bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydrogenation and Hydrogenolysis. IV. Catalytic Reductions of Cinnamyl Alcohols and 3-Phenylpropargyl Alcohol
Authors: Nishimura Shigeo , Onoda Takeru , Nakamura Akiya
Published: July 2006

1. The hydrogenation and hydrogenolysis of cinnamyl alcohol was studied with platinum, palladium, rhodium, and rhodium-platinum catalysts. The following results were obtained:

(i) The absorption of hydrogen increases with respect to the solvents in the following order; ethanol, acetic acid, ethanol with hydrochloric acid, and acetic acid with hydrochloric acid. The order was interpreted as that of the abilities of the solvents as proton donors.

(ii) With respect to the catalysts, platinum oxide causes the maximum absorption of hydrogen, and rhodium added to platinum decreases the hydrogenolysis markedly.

(iii) With respect to the activities of the three oxide catalysts in acetic acid, the order was; rhodium-platinum (3:1) oxide>palladous oxide>platinum oxide.

2. From the comparison of the hydrogen uptakes by 3-phenylpropargyl alcohol and by cis-cinnamyl alcohol, it was shown that little hydrogenolysis or none occurs before the reduction of the triple bond of the phenylpropargyl alcohol to the double bond.
Crystal Habit Modification of Strontium Sulfate. II. Characteristic Effect of Sodium Triphosphate on Crystallization and Mechanism of Spherulite Formation
Authors: Otani Sadaichi
Published: July 2006

1) The peculiar effect of sodium triphosphate (STP) on the crystallization and the crystal habit of strontium sulfate was studied systematically by measuring (a) the deposition rate and (b) the dissolution rate of strontium sulfate at various STP concentrations, (c) the surface adsorption of STP on strontium sulfate crystal, and (d) the coprecipitation of these salts.

2) The inhibiting action of STP on the deposition and dissolution of strontium sulfate is attributed to the adsorption of STP.

3) The fact that STP makes the growth rate predominant in the direction of c axis of strontium sulfate is ascribed to the small adsorption of STP on the (001) faces compared with that on the other faces.

4) The occurrence of the branching of crystallite was ascertained experimentally, and attributed to the ruptures appearing on the crystal faces as a result of the unfitness in the size and ionic charge of the adsorbed triphosphate.

5) The formation process of the spherulite can be interpreted from the fact that the frequent branchings are accompanied by the nearly one-dimentional growth of crystallite.

6) Possibilities of preparing spherulites from other substances are discussed.
The Structure of the Yellow Pigment from Drosophila
Authors: Nawa Saburo
Published: July 2006

The yellow pigment (Sepiapterin), occuring in the eyes of Drosophila melanogaster, decomposed to one mole each of 7, 8-dihydroxanthopterin and lactic acid accompanied by consumption of 0.5 mol. of oxygen. From this ragements and from the results of its photodecomposition and periodate oxidation, it is concluded that the compound has the structure 2-amino-4-hydroxy-7, 8-dihydro-6-lactylpteridine (III).
Diffusion in Glycerol-Water Mixture
Authors: Nishijima Yasunori , Oster Gerald
Published: July 2006

Diffusion studies of glycerol in glycerol-water mixtures ranging from zero to 93% glycerol were carried out using the microinterferometric method. For higher concentration of glycerol the diffusion coefficient decreases strongly with increasing concentration and the diffusion curves are highly skewed. Applying thermodynamic and hydrodynamic correction obtained from vapor pressure measurements and solution viscosities, respectively, the diffusion coefficient was found to be sensibly independent of glycerol concentration up to about 70% after which it rises. The increased mobility at very high glycerol concentrations is attributed to a decreased hydration of the glycerol molecules under these conditions.
Charge-transfer Complexes between Iodine and Various Aliphatic Amines
Authors: Yada Hiroshi , Tanaka Jiro , Nagakura Saburo
Published: July 2006

Mulliken’s charge-transfer type molecular complexes between iodine and various aliphatic amines were studied spectrophotometrically in n-heptane solutions. The electron donor components used in the present study include ammonia, primary amines (methyl-, ethyl- and n-butyl-), secondary amines (dimethyl-, diethyl-and piperidine), and also tertiary amines (tri-methyl-, tri-n-propyl- and tri-n-butyl-). The charge-transfer absorption bands characteristic of molecular complexes of this kind appeared between 229 and 281 mμ depending on the kind of amines used as electron donors. The stable equilibria of 1:1 complex formation were verified for all the systems. The equilibrium constants (K) were determined at various temperatures and the heats of formation (ΔH) and entropy changes (ΔS) were evaluated. The values of ΔH range from −4.8 kcal./mol. for ammonia complex to −12.3 kcal./mol. for tri-n-butylamine complex, and ΔS also changes from −8.0 e. u. for the former and −27.8 e. u. for the latter. The effect of successive replacement of hydrogen atoms of ammonia by methyl or ethyl groups on the value of ΔH was shown to be additive. From the data of ΔH and ΔS it was concluded that there exists a linear relation between these two quantities for the iodine complexes with all the primary amines and secondary amines having rather small substituent groups like methyl. The deviation from the linear relation was observed with the complexes including diethylamine and tertiary amines as electron donors. These amines with bulky substituent groups may be expected to exert a great steric hindrance in the case of the molecular complex formation. Further it was shown that the plots of ΔH’s against σ*’s (Hammett’s substituent constant) fit the straight line, except for those of the iodine complexes with triethylamine, tri-n-propylamine and tri-n-butylamine. With the aid of the spatial configuration derived from X-ray crystal analysis data for the trimethylamine-iodine complex, one could evaluate the three parameters (over-lap integral (s), exchange integral (β) and effective electron affinity (A)) which are necessary for explaining reasonably the relation between the transition energies of the charge-transfer bands and the ionization potentials of electron donors. For example, the β values thus estimated were −2.09, −2.20 and −2.32 eV. for the complexes with primary, secondary and tertiary amines, respectively.
Ultraviolet Absorption Spectra of o-, m- and p-Dinitrobenzene
Authors: Abe Takehiro
Published: July 2006

In ethanol, m-dinitrobenzene shows the maximum absorption band at shorter wavelengths than nitrobenzene, while p-dinitrobenzene gives the absorption maximum at the wavelength near to that of nitrobenzene. These bands have briefly been discussed from the concept of the intramolecular charge transfer. The absorption curve of o-dinitrobenzene, indicating no absorption maximum but shoulders, are different from those of the other dinitrobenzenes, probably owing to steric hindrance by the adjacent large nitro groups.
The Molecular Structure of Hexachlorobenzene by Electron Diffraction
Authors: Saito Takahide
Published: July 2006

The non-planar structure of hexachlorobenzene is fairly suitable rather than the planar structure and the values of principal interatomic distances are

&C-Cl=1.72±0.01 Å

&C’-Cl=2.69±0.02 Å

&Cl-Cl=3.15±0.02 Å

They are in agreement with Hassel’s data.

The author thinks that the re-investigation of the molecular structure of hexachlorobenzene by the precise sector method is necessary.
The Effect of Metallic Ions on Surface Chemical Phenomena. IV. Surface Tension Measurement on Aqueous Solutions of Metal Dodecyl Sulfates
Authors: Miyamoto Shigeru
Published: July 2006

The surface tension of aqueous solutions of various metal dodecyl sulfates with divalent cations was measured at various temperatures with a Du Noüy’s tensiometer. The values of surface tension were observed to decrease steeply with the increase of their concentrations up to their cmc’s, which are all nearly equal to 1×10−3 mol./1. These values of cmc of the metal dodecyl sulfates with divalent cations were found to be practically independent of temperature and the kind of these cations. Further, the dye titration methods were also performed to obtain the values of cmc of these, metal dodecyl sulfates using pinacyanol chloride and rhodamine 6G. The values of cmc obtained by these methods were found to coincide with those from the surface tension measurements.
Electronic Structure of Benzyl Radical
Authors: Mori Yuji
Published: July 2006

The electronic structure of benzyl radical was shown by the approximation of the composite system in which all of the interactions are ignored except only the interaction by exchange between π-electrons of the benzene ring and the methylene group (CH2). The results are qualitively in agreement with the experimental observations and the results of the other calculations. The discrepancy between the results of the present paper and the other calculations are discussed.

The lowest excited states of some conjugated free radicals are also discussed.
On the Structures of p-tert-Butyl Phenol Resin and α-Naphthol Resin. II. Infrared Absorption Spectra of p-tert-Butyl Phenol and α-Naphthol
Authors: Soda Reisuke
Published: July 2006

In connection with the work on a resin for dust respirator, the spectra of phenol, p-tert-butyl phenol and α-naphthol were observed in solid and in solution. Infrared absorption spectra can be explained by considering that these compounds associate by hydrogen bonding in solid form and that they hold the equilibrium between monomer and associated molecule in solution. Reasonable assignments were made to some of the bands observed. The deformation vibration of O–H (free) and stretching vibration of C–O seem to couple with each other and give rise to bands near 1340 and 1180 cm−1 in any of these three compounds. Bands due to the out-of-plane O–H deformation vibration could not be determined but it was found that the bands in the 550∼500 cm−1 region were concerned with this vibrational mode.
Preparation and Absorption Spectra of the Cobalt(III) Complexes of Amino Acids
Authors: Mori Motoshichi , Shibata Muraji , Kyuno Eishin , Kanaya Mitsuhiro
Published: July 2006

Three different methods were investigated of the preparation of trisglycinato-, trisalaninato- and trisleucinatocobalt(III). The method using cobalt(III) hydroxide is convenient for the α-form, the method using hexammine-cobalt(III) salt is advantageous for the β-form, and the method using tricarbonatocobaltate(III) gives both forms of the complexes. In addition, two new isomers of [Co en(ata)]·H2O and [Co(NH3)3cit]·H2O having trans-cis and cis-cis configurations with respect to the coordinated atoms were synthesized.

By comparing the visible and the ultraviolet absorption spectra, it was concluded that the α-form is a trans-cis isomer and that the β-form is a cis-cis isomer. Thermal decomposition of the complexes was performed in order to estimate the water of crystallization and the stability. The infrared spectra of the complexes were also measured.
Formation of Cyclohexano[c]1,2,5-oxadiazole from 1,2-Cyclohexanedione Dioxime. An Attempted Beckmann Rearrangement with Thionyl Chloride in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Tada Ritsuro , Yokoyama Kunio
Published: July 2006

An attempted Beckmann rearrangement of 1,2-cyclohexanedione dioxime with thionyl chloride in liquid sulfur dioxide resulted in the formation of cyclohexano [c] 1,2,5-oxadiazole in 70% yield. The structure of the oxadiazole was established by oxidation, reduction, and synthesis. The reason why the condensation was predominant over the rearrangement was discussed in comparison with the case of benzil dioxime.
The Thermal Decomposition of Dimethyl Ether in the Presence of Hydrogen Sulfide
Authors: Imai Naomi , Toyama Osamu
Published: July 2006

Dimethyl ether has been decomposed thermally in the presence and absence of hydrogen sulfide over the temperature range 360∼440°C. The rate of decomposition is enhanced by the presence of hydrogen sulfide, but the rate law is unchanged, i. e., the rate is proportional to the 3/2 power of the ether concentration, irrespective of the presence of hydrogen sulfide.

The catalytic action of hydrogen sulfide is satisfactorily explained by the steps, CH3+ H2S→CH4+HS (6), HS+CH3OCH3→H2S+ CH3OCH2 (7) and CH3OCH2→CH2O+CH3(4). Overall rate constants in the absence and presence of hydrogen sulfide are represented by 1015.16exp(−54,500⁄RT) and 1015.26exp(−51,800⁄RT) mol.−1⁄2cc−1⁄2sec−1⁄2 respectively. The combination of these gives k3⁄k7=0.8exp(−2,700⁄RT), where k3 refers to the reaction CH3+CH3OCH3→CH4+CH3OCH2 (3). If, therefore, the activation energy of reaction 3 is 9.5 kcal./mol. as reported by Trotman-Dickenson and Steacie, that for reaction 7 is 6.8 kcal./mol. The results obtained indicate that the decomposition of the formaldehyde formed intremediately is also catalyzed by hydrogen sulfide.
Optical Properties of Colored Colloidal Systems. II. Apparent Refractive Index and Extinction Coefficient of the System of Small Spherical Particles
Authors: Nakagaki Masayuki , Fujii Tomiko
Published: July 2006

The theoretical values of apparent relative refractive index m′ of colored particles was calculated as a function of particle size for various values of m0 and k0.

The theoretical values of m′ as well as x were calculated for infinitesimally small particles. It was shown that m′ increases and, after passing a maximum point, approaches a limiting value of 2.5 with the increase of k0, and that x approaches zero, after passing a maximum, with the increase of k0.

The values of m′ and x of Acid Orange R solutions were measured by a modified Brice type differential refractometer and by a spectrophotometer. A method to convert m′ and x values into m0 and k0 values was illustrated. The errors committed by assuming experimental m′ and x values as m0 and (4/3) k0 values of bulk phase are estimated for the dye solution. The error of x reached 21%, while the error of m′ was not larger than 2.6%.
Absorption Spectra of Nitrobenzene Derivatives. II. Effect of Solvent on Intramolecular Charge Transfer Spectra of Nitrobenzene Derivatives
Authors: Semba Kimio
Published: July 2006

Intramolecular charge transfer spectra of o−, m− and p-nitrobenzene derivatives were measured in solutions with various solvents. Frequency shifts induced by solvents were analyzed on the basis of current theories of solvent effects on absorption spectra. Results show that the frequency shifts in the absorption bands of nitrobenzene derivatives can be interpreted as arising from both the electrostatic and hydrogen bonding interactions.
Chemical Use of the Absorption of Soft γ-Rays, β-Ray-excited X-Rays and K-Capture X-Rays. III. Application to Column-chromatographic Separation of Halogen Compounds
Authors: Nozaki Tadashi
Published: July 2006

The absorption technique of soft γ-rays, β-ray-excited X-rays and K-capture X-rays was successfully applied to column-chromatographic separation and purification of halogen compounds. By this technique, the behavior of the iodine- and bromine-containing compounds in the column was determined in situ, and important information for column chromato-graphy, including the retention volume, was also satisfactorily applied to the frontal analysis of halogen compounds. An excellent method for the preparation of pure 4-iodobiphenyl by the use of the in-situ determination was provided.
Oxidaton of Tetralin with tert-Butyl Chromate
Authors: Matsuura Tamon , Suga Takayuki , Sakao Takashi
Published: July 2006

The oxidation of tetralin with tert-butyl chromate gave a relatively good yield of α-tetralone as the major product. Thus, it was seen that this oxidant oxidizes a methylene group of an alicyclic ring, adjacent to a benzene nucleus, to a ketonic group, forming α-ketone.
The Micro and Rapid Determination of Cobalt Carbonyl Anion in Organic Solvents by Titration with Methylene Blue
Authors: Iwanaga Ryoji
Published: July 2006

An accurate and rapid method is described for the direct titration of cobalt carbonyl anion in organic solvents. This method is based upon the oxidation reaction of the anion with methylene blue in acid media. The stoichio-metry of the reaction of 2 mol. of the anion with 1 mol. of methylene blue is found only at the pH range from 1.9 to 5.2 or in the acetic acid medium. By using a 1:1 acetic acid-toluene mixture as solvent, and by carrying out the titration at about 0°C, the anion in Lewis bases such as methanol and acetone is titrated successively without any interference by the base reaction. This method is very suitable for the determination of the cobalt carbonyl anion in solutions in the course of various reactions.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. VIII. Some Rheological Properties of Solutions of Cobalt Soaps. Specific Viscosities and Non-Newtonian Flow
Authors: Kambe Hirotaro
Published: July 2006

The specific viscosity of dilute solution of cobalt stearate in benzene has been measured. Intrinsic viscosities are 3.13 for red soap and 1.81 for blue soap. The specific viscosity of benzene solution is decreased markedly by the addition of a small amount of ethanol, owing to the subsequent decrease of solubility.

The non-Newtonian flow behavior of solutions in xylene, benzene, n-heptane and toluene are shown. At higher concentrations, in particular in xylene, these solutions are Bingham plastic. In benzene and n-heptane, flow curves with different concentrations are consistent with a flow curve of Newtonian behavior, which corresponds to that of a throughout this work, and to Messrs. Minoru saturated solution in benzene. In toluene, flow curves are scattered, possibly due to the the experiments, blockage of the capillary by a piece of gel.

Different flow curves are sometimes obtained with capillaries of different bores, owing to slippage at the wall. An antithixotropic flow curve was obtained in some solutions.
Absorption Spectra and Catalytic Behavior of the Copper(II) Chelates of Some Alkylated Ethylenediamines
Authors: Ojima Heijirô , Sone Kôzô
Published: July 2006

The absorption spectra of the copper chelates of ethylenediamine and several alkylated ethylenediamines were studied in their aqueous solutions, and an approximately linear relationship was found between the frequencies of their absorption maxima and the logarithms of their stability constants. The spectral changes caused by the addition of a strong base (sodium hydroxide) to these solutions, and the activities of these chelates to catalyze the chemilumi-nescent reaction of luminol with sodium peroxide in an alkaline solution, were also studied ; it was shown that the chelates with smaller stabilities show, in general, more drastic spectral changes and higher catalytic activities than those with larger stabilities.
Rheological Properties of Thermo-reversible Gels
Authors: Arakawa Kiyoshi
Published: July 2006

From the stress relaxation data of various kinds of thermo-reversible gels obtained by means of a chainomatic balance relaxometer, it has been found that:

1) The modified time-temperature superposition principle which includes the vertical shift along the log Er(t) axis as well as along the log time axis can be successfully applied to the hydrogels of agar-agar and gelatin, and composite relaxation curves are obtained with good coincidence;

2) The activation energy Δ\barH which is obtained from the τ1 vs. 1/T relation and which is regarded as the activation energy of the bond cleavage process at the junctions in the network is substantially equal to the value of the hydrogen bond in water and ethyl alcohol for the gels of the polyvinyl alcohol-glycerin-water system and for the hydrogels of agar-agar and gelatin; the value of Δ\barH is, however, a little larger for the gels of the polyvinyl alcohol-Congo red-water system.
Dehydration of Bile Acids and their Derivatives. X. A Study of the Physical Properties of Various 3α-Hydroxycholenates and their Derivatives, with Special Reference to their Optical Rotatory Dispersions
Authors: Osawa Ryuzaburo
Published: July 2006

Not only ultraviolet and infrared absorption spectra but also optical rotatory dispersions of various unsaturated bile acids were studied, and most of the data were found to be in good agreement with those hitherto obtained concerning the other steroids. The determination of the rotatory dispersion gave the following results:

1) The background rotation of the saturated bile acid is not affected by the introduction of a double bond in ring B, C or D.

2) The introduction of a double bond in ring C or D does not remarkably affect the RD curve of the saturated 3-keto bile acids, while the negative drift of the RD curve given by 3-keto-Δ6-cholenic acid is so very striking that this phenomenon could be utilized for the diagnosis of Δ6-3-keto bile acids (5β).

3) The positive Cotton-effect RD curve given by a saturated 12-keto bile acid is strongly inverted by the introduction of the Δ8(14)-bond, but not by that of the Δ8-bond.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. IX. Cobalt Complex Soap
Authors: Kambe Hirotaro
Published: July 2006

Soaps of cobalt complex ions and fatty acid have been prepared and investigated. Reflection spectra and infrared spectra show that these soaps are ionic in nature, as is simple cobalt soap. The magnetic susceptibility of complex soap shows that cobalt ion is in the electronic configuration of octahedral six-covalent cobalt-(III) ion. Thermogravimetric analysis of these soaps shows that they decompose at three stages, but the precise mechanism of these reactions has not yet been determined.
Rates of Solvolysis of Substituted 4-Biphenylyldimethylcarbinyl Chlorides. A Test of the Free-energy Relationship
Authors: Inukai Takashi
Published: July 2006

The rates of solvolysis of 4′-MeO-, 4′-Me-, 4′-H-, 4′-Cl-, 4′-Br- and 3′-Cl-4-biphenylyldimethylcarbinyl chlorides in 90% aqueous acetone have been determined and compared with those of the correspondingly substituted phenyldimethylcarbinyl chlorides. The effect of substituents is very much depressed in biphenyl derivatives as compared with that in phenyl derivatives, and a remarkable deviation from the linear free-enegy relationship was observed between these systems. This is attributed to the difference in the relative importance of the resonance effect and inductive effect of substituents between these two different systems.
Studies on Metal Complex Species using an Anion Exchange Resin. III. Uranium(VI)-Nitrate Complex and Zinc-Chloride Complex
Authors: Yoshimura Jun , Waki Hirohiko , Tashiro Shingo
Published: July 2006

1) The “indifferent electrolyte-adding” method described in previous papers was applied to the uranyl-nitrate and to the zinc-chloride complexes. A sodium nitrate-sodium perchlorate mixed medium was employed in the former, and a sodium chloride-sodium nitrate mixed medium in the latter.

2) The predominant species of the uranyl-nitrate complex adsorbed from sodium nitrate solutions was UO2(NO3)3− at the external nitrate concentration of about 2 m and UO2(NO3)42− at the 4∼6 m concentration. The coexistence of the two species may be presumed at 2∼4 m.

3) The principal zinc-chloride complex adsorbed on the resin from the chloride solution of 0.4∼3 m was simply ZnCl42−, accompanied by a small quantity of ZnCl3− in a low ionic strength. On the other hand, the predominant species in the aqueous phase were ZnCl3− and ZnCl42− for a sodium chloride concentration of 3 m, and Zn2+ and ZnCl+ for a 0.4 m concentration. These results were approximately consistent with those obtained in a hydrochloric acid medium by other investigators.
De-localization of Bond Eigenfunctions in π-Electronic Systems. III. Non-Empirical Calculation of the π-Electronic States of the Vinyl Chloride Molecule
Authors: Takekiyo Shozaburo
Published: July 2006

The π-electronic energy levels, wave functions, π-electron densities, and bond orders of the vinyl chloride molecule have been calculated by the approximate method proposed in part I. Slater orbitals have been employed for the atomic orbitals of the carbon and chlorine atoms. All kinds of overlap, single exchange, and multiple exchange integrals have been considered. The calculated values of the energies for the ground state and the first excited state are −100.56 and −87.58 eV. The values obtained by the HLSP method are −100.91 and −89.50 eV. π-Electron densities are Cl=1.957, C (in the center of the molecule) = 1.041, and C (in the edge of the molecule) = 1.002. These values, based on the HLSP method, are 1.915, 1.046 and 1.039 respectively. Bond orders between the neighboring carbon and chlorine atoms are 1.02 and 1.03 in the respective methods.
Long-chain Phosphates. II. Reactions of Crystalline Sodium Metaphosphates with Solutions of Various Metal Salts
Authors: Ohashi Shigeru , Nakamura Takashi
Published: July 2006

Three kinds of crystalline sodium metaphos-phates with a long-chain structure, NaPO3-II, NaPO3-III and NaPO3-IV, were prepared, and the cation exchange reactions of the solid sodium metaphosphates with aqueous solutions of bivalent metal salts, calcium, magnesium, iron(II), cobalt(II), nickel(II) and copper(II), were investigated. The tendency of the cation exchange of the sodium metaphosphates for these metal ions, except for copper (II), decreases in the order:

NaPO3-IV\gtrapproxNaPO3-III>NaPO3-II

which coincides with the order of the tendency of the hydration of the sodium metaphosphates. Only in the case of copper(II) ion were large amounts of the sodium metaphosphates dissolved in the course of the reactions.
Preparation and Properties of Alkyl Trifluorovinyl Ethers and Related Compounds
Authors: Okuhara Kunio , Baba Hajime , Kojima Rimpei
Published: July 2006

Trifluorovinyl methyl, ethyl, isopropyl and tert-butyl ethers have been prepared. These trifluorovinyl ethers show C=C absorption at such a short wavelength as 5.46∼5.50μ. The methyl and ethyl ethers can be polymerized by free-radical initiators. Halogen addition products of trifluorovinyl- and 1, 2-difluoro-2-chlorovinyl ethers have also been prepared. With α-halo or vinyl ethers, the reactions that are catalyzed by acids, including decomposition, are best interpreted as proceeding through the carbonium ion stabilized by carbonium-oxonium resonance.
Rotatory Dispersion of Metallic Co-ordination Compounds. III. Absorption Spectra and Rotatory Dispersion of Cobalt(III) Complexes of the [CoN2O4]− Type
Authors: Hidaka Jinsai , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

Three new complexes, cis(N)-K[Co(ada)2]·2.5H2O, tans(N)-K[Co(ada)2]·2H2O and cis(N)-K[Co(ata)gly]·H2O, have been synthesized. The visible and the ultraviolet absorption spectra of these complexes have been measured and discussed in relation to the geometrical structures of the complex ions compared with other complexes of the [CoN2O4]− type. Rotatory dispersion measurements have also been made for d-Na[Co en ox2] and d-K[Co en malo2].

It has been shown that the so-called anomalous rotatory dispersions of these complexes are explicable by assuming the overlap of the two inversive dispersions in their first absorption bands. The slight inversive dispersions are also observed in their second absorption band.
The Reaction of Hydrogen and Oxygen through a Silent Electric Discharge. III. The Ignition of the Hydrogen-Oxygen Gas by Silent Electric Discharge
Authors: Morinaga Kihei
Published: July 2006

The ignition of a hydrogen and oxygen gas mixture by a silent electric discharge was investigated.

The quantity of electricity which must be carried in the course of the discharge before a detonation will take place is almost independent of the composition of the gas mixture. Furthermore, for a gas mixture of fixed composition, the quantity of electricity increases along with the increasing pressure of detonative gas. A tentative view of the possible mechanism of the initiation of the detonation was briefly discussed.
On the Relationship between Electronic State of Molecules and their Biological Actions. I. The Nicotinic Action of Choline Phenyl Ether and the Enzymatic Decomposition of Phenyl Acetate
Authors: Inouye Akira , Shinagawa Yoshiya
Published: July 2006

1. Applying the frontier electron method of Fukui et al., it was attempted to explain the effectiveness of nicotinic action of some choline phenyl ether derivatives and the substrate specificity of some phenyl acetates in the enzymatic hydrolysis.

2. A fairly good correlation could be proved between the frontier electron density (fr) or its superdelocalizability (Sr) of a certain position of these compounds and their potency or susceptibility to hydrolysis.

3. Assuming that the active site of receptor (or enzyme) has also π-electron systems and a drug-receptor (or -enzyme) complex is formed by hyperconjugation through π-electron systems, a general formulation of the effect of such a hyperconjugation on the perturbation energy of their system was attempted. It was demonstrated, qualitatively at least, by our calculations, that the larger the fr of drug molecules or their Sr the larger the perturbation energy and so a possibility of above-mentioned correlation was predicted to some extent from the quantum-chemical basis.
Hot-atom Reaction in cis- and trans-Dinitrotetrammine Cobalt(III) Nitrate
Authors: Saito Nobufusa , Sano Hirotoshi , Tominaga Takeshi , Ambe Fumitoshi , Fujino Takeo
Published: July 2006

The Szilard-Chalmers reaction of cobalt in cis- and trans-dinitrotetrammine cobalt(III) nitrate have been investigated. After a given isomer was irradiated, 60Co was found in an appreciable amount in the other isomeric form. The distribution of 60Co in cis-[Co(NH3)4·(NO2)2]NO3 irradiated for one hour is 20.5 per cent in the cis form and 11.9 per cent in the trans form. The distribution in trans-[Co(NH3)4(NO2)2]NO3·H2O is 23.3 per cent in the trans form and 6.7 per cent in the cis form. This observation is consistent with a hot-zone model, where one would except that the original configuration would not be essentially preserved.
Oxidation of Ferrous Ions in Aqueous Solutions by Cobalt-60 Gamma Rays. III. The Effect of Cupric Ion in Air-free Acidic Solutions
Authors: Hotta Hiroshi , Ohno Shin-ichi , Suzuki Nobutake
Published: July 2006

The yield of ferric ions in the air-free ferrous acidic solutions by cobalt-60 gamma rays is reduced in the presence of cupric ion due to their reduction by the hydrogen atoms. The decrement depends on the composition of the solutions. That is, the apparent ratio of this reduction rate to the oxidation rate of the ferrous ions, estimated directly from the observed ferric yield by Eq. iiia increases with the decrease in acidity. On the other hand, the similar ratio for the reduction rate of ferric ions apparently varies according to the composition of the solutions. However, when these apparent ratios are analyzed by a fine composition of the solutions or reduced to the reaction rate for the fine species in solutions, the intrinsic ratios of the reduction rate of the free ferric and cupric ions to the oxidation rate of the free ferrous ions, by the hydrogen atoms, are 7 and 270 respectively and are independent of the composition of the solutions. On the other hand, the direct capture reaction of the cupric ions with the thermerized electrons is effective, in addition to the above reduction reaction with the hydrogen atoms, in the cupric solutions more concentrated than 0.004 m.
The Crystal Structure of d-Tris-ethylenediamine-cobalt(III) Bromide Monohydrate, d-[Co en3]Br3·H2O, and the Absolute Configuration of the d-Tris-ethylenediamine-cobalt(III) Ion, d-[Co en3]3+
Authors: Nakatsu Kazumi
Published: July 2006

The absolute crystal structure of d- [Co en3]·Br3·H2O was determined by means of X-rays. The space group is P43212-D48, with four formula units in a cell of the dimensions a=9.95 and c=16.73Å. The complex ion takes the “lei” form designated by Corey and Bailar and is in the same configuration as had been determined previously. The structure can be most easily described as consisting of layers of complex ions, two types of bromine ions and water molecules perpendicular to the c-axis. The water molecules link the positive and negative ions to form a layer.

A definition of “absolute structure” and “absolute configuration” was proposed. The absolute structure was determined by means of the X-ray absorption edge technique of Bijvoet. CuKa rays were used to observe visually the effect of the anomalous dispersion between the reflections (hkl) and (hk\barl), and quantitative measurements of the effect were attempted for some reflections. The absolute configuration of the complex ion deduced from the absolute structure of the crystal is in agreement with the one previously determined for the crystals d- and l-2[Co en3]Cl3·NaCl·6H2O.
Electronic Spectra and Electronic Structures of Some Basic Heterocyclic N-Oxides
Authors: Kubota Tanekazu
Published: July 2006

The ultraviolet absorption spectra of pyrazine mono-N-oxide, 4-methylpyrimidine N-oxide and pyrazine di-N-oxide have been measured under various conditions, and band analyses of those spectra have been carried out. In order to interpret the spectra and other physicochemical properties of pyrazine di-N-oxide, semi-empirical LCAO MO calculations including the treaments of configuration interactions, have been undertaken in a manner similar to previous calculations on pyridine N-oxide. On the other hand, the spectra of pyrazine mono-N-oxide and 4-methylpyrimidine N-oxide have been interpreted on the basis of the calculated results on pyridine N-oxide described in a previous paper. The high intensity bands (278, 274 and 323.6 mμ for 4-methylpyrimidine N-oxide, pyrazine mono- and di-N-oxides respectively) can reasonably be assigned to charge transfer bands such as the 282 mμ band of pyridine N-oxide.

The above substances also exhibit weak bands in the longest wavelength region in non-polar solvents. These weak bands may possibly be due to the n→π* transitions. SMO calculations on isoquinoline N-oxide and acridine N-oxide have also been carried out with the same parameters as those in the case of pyridine N-oxide in non-polar solvents, and various physicochemical properties have been discussed on the basis of these calculations. As has been pointed out in a previous paper, the parameter for the oxygen atom used here is too small. To estimate the most reasonable value, SMO calculations were carried out many times on pyridine N-oxide, which was used as a model compound. As a result, it was found that ko (in Eq. 8) ≈0.8 is the best value.
The Crystal Structure of Nickel Dialpha-amino Isobutyrate Tetrahydrate
Authors: Noguchi Teruo
Published: July 2006

The unit cell of nickel(II) dialpha-amino isobutyrate tetrahydrate has the follwing dimensions; a=9.92, b=14.24, c=11.42Å, β=107.5°, and contains four chemical units. The space group is determined to be P21/a.

Buerger’s minimum-function method was applied to the structure analysis, and the newly designed image-seeker was used. Two of the four water molecules are coordinated to the nickel ion, forming a distorted octahedron with the carboxylic oxygen and the amino nitrogen atoms. The other two water molecules play the role of binders for these octahedrons. The chelation of the amino acid molecules is of the cis-form. The structure of the skeleton of α-amino propionic acid in this complex is not planar, in contrast to that of its free acid.
The Crystal Structure of trans-Dichloro-bisethylenediamine-cobalt(III) Nitrate, [Co en2Cl2]NO3
Authors: Ooi Shun’ichiro , Kuroya Hisao
Published: July 2006

The crystal structure of trans-[Co en2 Cl2]·NO3 has been determined by means of X-ray analysis. The space group is P21/c with two formula units in a cell of the dimensions of a=6.33Å, b=9.25Å, c=10.62Å, and β=114.5°. The crystal is composed of [Co en2 Cl2]+ and NO3−. The geometry of the complex ion herein determined is not significantly different from those reported before. It has been proposed that the nitrate ion is in a disordered arrangement.
The Production of High Specific Activities of Tin
Authors: Fukushima Shouzow , Hayashi Satori , Kume Sanshiro , Okamura Hideo , Otozai Kiyoteru , Sakamoto Koh , Tsujino Ryuzo , Yoshizawa Yasukazu
Published: July 2006

The production of high specific activities of tin, 113Sn and 117mSn, with a cyclotron had been studied. Thick target yields for the reactions (A) 113In(d,2n)113Sn, (B) 115In(α,pn)-117mSn and (C) 110Cd(α,n)113Sn+111Cd(α,2n)-113Sn+ 114Cd(α,n)117mSn were determined for several incident particle energies. The reactions A and B are available for the production of the single tin activity. Reaction C is preferable to the others in the total yields of tin activities for the energy range studied, i. e., up to the energy of about 5 MeV. per nucleon of the incident particle. A thick target yield for reaction B has also been obtained from the excitation function up to the alpha particle energy of 40 MeV. The procedures for the carrier-free isolation of the tin activity from indium and cadmium targets by coprecipitation and ion exchange have also been described.
Chemical Reaction in a Shock Wave. I. The Ignition Delay of a Hydrogen-Oxygen Mixture in a Shock Tube
Authors: Fujimoto Shiro
Published: July 2006

The values of the ignition delay of a hydrogen-oxygen mixture with a diluent in the reflected shock waves were measured by using a shock tube equipped with a piezo gauge for shock velocity measurements and a photomultiplier or another piezo gauge for the measurement of the time of ignition.

There was the following relationship between the ignition delay, τ, and the temperature, Tr, behind the reflected shock wave:

log10τ[O2](mol.l−1sec.)=−9.581+3559⁄Tr

where 825≤Tr≤1360°K and 7.6×10−4≤[O2]≤3.0×10−3 mol./l. The difference between this relationship and that set forth by other authors has been discussed.
The Application of the Archibald Ultracentrifugal Method to the Determination of the Micellar Molecular Weight of the Anionic Surface Active Agents
Authors: Kakiuchi Kinji , Hattori Ken’ichi , Isemura Toshizo
Published: July 2006

(1) The values of the micellar molecular weight of SDS in water and in a sodium chloride solution could not be obtained by the Archibald method, whereas the observed Mo may represent the relative values, each corresponding to a given instant of centrifugation. However, a CMC could be definitely determined which agreed with the values reported by other workers. As may be noted from the slope of the dependency of M0 on time, the SDS solution is non-ideal above the CMC while it is polydisperse below the CMC. The abnormally high association in the critical micelle region might be caused by the incomplete dissociation of counter ions, accompanied by a change in the equilibrium between the micelle and the free ion of SDS at a given instant of centrifugation.

(2) When the electrolyte is absent, β-NF’s presumably exist in a monomeric state, but in a 0.1 m sodium chloride solution they associate, the degree of association being proportional to the x. In the region of 0.25∼1.0% concentration, micelles of β-NF were observed to be polydisperse.
Crystal Structure of m-Methylbenzamide
Authors: Orii Seiki , Nakamura Toshio , Takaki Yoshito , Sasada Yoshio , Kakudo Masao
Published: July 2006

The crystal structure of m-methylbenzamide has been determined by two-dimensional X-ray methods. The atomic positions obtained from the trial and error method are refined by the modified (Fo–Fc) synthesis.

1. The mean C-C distance in the benzene ring is 1.375Å, while C3–C8=1.526, C1-C7=1.504, C7-N=1.294 and C7-O=1.246Å.

2. The amide group twists around the C1–C7 axis with an angle of 28.7° because of the steric hindrance on the contact of H6 and HN2.

3. The molecules are connected by NH–O hydrogen bonds, 3.22Å, forming dimers which are linked with each other by other NH–O hydrogen bonds, 2.97Å, into endless chains.

The crystal structure is of a type analogous to benzamide and δ-pyrazinamide.
The Spectrophotometric Determination of Aluminum with Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

Aluminum reacts with xylenol orange in a slightly acidic solution to form two red complexes which are in equilibrium with each other. At pH 3.4±0.1, Beer’s law is obeyed up to an aluminum concentration of 1.0 p.p.m. in 1 cm. absorption cells. The absorbance was measured at the isosbestic point of 536 mμ. The molar extinction coefficient was found to be 21100. This method seems to be the most favorable one for aluminum determination if the aluminum is first separated from any interfering ions. The composition of the complexes has also been discussed.
A Cobalt Complex Catalyst for the Linear Dimerization of Butadiene
Authors: Saito Taro , Uchida Yasuzo , Misono Akira
Published: July 2006

In the linear dimerization of butadiene, the mixing order of butadiene and catalyst components, cobalt acetylacetonate and triethylaluminum affects the activity of the catalyst. When cobalt acetylacetonate and triethylaluminum react in the presence of butadiene, the solution possesses marked catalytic activity. In the infrared spectrum of this system, the intensity of the absorption peaks of the CH-(1008 cm−1) and CH2- (908 cm−1) wagging vibrations of butadiene decrease significantly as compared with the case when butadiene is added last. In both cases, the absorption of Co–O (466 cm−1) disappered and that of Al–O (490 cm−1) was found. These results indicate that triethylaluminum reduces cobalt acetylacetonate and coordinates butadiene to cobalt. When butadiene is absent, triethylaluminum and cobalt acetylacetonate react to form a complex to which butadiene coordinate scarcely at all afterwards. The former solution shows a weak paramagnetism (μeff=1.4), while the latter shows a strong paramagnetism (μeff=4.0), From these results, the catalyst of the reaction is considered to be a diamagnetic complex of cobalt coordinated by butadiene.
ESR Studies of the Negative Ions of Biphenyl Derivatives. II. Electron Spin Resonance Hyper fine Spectra of 3-Methyl Biphenyl, m,m′-Bitolyl, 2-Methyl Biphenyl, and o,o′-Bitolyl Mononegative Ions
Authors: Ishizu Kazuhiko
Published: July 2006

The electron spin resonance of 3-methyl-biphenyl, 2-methyl-biphenyl, m,m-bitolyl, and o,o′-bitolyl has been observed. The overall width and ring-proton coupling constants of the mononegative ions of each methylated biphenyl have been interpreted by utilizing the calculated spin density derived by Hückel’s MO treatment. It has been found that the splitting parameters of the ring proton and the methyl proton were both about 28 gauss.

Hyperconjugation has been effected through the π-π interaction in the case of the para-derivatives, while spin polarization is important in the case of the meta-derivatives. In the case of the ortho-derivatives, the magnitude of the methyl splitting decreased with steric hindrance, which either brought about a fair amount of unbalanced spin density on biphenyl carbon atoms, or markedly reduced the magnitude of the ortho-proton splitting.

From Hückel’s calculation, one may conclude that both of the phenyl rings are twisted about 30°∼45° in the o,o′bitolyl negative ion, in which the twisting angle is much smaller than that in the neutral molecule.
The Thermal and Radiation Oxidation of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. V. The Thermal Oxidation of Phenol and Maleic Acid
Authors: Shimada Kazuo , Suzuki Nobutake , Itatani Nobue , Hotta Hiroshi
Published: July 2006

The products of the oxidation of phenol in the aqueous solution (100∼200°C) were analyzed by gas chromatography and by thinlayer chromatography. The amounts of the decomposition products, acetic acid, formic acid, acetaldehyde, formaldehyde, acetone and carbon dioxide, increase with a rise in temperature. On the other hand, maleic acid, fumaric acid and dihydroxybenzene decrease with a rise in temperature. Since the oxidation of maleic acid gives acetaldehyde, formaldehyde, and acetic acid, these products are considered to be produced through maleic acid from phenol. However, acetone is not given from maleic acid, but from phenol.
The Redox Reaction of 1-Ethoxy-n-heptyl Hydroperoxide
Authors: Murai Shinji , Sonoda Noboru , Tsutsumi Shigeru
Published: July 2006

1) The reaction of 1-ethoxy-n-heptyl hydroperoxide with ferrous sulfate has given ethyl formate, n-heptanal, ethyl heptanoate and n-dodecane, while the reaction with a mixture of cuprous and cupric chlorides has given ethyl formate, n-hexyl chloride, n-heptanal and ethyl heptanoate.

2) The formation of n-heptanal in both reactions has been attributed to the reduction of the 1-ethoxy-n-heptanoxy radical with ferrous or cuprous ions to the corresponding anion, followed concertedly by the leaving of the ethoxide ion.

3) The probable reaction pathway, especially the difference between the natures of the heterocyclic ether syetem and the linear ether system, has been discussed.
High-kinetic Energy Fragment Ions from Organic Compounds under Electron Impact. IV. Methanol
Authors: Tsuchiya Toshikazu
Published: July 2006

Fragment ions with high kinetic energies have been produced from methanol by electron impact, as in the cases of many hydrocarbons. Assuming that a fragment has a rotational energy of the order of 0.5 eV. most of the high-energy ions from methanol can be ascribed to a doubly-charged molecule ion that dissociates into two singly-charged fragments.
The Catalytic Effects of Copper Complexes on the Oxidation of l-Ascorbic Acid
Authors: Onishi Isao , Hara Tadashi
Published: July 2006

The stability constants of various kinds of copper complexes have been estimated on the basis of the decrease in the catalytic activity of copper (II) in the presence of chelating agents. The rate constant, k, has been found to be inversely proportional to log (1+Ks[Y]n).
The Effect of the Type of Radiation on the Radiation-Induced Addition of Acetaldehyde to Cyclohexene
Authors: Shingyouchi Akira , Hatada Motoyoshi , Hirota Kozo
Published: July 2006

Several kinds of products have been found to be formed from mixtures of cyclohexene and acetaldehyde by the irradiation of γ-rays, electron beams, and ultraviolet. Both the yields and the kind of product seem to depend on the type of radiation because of their dose rate and bond-dissociating power.
Effect of Solvation on the Menschutkin Reaction in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Kondo Yasuhiko
Published: July 2006

1) The effect of the solvent solvation has been compared in the reaction between methyliodide and various bases in liquid sulfur dioxide, methanol and nitrobenzene. The reaction rate in liquid sulfur dioxide is very much depressed, and the differences in the relative rates among bases are reduced in sulfurdioxide (a leveling effect) as compared to the other two solvents.

2) The order of the relative rates is reversed in liquid sulfur dioxide; pyridine>triethylamine >N,N-dimethylaniline>N,N-dimethylbenzylamine, whereas in methanol and in nitrobenzene, N,N-dimethylbenzylamine is the fastest of the bases. The reasons for this have been discussed.

3) The effect of the o-methyl substituent of the bases on the reaction rate has been examined. In liquid sulfur dioxide, the rate ratios ko−Me⁄kH are again leveling, while in methanol the ratios are differentiating. The solvation of sulfur dioxide has been considered to be the reason.

4) An isokinetic relation between ΔE\eweq and ΔS\eweq has been observed, and the isokinetic temperature calculated as 350°K; however, no linear dependence was obtained between ΔE\eweqo−Me–ΔE\eweqH and ΔHp–ΔHo.