodium sulfate becomes red, whereas the pure single crystal remains colorless. The glass and the doped single crystal exhibit ESR spectra which can be attributed to the hole trapped in the non-bonding orbital on the oxygen atom. The pure single crystal, of course, exhibits no ESR spectra. The determination of the degree of polymerization in the aqueous solution of the glass showed a decrease in the length of the main chain caused by the γ-ray irradiation. It may be concluded from these facts that the P–O–P bond is ruptured under the irradiation and that the effect of γ-rays on sodium polyphosphate is closely correlated with the local strain of the P–O–P bond.
The Determination of Oxygen in Metals with High Melting Points by the Inert Gas Fusion Method: A Silicon Fusion Technique
Authors: Kashima Jiro , Yamazaki Takuo
Published: July 2006

The determination of oxygen in metals with high melting points is important for the development of metallurgy. This paper will describe a very simplified apparatus and a procedure which gives precise results almost without a blank test. A silicon fusion technique developed by the present authors is used instead of the platinum bath method for the purpose of decomposing oxides in metals. It enables us to determine oxygen in a small quantity of a sample by the use of a highly-sensitive gas chromatograph. The amount of oxygen in the purified tantalum and niobium was determined within a standard deviation of 0.0038%. The precision established in tests of titanium samples containing 0.074% of oxygen was 0.0018%; this observed value is in good agreement with that obtained by the vacuum fusion method.
The Routine Determination of Nitrogen in Cast Iron by the Chemical Distillation and Inert Gas Fusion Methods
Authors: Kashima Jiro , Yamazaki Takuo
Published: July 2006

Although the chemical distillation method is generally employed for the determination of nitrogen in metals, it has been found that this method involves some difficulties in cast iron and pig iron samples. This paper will, therefore, describe new, repreoducible methods for the determination of nitrogen in chilled cast iron. They are the inert gas fusion and the chemical distillation methods. The most suitable sample for obtaining almost the same results with regard to ordinary cast iron by both methods was found to be a thin plate chilled by a copper mold. The accuracy of both methods was ±0.0004% when thin-plate samples containing from 0.0030 to 0.010% nitrogen were used.
The Chlorine and Fluorine Contents of Tertiary Sediments on the Miura Peninsula
Authors: Iwasaki Bunji , Kitayama Kenzo , Katsura Takashi
Published: July 2006

Tertiary sediments were collected from the Miura group on the Miura Peninsula, and the total chlorine and fluorine in these sediments were determined colorimetrically, together with the water-soluble chlorine and fluorine. There was little correlation of the contents of insoluble chlorine and fluorine in the sediments to their locations and ages. The insoluble chlorine contents of the psammitic rocks were higher than those of the pelitic rocks, whereas the insoluble fluorine contents of the former were lower than those of the latter. There seemed to be a moderately negative correlation between the contents of insoluble chlorine and fluorine in the sediments. All the sediments analyzed contained very small amounts of water-soluble fluorine (0.001 to 0.002% F). The frequency distributions of the insoluble chlorine contents in both the psammitic and pelitic rocks were lognormal.
The Preparation of Ethylenes with Polyfluorocyclobutenyl and Polyfluorocyclopentenyl Groups
Authors: Muramatsu Hiroshige , Moriguchi Soyao , Inukai Kan
Published: July 2006

The new ethylenes, with a 2-hydroperfluorocyclobutyl, 2-chlorotetrafluoro-1-cyclobutenyl or 2-chlorohexafluoro-1-cyclopentenyl group, were synthesized in good yields by the dehydration of the 1 : 1 adducts prepared by the addition of the alcohols to perfluorocyclobutene, 1, 2-di-chlorotetrafluorocyclobutene or 1, 2-dichlorohexafluorocyclopentene respectively. The dehydro-fluorination of 2-hydroperfluorocyclobutylalkylethylenes gave a mixture of perfluoro-1-cyclo-butenyl- and perfluoro-2-cyclobutenylethylene. In the mixture, the former was predominant over the latter. Some polyfluorocycloalkenylethylenes prepared polymerized in the presence of peroxide to yield transparent polymers.
Studies of the Organic Reaction of Metal Carbonyl. IX. The Formation of o-Toluylcobalt Carbonyl in the Reaction of Benzyl Chloride with Potassium Cobalt Carbonylate
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Masada Hiromitsu , Yokokawa Chikao
Published: July 2006

The reaction between benzyl halide and potassium cobalt carbonylate has been studied. o-Toluylcobalt carbonyl is found among the reaction products. This carbonyl seems to be formed by the isomerization of benzyl cobalt carbonyl via phenylacetylcobalt tricarbonyl or o-tolylcobalt carbonyl. This isomerization occurs only at relatively high temperatures (30–50°C). At 0°C, only phenylacetyl cobalt carbonyl is formed in a good yield. The isomerization is highly promoted by the addition of cobalt hydrocarbonyl. The reaction atmosphere (carbon monoxide and nitrogen) also has a great effect on the isomerization. Such additives as oxalic acid, p-toluenesulfonic acid, trichloroacetic acid, and ethyl alcohol-hydrogen chloride have no promoting effect on the isomerization.
Maackiain
Authors: Suginome Hiroshi
Published: July 2006

This isolation and determination of the structure of a new, naturally-occurring chromano-coumaran, maackiain (I) R=H, are described. On the basis of these results, the structure of pterocarpin is revised to (I) R=CH3.

(Remark: Graphics omitted.)
The Synthesis of d, l-Homopterocarpin
Authors: Suginome Hiroshi , Iwadare Tsukasa
Published: July 2006

The synthesis of chromanocoumaran (I) (R1= R2= H), the skeleton of pterocarpinoids, is described. This method, which follows a plausible biogenetic pathway, is then extended to the synthesis of d, l-homopterocarpin (I) (R1= R2= OMe). The synthesis and NMR studies allow us to assign a cis B/C ring junction to the compounds of this class.

(Remark: Graphics omitted.)
Methylene-hydantoin and Related Compounds. I. On the Reaction of Pyruvic Acid and Urea: The Synthesis of 5-Methylene-hydantoin
Authors: Murahashi Shunsuke , Yuki Heimei , Kosai Koichi , Doura Fumihiro
Published: July 2006

Various condensation products were obtained by the reaction between pyruvic acid and urea. They are 5-hydroxy-5-methyl-hydantoin, homoallantoin, homoallantoic acid, and dipyruvic triureide. 5-Methylene-hydantoin was prepared from some of these compounds, or directly from pyruvic acid and urea, by reactions in organic acid. The most convenient method was the dehydration of 5-hydroxy-5-methyl-hydantoin, which is a new compound melting at 166°C. 5-Methylene-hydantoin, m. p. 214°C, is a new monomer of the vinylidene type which polymerizes easily by means of a free radical mechanism. 3-Methyl-5-methylene-hydantoin was also prepared from 5-hydroxy-5-methyl-hydantoin through its 3-methyl derivative.
Altenin. I. The Isolation of Altenin from Alternaria Kikuchiana Tanaka
Authors: Sugiyama Noboru , Kashima Choji , Yamamoto Makoto , Sugaya Toki , Mohri Ryotaro
Published: July 2006

Alternaria Kikuchiana Tanaka is a fungus which produces a black spot disease in pears. The metabolite of this fungus contains a phytopathogenic substance for which the name “Altenin” has been proposed. A drop of an aqueous solution of altenin (2×10−5 mg./ml.) produces a black spot on pear leaves. The stability of altenin at 80, 60, and 40°C, and the behavior of altenin in relation to some adsorbents and solvents, were studied. Its isolation from the culture filtrate was found to be properly accomplished by adsorption with active charcoal, elution with acetone, and chromatography with silica gel and alumina columns. By these procedures, besides altenin, six metabolites, diheptyl phthalate, myristic acid, succinic acid, and the ester of C15-carboxylic acid, C19-steroid and trihydroxy anthraquinone, were obtained.
The Effects of Some Antioxidants on a Polyurethane Fuel Binder
Authors: Mazaki Kiroku , Tokui Harusuke
Published: July 2006

The antioxidation effect of N,N′-diphenyl-p-phenylene diamine and N,N′-di-(2-naphthyl)-p-phenylene diamine was studied with polyol-cured polyurethane containing an organo-ferric compound as a curing catalyst. These antioxidants, after weathering for one year, were found to be very effective. The same polymer without the antioxidants was degraded and flowed after only three weeks exposure (during the month of May). Although most of the inhibited polymers showed no depression in tensile properties after being exposed for one year, it was noted that the reddish transparent polymers turned dark brown and became opaque. Polyurethane is, in general, strong and resistant to weathering and aging. The degradation mentioned in this study, however, should be attributed to the degradative action of sunlight and the atmospheric conditions. The characteristics of the specimens for tensile strength and elongation at the breaking point have generally been improved without any remarkable change in the tensile modulus, the effect of the “after cure” should be taken into account in addition to the degradative action of sunlight and air.
Reactive Species in the Photochemical Hydrogenation of Acridine in Ethanol
Authors: Kira Akira , Ikeda Yoshinori , Koizumi Masao
Published: July 2006

In order to determine the reactive state of acridine when it is photoreduced by ethanol, two types of experiments were undertaken. The first was to study the concentration effect of ethanol on the quantum yield in a benzene solution. These results, however, could not give any unequivocal answer. The second type of experiment was, therefore, made from the standpoint of the triplet energy transfer, using eosine as an energy acceptor for the photoreduction of acridine in an ethanol solution. It was found that, in a deaerated solution, the quantum yield of acridine photoreduction is not affected by the addition of eosine, whereas it was established by the flash technique that, under similar conditions, the energy transfer from the acridine triplet state to eosine occurs at approximately the diffusion-controlled rate. These results lead to the conclusion that the reactive state is not the lowest triplet state.
Studies of Calcichrome as a Spectrophotometric Reagent. IV. A New Spectrophotometric Method for the Determination of Aluminum with Calcichrome and Its Basic Study
Authors: Ishii Hajime , Einaga Hisahiko
Published: July 2006

It has been found that Calcichrome forms a stable complex with aluminum; the reaction has been studied spectrophotometrically in order to find the optimum conditions for the determination of aluminum. The aluminum-Calcichrome complex is formed gradually at about pH 6; its composition has been found to be 1 to 1. The complex has two absorption maxima, at approximately 312 and 560 mμ, when measured against water. On the other hand, two absorption maxima were found, at approximately 317 and 620 mμ, in the curve obtained as the difference between Calcichrome and its aluminum complex. A linear relationship was noticed between the concentration of aluminum and the absorbance under the conditions recommended. The molar extinction coefficients of the complex at 317 and 620 mμ were 11500 and 7200. and the sensitivities were 2.3×10−3 and 3.7×10−3 μg. Al/cm2 respectively, which correspond to log(I0⁄I)=0.001. Some other metals, such as copper(II), iron(III), titanium(IV), vanadium(V), and zirconium(IV), interfere with the determination.
Studies of Peptide Antibiotics. V. Syntheses of Cyclic Penta- and Decapeptides with the l-Valyl-l-ornithyl-l-leucyl-d-phenylalanylsarcosyl Sequence
Authors: Aoyagi Haruhiko , Izumiya Nobuo
Published: July 2006

A cyclic decapeptide dihydrochloride cyclo-(l-valyl-l-ornithyl-l-leucyl-d-phenylalanylsarcosyl)2·2HCl, which is an analog of gramicidin S and a cyclic pentapeptide monohydrochloride cyclo-l-valyl-l-ornithyl-l-leucyl-d-phenylalanylsarcosyl·HCl, were synthesized for the purpose of comparing their antibacterial activities with gramicidin S. The cyclic decapeptide dihydrochloride was obtained by hydrogenolysis in the presence of hydrogen chloride of a cyclic benzyloxycarbonyl-substituted decapeptide, which had been prepared by the cyclization of a corresponding linear decapeptide active ester. The cyclization reaction of a linear pentapeptide active ester yielded a mixture of a cyclic benzyloxycarbonyl-substituted pentapeptide as a major component, and a cyclic decapeptide and an unidentified cyclic peptide as minor components. The effects of two cyclic peptide hydrochlorides on bacterial growth were tested. The cyclic decapeptide was as active as gramicidin S; however, the cyclic pentapeptide showed no activity in relation to any of the microorganisms tested.
The Synthesis of 2,7-Dideoxy-l-manno-heptose
Authors: Yoshimura Juji , Komoto Hachiro , Ando Hiroaki , Nakagawa Toshio
Published: July 2006

2,7-Dideoxy-l-manno-heptose was synthesized from 1-C-nitro-1,7-dideoxy-l-glycero-l-talo-heptitol by the elimination of the C-2 hydroxyl group (nitroolefin formation), by hydrogenation and by the Nef reaction. The corresponding ethyl α-glycoside, its acetate, and a few related 1-amino-1-deoxy derivatives were also described.