bluuebunny/crossref_metadata_2025 huggingface dataset:
The Ultraviolet Absorption Spectra of Olefins Adsorbed on the Platinum Catalyst
Authors: Soma Yuko
Published: July 2006

The ultraviolet absorption spectra of olefins adsorbed on the platinum catalyst supported on silica were studied. By comparing the absorption bands of olefins adsorbed on the platinum catalyst with the chrage-transfer bands of platinum-olefin complexes, the observed bands could be interpreted as being due to the electronic transition from filled platinum 5d orbitals to the empty π* orbital of adsorbed olefins.
Dependence of ζ-Potential upon Particle Size and Capillary Radius at Streaming Potential Study in Nonaqueous Media
Authors: Kitahara Ayao , Fujii Tadashi , Katano Seiji
Published: July 2006

The effect of particle size and capillary radius on electrokinetic potential (ζ-potential) was studied in order to check the influence of overlapping of the electrical double layer and radius effect on the measured ζ-potential by the streaming potential method. The streaming potential was measured with varying particle size and capillary radius of glass in the benzene solution of (C4H9)4NI. The measurement was carried out over the range where the laminar flow and the Quincke’s law hold. The surface conductance was corrected experimentally. ζ-Potential increased with increase of the particle size in the glass column. It was unsuccessful to obtain the ζ-potential independent of the reduced radius of the capillary pore with the Oldham’s treatment. ζ-Potential increased with increase of the capillary radius. The increase was elucidated by the Wood’s method using the appropriate constants, and the constant ζ-potential which was not affected by the capillary radius was obtained. The value was still different from that obtained by the electrophoretic method, but the difference was considerably small as compared with the previous data.
Infrared Spectra and Lattice Vibrations of Li2SO4·H2O
Authors: Meshitsuka Shunsuke , Takahashi Hiroaki , Higasi Keniti
Published: July 2006

Infrared spectra of Li2SO4·H2O and Li2SO4·D2O have been measured from 4000 to 30 cm−1 at room temperature and liquid-nitrogen temperature. Librational bands of the water of crystallization have been observed and the modes of libration are discussed. The normal coordinate analysis of the crystal as a whole has been performed and the observed bands are interpreted. Translational bands of H2O and librational bands of SO4 are also discussed.
Measurements of Optical Absorption Spectra under 60Co-γ Irradiation. Aqueous Methylene Blue Solutions Containing Oxygen
Authors: Ohno Shin-ichi , Sakumoto Akihisa , Sasaki Teikichi , Kawatsura Kiyoshi , Furukawa Katsutoshi
Published: July 2006

Aerated aqueous solutions of methylene blue (MB+; 3×10−7  m) were subjected to 60Co-γ rays in the presence of added methanol, ethanol, or d-glucose at dose rates up to 4×1015 eV g−1s−1, and the change in the optical absorption spectrum in the 300–700 nm region was studied using a rapid-scan spectrophotometer (scanning speed: 30 ms/100 nm). In the presence of high concentrations (>10−2  m) of organic substances, it was found that radiation caused a decrease in the absorption due to MB+ at 650 nm (the magnitude of the decrease was proportional to the radiation intensity), and that, on the removal of the radiation source, the original absorption spectrum was restored. This was interpreted as meaning that the radiation-produced leuco-form of methylene blue (MBH) was rapidly oxidized by oxygen. The rate constant, k(MBH+O2), was estimated to be (0.6±0.2)×104  m−1s−1 at neutral pH. In the absence of added organic substances, the permanent decoloration of MB+ took place; this was interpreted as being due to the reaction of MB+with OH-radicals. From the competition kinetic study using 10−4  m methanol, the rate constant, k(OH+MB+), was estimated to be 1.1×10−10  m−1s−1.
Thermoelectric Power of the Iodine Complexes of Aromatic Diamines and Thiazines
Authors: Sano Mizuka , Ohno Koichi , Akamatu Hideo
Published: July 2006

The thermoelectric power of N,N′-diphenyl-p-phenylenediamine·I2, N,N′-di-β-naphthyl-p-phenylenedia-mine·I3.5, phenothiazine·I3, and N-methylphenothiazine·I3 was measured in the temperature range from −35 to 140°C. The observed power for each complex was explained by means of the mechanism of mixed conduction of electrons with holes, and the ratio of electron-conduction to hole-conduction was estimated as a function of temperature. In the iodine complexes of the substituted p-phenylenediamines the conductivity due to electrons is found to be larger than that due to holes, while in phenothiazine·I3 holes contribute more to the conductivity. In N-methylphenothiazine·I3, the hole-conduction is predominant in the higher temperature region and the electron-conduction in the lower temperature region.
Anharmonic Potential Functions of Simple Molecules. I. Direct Numerical Diagonalization of Vibrational Hamiltonian Matrix and Its Application to CO and HCl
Authors: Suzuki Isao
Published: July 2006

The vibrational energy levels of diatomic molecules are related with the harmonic and anharmonic force constants by solving the vibrational Hamiltonian matrix numerically. The associated rotational levels are computed by two different methods; (1) perturbation treatment which utilizes the wave functions obtained, and (2) direct numerical diagonalization of the vibration-rotation submatrices. This approach, combined with the least-squares procedure, is applied to the determination of anharmonic force constants for CO and HCl molecules. Special attention is paid to the truncation effect of potential functions upon the calculated energy levels. Limitations in the usual perturbation method as well as the applicability of the present method to triatomic molecules are discussed.
Time-Resolved Fluorescence Studies on Charge Transfer Interactions in 1,2,4,5-Tetracyanobenzene-Toluene Complex
Authors: Egawa Keiichi , Nakashima Nobuaki , Mataga Noboru , Yamanaka Chiyoe
Published: July 2006

Time-resolved CT (charge transfer) fluorescence spectra and the fluorescence rise and decay curves at various wavelengths of the CT fluorescence band have been measured for the 1,2,4,5-tetracyanobenzene (TCNB)–toluene system at various temperatures. The results and detailed studies of the effect of solvent polarity on the fluorescene wavenumbers have demonstrated that the relaxation process is due to the change of structure including the surrounding solvent molecules from the Franck–Condon (F.C.) state to the equilibrium (e.q.) state of the excited complex. This relaxation process causes a large Stokes shift of the CT fluorescence.
Magnetic Properties of Diisothiocyanatobis(thiourea)nickel(II) and Related Complexes
Authors: Emori Shuji , Inoue Motomichi , Kubo Masaji
Published: July 2006

The magnetic susceptibilities of diisothiocyanatobis(thiourea)nickel(II), diisothiocyanatobis(N,N′-dimethyl-thiourea) nickel(II), diisothiocy anatobis(2-thioimidazolidinone)nickel(II), diisothiocyanatobis(2-thiopyrrolidone)nickel(II), and diisothiocy anatobis(thioacetamide)nickel(II) were observed between the liquid-helium temperature and room temperature. Except for the second complex, antiferromagnetic interaction operates between one-dimensional nickel chains, within each of which ferromagnetic spin coupling exists. The exchange integrals, J within a chain and J′ between chains, were evaluated on the basis of the coupled-double-chain model and the molecular-field model. The absence of interaction between chains in the crystals of the second complex can be accounted for by the presence of bulky N,N′-dimethylthiourea molecules between chains. The antiferromagnetic interactions between chains in the crystals of other complexes are attributable to the presence of bridging arrangements between chains, as is indicated by X-ray analysis.
Infrared Absorption Spectra of Silica Gel-H216O, D216O, and H218O Systems
Authors: Hino Masao , Sato Toshio
Published: July 2006

Infrared absorption spectra of the systems of silica gel - H216O,D216O,H218O, and some organic vapors were measured in order to assign the bands senstive to adsorption at 870 and around 950 cm−1. Deuteration of silica gel caused the absorption decrease at 870 cm−1 and the appearance of a band at 620 cm−1. The band around 950 cm−1 appearing by adsorption not only of water but also of organic vapors showed no shift on deuteration, but shifted toward low frequency side by 25 cm−1 on the substitution of 16O of surface silanol groups with 18O. From these facts the bands at 870, 620 and 950 cm−1 were assgned to Si–OH bending, Si–OD bending and Si–O stretching vibrations of surface silanol groups, respectively. The oxygen atom of silanol groups of silca gel was found to exchange with that of adsorbed water molecules even at room temperature for a sample treated at temperature below 300°C. On the other hand, higher reaction temperature of ca. 200°C was necessary for a sample calcined at 800°C. mechanism of the oxygen atom exchange recation was discussed.
A Nuclear Magnetic Relaxation of 139La in Ionic Aqueous Solutions
Authors: Nakamura Keikichi , Kawamura Kazutaka
Published: July 2006

The nuclear magnetic relaxation rates of the 139La ion in aqueous solutions of halides, nitrate, sulfate, and perchlorate have been measured. The observed relaxation rates increased as the concentration of the salts increased. However, in the low concentration range, the relaxation rate divided by the relative viscosity, Δv/ηr increased only in the cases of nitrate and sulfate, while it decreased in the cases of halides and perchlorate. It was found that the formation of inner-sphere complexes is a satisfactory explanation of the increase in the Δv/ηr of nitrate and sulfate solutions in the low to middle concentration range. With the fact, proved by various authors, that the lanthanide ions have several coordination numbers, the decrease in the Δv/ηr of halide and perchlorate solutions in the same concentration range can be explained in terms of the existence of an equilibrium between two hydrated species, such as:

La(H2O)93+\ightleftharpoonsLa(H2O)83++H2O

and the symmetrical species, La(H2O)83+, contributes to the decrease in Δv/ηr. At a high nitrate concentration, after reaching the maximum value Δv/ηr decreases, demonstrating that a symmetrical trinitrato species may be formed in the solution.
Dynamic Behaviors of the Electron Donor-Acceptor Complex in its Lowest Excited Singlet State
Authors: Masuhara Hiroshi , Shimada Motoo , Tsujino Nobuyuki , Mataga Noboru
Published: July 2006

Dynamic behaviors of the weak electron donor-acceptor (EDA) complex in its lowest excited singlet state have been investigated by the nsec flash photolysis method and measurements of fluorescence and transient photocurrent. In polar solvents the weak EDA complex in its lowest excited singlet state dissociates spontaneously into ions. The dynamic behaviors of s-tetracyanobenzene(TCNB)-benzene and TCNB-toluene complexes were studied in some solvents and the existence of the direct radiationless process at the excited Franck-Condon (FC) state as well as in the course of relaxation process from the excited FC state to the fluorescent state has been confirmed in the case of 1,2-dichloroethane solution. The nature of the intra-complex radiationless processes was discussed on the basis of this result. It has been pointed out that the lifetime of excited states is of crucial importance for understanding the dynamic behaviors of excited weak EDA complexes.
Charge-Transfer and Proton-Transfer in the Formation of Molecular Complexes. I. The Complex Isomerization of Some Anilinium Picrates by Melting
Authors: Saito Gunzi , Matsunaga Yoshio
Published: July 2006

o-Chloroaniline, m-nitroaniline, 3-nitro-4-methylanilme, and N,N-dimethylamino-p-benzaldehyde form true phenolates with picric acid. However, their electronic and vibrational spectra were found to be drastically modified by melting. The appearance of a new electronic absorption located near the place where the corresponding s-trinitrobenzene complex exhibits the charge-transfer band is noted above the melting point. At the same time, the vibrational bands due to the anilinium ion observed at room temperature are replaced by those due to the aniline. On the basis of these observations, it was concluded that complex isomerization from a true phenolate to a charge-transfer complex takes place by melting in these cases. On the other hand, the spectra of N,N-diethylanilinium and m-chloroanilinium picrates were shown to remain the same below and above the melting points.
The Electron Spin Resonance of Binuclear Vanadyl Tartrates
Authors: Hasegawa Akinori , Yamada Yoshio , Miura Masaji
Published: July 2006

The ESR spectra of aqueous solutions of binuclear vanadyl tartrates remarkably varied with their pH values. This variation was found to be directly correlated with the change in the form of the carboxyl group, i.e. whether it was dissociated or acidic. Thus, the frozen solution spectra were observed in water-ethylene glycol at 77°K and analyzed in terms of several magnetic parameters containing the parameter of magnetic dipolar interaction, D. From these D values, the intramolecular V···V distances were estimated to be ca. 4.2, 5.2, and 6.5Å in the solutions at pH 9, 4.8, and 2.8 respectively. Such a remarkable change in the V···V distances as interpreted to be caused by the dissociation of the coordinate bonds between the vanadium atom and the carboxyl oxygen atom and the change in the molecular structure of the tartrates, brought about the change in the form of the carboxyl groups.
The Semiconductive Property and the Phase Transition of the [(C6H5)3PCH3]+(TCNQ)2\ewdot Anion Radical Salt. The Entropy Change Due to Electrons and Holes
Authors: Iida Yôichi
Published: July 2006

The semiconductive organic crystal of [(C6H5)3PCH3]+(TCNQ)2− is known to undergo a first-order phase transition at 315.7°K. The discontinuity in the temperature dependence of the electrical conductivity takes place at the transition temperature, above which the populations of the electrons and the holes in the electrical conductivity increase abruptly. A theoretical consideration of the system of conduction carriers in an intrinsic semiconductor was developed in order to evaluate the entropy change of the electrons and holes at the phase transition. For [(C6H5)3PCH3]+ (TCNQ)2−, this kind of entropy change was found to be much less than the total entropy change determined from the heat-capacity measurements by Kosaki et al. In view of these results, it was concluded that the anomaly in the electrical conductivity was induced by the change in the crystal structure.
The Solvent Effect on the Electron-Transfer Reactions of Cobalt(III) Complexes. The Reduction of the cis-Chloro-2-aminoethanolbis(ethylenediamine)cobalt(III) Ion by Iron(II) in Aqueous Solutions of Organic Solvents
Authors: Ohashi Kousaburo , Yamamoto Katsumi , Suzuki Toshio , Kurimura Yoshimi
Published: July 2006

The solvent effect on the reduction of the textitcis-chloro-2-aminoethanolbis(ethylenediamine)cobalt(III) ion by iron(II) was investigated in aqueous solutions of dimethylsulfoxide (DMSO), dimethylformamide (DMF), ethanol, and acetone. The second-order rate constants for the reduction are 4.4×10−5  m−1sec−1 in the absence of an organic solvent, 1.4×10−3  m−1sec−1 in 0.20 Mf DMSO, 7.3×10−4  m−1sec−1 in 0.20 Mf DMF, 1.1×10−4  m−1sec−1 in 0.20 Mf ethanol, and 1.0×10−4  m−1sec−1 in 0.20 Mf acetone, at 25°C and at 0.16 m HClO4 and Σ[ClO4−]=0.60 m (Mf= mol fraction of organic solvent). From the kinetic and spectral data, it is suggested that the increase in the rate upon the addition of an organic solvent may be mainly due to a change in the solvation sphere of the reductant by replacing the water molecules by the organic molecules.
Gas-Chromatographic Determination of Ultramicro Amounts of Selenium in Pure Tellurium Metal
Authors: Shimoishi Yasuaki
Published: July 2006

Selenium (IV) reacts with 4-nitro-o-phenylenediamine to form 5-nitropiaselenol, which is detected by means of a gas chromatograph equipped with an electron-capture detector. By this highly sensitive method, the selenium in pure tellurium metal (99.9–99.999%) can easily be determined. Aqua regia oxidizes both selenium and tellurium to the quadrivalent state, and no loss of selenium is found upon this treatment. This method requires only 10–30 mg of a tellurium sample, and the presence of foreign ions does not interfere. It was found that pure tellurium, commercially available, always contains 10−3–10−4% selenium.
The Stereochemistry of Nucleophilic Addition. II. The Reformatsky Reaction of Methyl (+)-α-Bromopropionate, 2-Phenylpropanal, and 3-Phenyl-2-butanone
Authors: Matsumoto Takashi , Tanaka Isao , Fukui Kenji
Published: July 2006

The Reformatsky reaction of methyl (+)-α-bromopropionate with benzaldehyde was carried out in order to study the reaction mechanism, and two epimeric methyl 3-hydroxy-2-methyl-3-phenylpropionates (IIa and IIb) were obtained in a 59 : 41 ratio. From a comparison of the optical activity of IIb with that of pure (−)-IIb, it was estimated that lib consists only seven percent of an optically-active compound; this results supports the hypothesis of the enolate anion mechanism. Subsequently, the stereochemistry of this reaction with 2-phenyl-propanal (IV) and 3-phenyl-2-butanone (VIII) was studied. The condensation of IV with methyl bromo-acetate gave a mixture of the epimeric methyl 3-hydroxy-4-phenylvalerates (Va and Vb), which were separated in a 26 : 74 ratio by means of column chromatography on silica gel. Similarly, VIII was also condensed with methyl bromoacetate to give the epimeric methyl 3-hydroxy-3-methyl-4-phenylvalerates (IXa and IXb) in a 31 : 69 ratio. The configurations of these esters were assigned by correlation with the products of the Grignard reaction, the stereochemistry of which is well known. From the present study, it is clear that the Reformatsky and the Grignard reactions of the carbonyl compound having an asymmetric α-carbon atom proceed in a similar fashion; that is, the entering group predominantly approaches the carbonyl group from the least-hindered side. Therefore, Gram’s rule of asymmetric induction can be applied in the stereochemistry of the Reformatsky reaction.
Stereochemical Studies in Friedel-Crafts Reactions. I. The Reactions of cis-and fraws-4-Tetrahydrophthalic Acid and Its Dimethyl Ester with Benzene
Authors: Sugita Kaichiro , Tamura Shuzi
Published: July 2006

The aluminum chloride-catalyzed reactions of cis-Δ4-tetrariydrophthalic acid (1A) and its dimethyl ester (3A) with benzene gave, stereoselectively, t-4-phenyl-cis-bexahydrophthalic acid (2A) and its dimethyl ester (12) respectively. Similarly, the reactions of trans-Δ4-tetrahydrophthalic acid (1B) and its dimethyl ester (3B) with benzene gave, stereoselectively, c-4-phenyWrtrans-hexahydrophthalic acid (2B) and its dimethyl ester respectively, accompanied by a small amount of the c-4,t-2,r-1-isomer. The mechanism can be explained by presuming the interaction of the lone-pair electrons of carbonyl oxygen in the axial carboxyl group with a vacant p-orbital of the carbonium ion, which is produced by protonation to the double bond of the cyclohexenes (1A, 1B, 3A, 3B).
Stereochemical Studies in Friedel-Crafts Reactions. II. The Reactions of 4-Substituted Cyclohexenes with Benzene
Authors: Sugita Kaichiro , Tamura Shuzi
Published: July 2006

The addition reactions of benzene to the double bonds of 4-substituted cyclohexenes, such as 4-benzoyl-cyclohexene (5), 4-acetylcyclohexene (6), methyl 4-cyclohexenecarboxylate (7), and 4-cyclohexenecarboxylic acid (8) have been studied in the presence of aluminum chloride. In all cases, the reactions gave mainly 1,4-disubstituted cyclohexane with the trans configuration stereoselectively. A possible mechanism for this reaction is suggested.
Studies on Separation of Amino Acids and Related Compounds. V. A Racemization Test in Peptide Synthesis by the Use of an Amino Acid Analyzer
Authors: Izumiya Nobuo , Muraoka Masako , Aoyagi Haruhiko
Published: July 2006

Several tripeptides, H-Gly-Dl-Ala-B-OH, in which B residues are Dl-alanine, l-valine, l-leucine, l-phenyl-alanine, l-proline, and l-serine have been synthesized and the separation of each glycyltripeptide diastereomers by an amino acid analyzer have been studied. Among six peptides studied, diastereomeric mixtures of H-Gly-Dl-Ala-l-Val-OH and H-Gly-Dl-Ala-l-Leu-OH were separated completely. A procedure to determine the amounts of Ll and Dl diastereomer of H-Gly-Ala-Leu-OH by the use of the analyzer was developed, and this procedure was applied to examine the influence of coupling reagents for racemization during coupling of benzyl-oxycarbonyl-glycyl-l-alanine and l-leucine benzyl ester by several reagents.
The Carboxylation Reaction using Nickel Catalysts. V. The Catalytic Reaction of Propene with Nickel Carbonyl and Nickel Carbonyl-Triphenylphosphine
Authors: Kunichika Sango , Sakakibara Yasumasa , Okamoto Tadashi , Takagi Kentaro
Published: July 2006

The carboxylation reaction of propene catalyzed by nickel carbonyl was studied undeer various conditions. Iso- and n-butyric acids were obtained in good yields under mild conditions in the presence of a large amount of an organic acid. The catalytic carboxylation area was examined in detail. The carboxylation reaction proceeded smoothly in tetrahydrofuran, acetic acid, and dioxane. The proportion of isobutyric acid was largest in acetic acid (72.5–77.5%). Triphenylphosphine (TPP) had a great effect on the reaction rate, the catalytic reaction area, and the product distribution. On the reaction mechanism, an active species (HNi(CO)(TPP)X) was taken to account for the experimental results.
Mechanistic Studies on the Photochemical Oxidation of Phenothiazine with Oxygen in Ethanol
Authors: Iwaoka Teiki , Kokubun Hiroshi , Koizumi Masao
Published: July 2006

It has been established that phenothiazine (PTH) undergoes photooxidation, PTH+O2\oversethν→PT·+HO2 in the aerated ethanol (dehydrated!) yielding a neutral radical as a stable product. The reaction is a one photon process and the reactive state is triplet PTH. It has further been established that the reaction occurs via a molecular complex (PTH-O2) most likely of C-T type, which has the absorption at ∼385 nm and decays with the first order rate constant of 1.6×102 sec−1. A similar transient C-T complex has been found to be produced from triplet PTH and dimethylisophthalate (weak electron acceptor) (absorption ∼385 nm, decay constant 2×103sec−1) with almost the diffusion controlled rate constant, although the eventual reaction does not occur. Thus in case of (PTH-O2), reaction (PTH-O2)→PT·+HO2 occurs while in case of (PTH-DMIP), the analogous reaction does not. Behavior of radical species (containing radical cation and (PTH-O2)) produced in the rigid aerated ethanol at 77°K has also been studied. The present C-T complex is interesting in the point that it is produced via triplet state of donor and has a rather long lifetime.
Conformations of the Esters. V. The Conformations of Carbonates
Authors: Oki Michinori , Nakanishi Hiroshi
Published: July 2006

In alkyl or aryl carbonates, the presence of conformational isomers (s-cis and s-trans) has been confirmed by infrared and nuclear magnetic resonance spectroscopic techniques. The dipole-moment measurements also support the conclusions obtained from the spectroscopic data.
Preparation of Carboxylic Esters and Phosphoric Esters by the Activation of Alcohols
Authors: Mitsunobu Oyo , Eguchi Masahiko
Published: July 2006

The reaction of dibenzyl hydrogen phosphate with alcohols in the presence of diethyl azodicarboxylate and triphenylphosphine, followed by catalytic hydrogenation, resulted in the formation of the corresponding alkyl dihydrogen phosphates. When p-tolyl dihydrogen phosphate and ethanol were allowed to react with diethyl azodicarboxylate and triphenylphosphine, ethyl p-tolyl hydrogen phosphate and diethyl p-tolyl phosphate were obtained. On the other hand, dipyridinium p-tolyl phosphate gave ethyl p-tolyl hydrogen phosphate and di p-tolyl pyrophosphate. The reaction of alkyl N,N′-tetraethylphosphorodiamidites with carboxylic acids in the presence of diethyl azodicarboxylate resulted in the formation of corresponding carboxylic esters. When these reactions (benzoylation) were carried out with the use of optically active 2-octanol, 2-octyl benzoate was obtained with inverted configuration.
Synthesis and the Iodine-Catalyzed Rearrangement of Isohibaene
Authors: Kitadani Masayuki , Ito Ken , Yoshikoshi Akira
Published: July 2006

A partial synthesis of isohibaene (VI) starting with nezukol (V) has been accomplished. It involves, as the key step, the intramolecular insertion reaction of a ketocarbene generated by cuprous oxide-catalyzed decomposition of diazoketone (XI) under irradiation. It has been found that isohibaene undergoes rearrangement into a mixture of phyllocladene (XIV) and isophyllocladene (XV) by iodine catalytically.
Studies of Hydroxy Amino Acids. II. The Separation of Diastereoisomers of Hydroxy Amino Acids
Authors: Ariyoshi Yasuo , Sato Naotake
Published: July 2006

It has been found that erythro-β-hydroxy-Dl-norvaline, and erythro-β-hydroxy-Dl-norleucine, and threo-β-hydroxy-Dl-leucine form scarcely-soluble compounds in water with α-naphthylphosphoric acid, tetrachlorophthalic acid, and chlorendic acid, respectively. On the other hand, the compounds of their diastereoisomers with the reagents were soluble in water. On the basis of these facts, β-hydroxy-Dl-norvaline, β-hydroxy-Dl-norleucine, and β-hydroxy-Dl-leucine were successfully separated into their diastereoisomers. The configurational assignment of α-amino-β-hydroxy acids without a branched side chain on the γ-carbon atom was established by means of NMR spectroscopy.
The Photochemistry of Large-ring Cycloalkanones
Authors: Matsui Kiyohide , Mori Takasi , Nozaki Hitosi
Published: July 2006

The photoreactions of 11-, 12-, and 13-membered cycloalkanones (Ia, Ib, and Ic) are described. The major products are cis, trans isomers of bicyclo[n.2.0]alkan-1-ol (n=7, 8, and 9; II, III). The stereochemistry and multiplicity of the reactive species have been discussed with emphasis on the effect of the ring size. The Ib cyclododecanone is most readily susceptible to the photochemical cyclization via its S1 state, affording the cis-cyclobutanol IIb stereoselectively.
Decomposition of Saturated Gaseous Hydrocarbons in Induction-Coupled Argon Plasma Jet
Authors: Nishimura Yukio , Satoh Arata , Takeshita Kenjiro , Sakai Wataru
Published: July 2006

The decomposition of methane, ethane, and isobutane has been studied in an induction-coupled argon plasma jet at atmospheric pressure. Methane was decomposed to give mainly acetylene, soot, and hydrogen, and to give the traces of ethylene and ethane. From the dependence of both the conversion of methane and the product distribution on methane feed rate, the input and argon flow rate, it was concluded that methane was not completely mixed with the plasma jet but the decomposition of methane took place mainly in the outer flame of the plasma jet and its surroundings. In the decomposition of ethane, ethylene, and methane were formed in 20–27% and 3–5% selectivity based on carbon, respectively, in addition to acteylene, soot, and hydrogen. In the decomposition of isobutane, propylene was produced in 10–14% selectivity based on carbon, besides the above mentioned products. From these results together with those on propane and n-butane,it was suggested that radicals formed by a fission of C–H or C–C bond played the main role in the decomposition of saturated gaseous hydrocarbons in the induction-coupled argon plasma jet.
The Electronic Structure of Zeise’s Salt, [PtCl3C2H4]−
Authors: Katô Hajime
Published: July 2006

A semiempirical SCF MO method including all the valence electrons in a molecule has been applied to Zeise’s salt, which is one of the most simple metal-olefin π-complexes. The electron-repulsion integrals are included explicitly in the present method. The results agree well with the available experimental data, indicating that the C-C bond order is equal to 1.545 and that the ethylene is tightly bound to platinum. An attempt to assign the observed bands to particular electron transitions has been made on the basis of a calculation of the transition energies and transition moments. We identify the band at 40700 cm−1 as the charge-transfer band corresponding to the electronic transition from ethylene to platinum. Several properties of Zeise’s salt are calculated, and much information on the bonding is obtained.
Diffuse Reflection Spectra of Filter Papers Dyed with 1-Arylazo-2-naphthols
Authors: Matsunaga Yoshio , Miyajima Nobuhiko
Published: July 2006

The diffuse reflection spectra of filter papers dyed with sixteen 1-arylazo-2-naphthols were examined in the range from 350 to 700 mμ. The absorption bands due to both the azo and hydrazone tautomers were observed in this state. Appreciable changes in the hue of the dyed papers caused by moisture were attributed to the deviation from the Kubelka-Munk theory due to the increased regular reflection; however, the movement of the tautomeric equilibrium caused by moisture was also clearly demonstrated in many cases. The direction was found to depend upon the kind and position of the substituents, e.g., towards the azo tautomer in the case of the p-Cl and o-NO2 derivatives and towards the hydrazone tautomer in the case of the m-Cl and o-MeO derivatives.
Low Frequency Infrared Absorption Bands of Water of Crystallization at Low Temperature
Authors: Fukushima Kunio
Published: July 2006

The low temperature infrared absorption spectra of water of crystallization of BaCl2·2H2O, CuCl2·2H2O and K2C2O4·H2O, which have water of crystallization in different bound states, were measured and compared with the room temperature spectra. Corresponding to the change of temperature of the samples, remarkable change in frequencies and intensities was observed for the bands due to the lattice vibrations associated with water of crystallization.
The Recombination of Iodine Atoms Generated by a C. W. Argon Ion Laser
Authors: Harada Naohiko , Mori Yuji , Tanaka Ikuzo
Published: July 2006

The rate constants of iodine-atom recombination in various foreign gases were determined by measuring the relative concentrations of iodine atoms in the photostationary state, through irradiation by a c.w. argon-ion laser at 4880 Å. The relative concentration has been obtained from the absorption intensity for the emission line from an iodine discharge lamp at 1830 Å. The rate constants have been given for the diffusion of iodine atoms and for the second-order recombination of iodine atoms. The values of the diffusion rate constants in various foreign gases have been compared with the calculated values. The logarithmic second-order rate constants in various gases were plotted against their ionization potentials. The plot yielded a straight line, indicating that the formation of the charge-transfer complex between iodine atoms and foreign gas molecules is important in the recombination process, as has been suggested by Porter et al.
Charge Transfer Interaction and Chemical Reaction. III. Reactions of m-Phenylenediamine and Related Compounds with Chloranil
Authors: Nogami Takashi , Yamaoka Tsuguo , Yoshihara Keitaro , Nagakura Saburo
Published: July 2006

The interactions of chloranil with several aromatic amines were studied by measuring visible and ultraviolet absorption spectra at various temperatures between 70°K and 300°K, m-aminophenol, m-phenylenediamine, N,N-dimethyl-m-phenylenediamine, 1,3,5-triaminobenzene, and 1-methyl-2,4,6-triaminobenzene being taken as electron donors. The m-phenylenediamine-chloranil system was studied in detail and outer and inner complexes were found to exist as reaction intermediates. The structure and stability of the inner complex were discussed. Kinetic studies were made for the m-phenylenediamine-chloranil and 1,3,5-triaminobenzene-chloranil systems. The enthalpy change, ΔH, for the formation of the outer complex was determined from the temperature dependence of the equilibrium constant. The activation energies, ΔE1 and ΔE2, for the processes from the outer complex to the inner complex and from the inner complex to the succeeding intermediate, respectively, were determined by analysing the time dependence of the absorptionpeak intensity of the inner complexes measured at several temperatures. The results are as follows: ΔH=−3.7, ΔE1=10, and ΔE2=22 (kcal/mol) for the m-phenylenediamine-chloranil system; ΔH=−2.6, ΔE2=16, and ΔE2=14 (kcal/mol) for the 1,3,5-triaminobenzene-chloranil system.
Paper Electrophoresis and Polarography of the Reaction Product between the Chromium(III) Ion and Potassium Hexacyanoferrate(II)
Authors: Shirai Michiko
Published: July 2006

In continuation of the previous work (Y. Matsumoto and M. Shirai, Bunseki kagaku, 12, 608 (1963); Y. Matsumoto and M. Shirai, This Bulletin, 39, 59 (1966).), results of a study of the colored products resulting from the reaction between the chromium(III) ion and potassium hexacyanoferrate(II) by paper electrophoresis and polarography will be presented in this paper. Paper-electrophoretical experiments illustrated that the negatively-charged complexes containing both Cr and Fe were gradually formed by reaction. In the presence of excess potassium hexacyanoferrate(II), the resulting complexes were constant in color and situation in the electrophoretical patterns, regardless of the molar ratio of reactants. On the other hand, in the case of a reactant molar ratio (Fe(CN)64− to Cr3+) below 2.5, the patterns varied with the ratio. The product, sampled either in the form of a reaction mixture or as isolated state (Y. Matsumoto, M. Shirai, and H. Saito, This Bulletin, 41, 2542 (1968).), was found to present no reduction wave of Cr3+ on polarography at the dropping mercury electrode.
Transition-metal Complexes of Pyrrole Pigments. III. Copper(II) and Zinc(II) Complexes of 1,19-Dideoxy-8,12-dicarbethoxy-1,3,7,13,17,19-hexamethylbiladiene-ac
Authors: Murakami Yukito , Matsuda Yoshihisa , Kanaoka Yukiko
Published: July 2006

The copper(II) and zinc(II) complexes of 1,19-dideoxy-8,12-dicarbethoxy-1,3,7,13,17,19-hexamethylbiladiene-ac were synthesized and investigated by near-ultraviolet, visible, near-infrared, infrared, NMR, and ESR measurements as well as X-ray diffraction measurements of powdered samples. The ligand-field bands appeared at 701 and 752 mμ for the copper complex provided information on its geometry around the central metal atom. Namely, the copper atom is subjected to the square-planar ligand-field in the complex. Infrared bands characteristic of asymmetric stretching vibration of the carbethoxy groups at 8 and 12, and X-ray powder diffraction pattern gave another support to this structure by referring to the corresponding data for the nickel complex. ESR measurements also provided the spin Hamiltonian parameters consistent with the square-planar coordination. The most plausible structure for the zinc complex was concluded to be the binuclear form with tetrahedral coordination in conformity with that for the cobalt complex, which was revised in this work. Infrared bands in the 1100–1300 cm−1 range due to asymmetric vibration of the ester groups at 8 and 12, and X-ray powder pattern provided the evidence for this structure in reference to the corresponding data for the cobalt complex. The up-field shift of proton signals due to the methyl groups at 1, 7, 13, and 19, the 10-methylene group, and to the ethyl moiety of carbethoxy groups at 8 and 12 upon coordination are consistent with the tetrahedral coordination with dimeric structure. The molecular weight determination also confirmed the dimeric nature of the zinc complex.
Chloropentakis(trichlorostannato)ruthenate(II)
Authors: Okuno Hisateru , Ishimori Tatsujiro , Mizumachi Kunihiko , Ihochi Haruhiko
Published: July 2006

The cesium and triethylammonium salts of chloropentakis(trichlorostannato)ruthenate(II), Cs4[RuCl(SnCl3)5]·CsCl and (Et3NH)4[RuCl(SnCl3)5], were prepared. Their IR absorption bands near 210 cm−1are thought to be due to the Ru–Sn stretching vibration. The electronic spectra of dilute hydrochloric acid solutions of the complex salts were the same as the spectrum of a single crystal of the cesium salt. This suggests the presence of the complex ion, [RuCl(SnCl3)5]4−, in acid solutions. A hydrolysis product of the complex ion contained ruthenium, tin and chlorine in the atom ratio of 1 : 5 : [α(<1)], and the cesium salt was yielded from a dilute hydrochloric acid solution of the hydrolysis product. The observations show the presence of the Ru–Sn bonds in the complex ion.
Circular Dichroism of Mixed Biguanide Ethylenediamine Cobalt(III) Complexes
Authors: Igi Kozo , Yasui Takaji , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Two kinds of mixed biguanide ethylenediamine complexes, [Co(bgH)2(en)]Cl3·3H2O and [Co(bgH)(en)2]Cl3·2H2O, have been resolved into their optically active isomers. The circular dichroism spectra of a complete series of the mixed complexes, (−)589-[Co(bgH)3]3+, (+)589-[Co(bgH)2(en)]3+, (+)589-[Co(bgH)(en)2]3+, and (+)589-[Co(en)3]3+, have been investigated in neutral and alkaline aqueous solutions. In alkaline solutions, the circular dichroism and absorption curves of the biguanide complexes shift to longer wavelengths than those in neutral solutions; this may be caused by the change of the coordinated biguanide (bgH) to the uninegative ligand (bg−) by deprotonation. A mixed guanylurea complex, [Co(guH)(en)2]Cl3·2H2O, has been newly prepared and optically resolved.
The Reaction of Azoxybenzene with Acetic Anhydride
Authors: Oae Shigeru , Maeda Tetsuya , Kozuka Seizi
Published: July 2006

When azoxybenzene was allowed to react with equimolar amount of acetic anhydride, a mixture of azobenzene, acetanilide, and acetic acid was obtained along with such gaseous products as carbon dioxide, carbon monoxide and methane. In the reaction of azoxybenzene with an excess acetic anhydride, however, azobenzene was not isolated, and only acetanilide was obtained. Acetanilide and acetic acid were also obtained in the reaction of azobenzene with acetic anhydride. The results suggest the initial formation of azobenzene which is eventually converted to acetanilide in the subsequent reaction with an excess acetic anhydride. The formation of acetanilide was inhibited by the addition of such radical scavengers as iodine, hydroquinone, and nitrobenzene. A free radical mechanism is suggested for the reaction. Phenazine N-oxide also apparently undergoes similar reaction.
The Tracer Study of the Reaction of Diphenyl Sulfone-1-14C with Elemental Sulfur Using a Convenient Degradative Method
Authors: Oae Shigeru , Nakai Mamoru , Tsuchida Yoshiyuki , Furukawa Naomichi
Published: July 2006

The reaction of diphenyl sulfone with elemental sulfur to give diphenyl sulfide and sulfur dioxide at above 300°C was investigated using diphenyl sulfone-1-14C. By the degradation of the product, diphenyl sulfide-x-14C, it was found that no migration of sulfide group took place. β-Naphthyl phenyl sulfone was also subjected to the same reaction, and not only β-naphthyl phenyl sulfide but also di-β-naphthyl sulfide and diphenyl sulfide were found among the products. These observations appear to indicate the reaction to be a rather simple displacement reaction that involves the initial attack of polymeric sulfur radical chain at C-1 bearing sulfonyl function.
Studies on Electron Spin Resonance Spectra of 2-Substituted Prop-2-yl Radicals
Authors: Ohno Atsuyoshi , Kito Noboru , Ohnishi Yutaka
Published: July 2006

Electron spin resonance spectra of 2-substituted prop-2-yl radicals have been obtained. The substituents reported herein are phenylthio, phonoxy, benzyl, ethylthio, ethoxy, and n-propyl groups. Spectra were not obtained for phenylthio- and ethoxy-substituted radicals. It has been elucidated that α-heteroatoms greatly delocalize the odd electron. The mechanism of heteroatom-participation is discussed. Time dependency of intensities of signals in ESR spectra has revealed a qualitative order of the lifetime of these free radicals.
Studies on Seven-Membered Heterocyclic Compounds Containing Nitrogen. XI. The Schmidt Reaction of 1-Benzyl-1-azacycloheptan-4-one, Menthone, and 2-Methyl-4,5,6,7-tetrahydrobenzo[b]thiazol-7-one
Authors: Sakakida Yoshifumi , Kumanireng Anthonius Sina , Kawamoto Heizan , Yokoo Akira
Published: July 2006

The Schmidt reaction of 1-benzyl-1-azacycloheptan-4-one afforded a mixture of 1-benzyl-1,4-diazacyclooctan-5-one (IV) and a tetrazole derivative (V). The treatment of menthone (VIII) was found to give a lactam (IX), plus a tetrazole derivative (X) as a minor product. 2-Methyl-4,5,6,7-tetrahydrobenzo[b]thiazol-7-one (XII) was subjected to the Schmidt reaction to give a lactam XIIIa; it did not afford a tetrazole derivative. The structures of these products were determined on the evidence of the NMR spectra.
Optical Rotatory Dispersion and Circular Dichroism of the Osmate Esters of Cyclic Mono-olefins
Authors: Sakota Naokazu , Tanaka Shunsaku
Published: July 2006

The osmate esters (as the di-pyridine adducts) of optically active mono-, di- and tricyclic mono-unsaturated terpenes were prepared for measurements of optical rotatory dispersion (ORD) and circular dichroism (CD). All the osmate esters of the cyclic olefins examined exhibited a strong Cotton effect in 470 mμ regions and a weak Cotton effect near 600 mμ regions, which were similar to those of the osmate esters of the open chained olefins reported in our previous paper. The sign of CD maximum in 470 mμ regions was found to be correlated to the chirality of gauche structure of the chelate ring containing an osmium chromophore. Furthermore, their absolute configurations were deduced from the data of circular dichroism of two diastereoisomers of cis-α-pineneglycol.
Optical Activity of Bis-1,1′-spiroindanes. I. Optical Resolution and Absolute Configuration
Authors: Hagishita Sanji , Kuriyama Kaoru , Hayashi Masanori , Nakano Yasuko , Shingu Keiji , Nakagawa Masazumi
Published: July 2006

The resolutions of 6,6′-dihydroxy-3,3,5,3′,3′,5′-hexamethyl-bis-1,1′-spiroindane (IIIa), 3,3,3′,3′-tetramediyl-bis-1,1′-spiroindane-6,6′-dicarboxylic acid (IIIc), and 5,5′-dihydroxy-bis-1,1′-spiroindane (VIII) are reported. The circular dichroism and absorption spectra of these optically active compounds and their derivatives were measured. The spectra were analysed by means of a coupled oscillator model. The relative frequencies and signs of the rotational strengths associated with the p-band transition calculated for the (S)-configuration of 6,6′-disubstituted-bis-1,1′-spiroindanes agree with the positions and signs of the CD bands observed for the compounds derived from (−)-IIIc, establishing the absolute configuration of this series. The result was confirmed by the X-ray diffraction study of (−)-7,7′-dibromo-derivatives prepared from (+)-IIIa. It was found that these spiro compounds having the (S)-configuration showed a negative CD band in the longest wavelength region, except for the case in which the effect of the charge transfer between two aromatic chromophores overwhelmed that of the dipole-dipole interaction.
The Formation of Triaryl-s-triazine in the Chemiluminescence Reaction of Triarylimidazole and in the Photo-oxygenation of Triarylimidazole in the Presence of Ammonia
Authors: Maeda Koko , Hayashi Taro
Published: July 2006

2,4,6-Triphenyl-s-triazine (II) is formed either in the chemiluminescence reaction of 2,4,5-triphenylimidazole (I) in the presence of oxygen and a strong base or in the photolysis of I in alcohol in the presence of ammonia and oxygen. II is also formed in the sensitized photo-oxygenation of I in alcohol containing ammonia. It was found that II was produced by the reaction between the lophyl hydroperoxide (V), which was prepared from I and was known to be one of the intermediates in chemiluminescence reaction of I, and ammonia. Chemical and spectroscopic evidence that II is produced from V and not via the dioxetane-type peroxide (VI) nor N,N′-dibenzoylbenzamidine (IV), is given. II and several other 2,4,6-triaryl-s-triazines were found to be easily prepared from the corresponding triarylimidazoles by the sensitized photo-oxygenation in methanol in the presence of ammonium acetate and this provides a new method for the synthesis of triaryl-s-triazine.
The Crystal and Molecular Structures of a 3 : 2 Adduct of Acetylene and Isonitrile Derivatives
Authors: Suzuki Yoshio , Iitaka Y\={o}ichi
Published: July 2006

In order to determine the structure of the 3 : 2 adduct (acetylene : isonitrile) obtained by cycloaddition reaction of dimethyl acetylenedicarboxylate with 2,6-dimethylphenylisonitrile and to elucidate the route of the reaction, a heavy atom derivative of this adduct was prepared and subjected to X-ray diffraction analysis. The crystal grown from acetone solution has the composition C36H34N2O12Br2·CH3COCH3 and belongs to monoclinic system with the lattice constants: a=34.13±0.04, b=14.66±0.02, c=8.10±0.01 Å, β=90.5±0.2°. The space group is P21⁄n containing four formula units in the cell. The structure was solved by the heavy atom method and refined by the block-matrix least-squares method for 1482 observed reflections allowing the anisotropic thermal motions for each atom. It has been shown that the chemical structure of the adduct is 1-(4-bromo-2,6-dimethylphenyl)-2-(4-bromo-2,6-dimethylphenyl)imino-1,2-dihydro-3,4,5,5,6,7-hexacarbomethoxy-5H-1-pyrindine.
The X-Ray Emission Spectra of the Compounds of Third-period Elements. I. The K Spectra of Chlorine in Compounds
Authors: Takahashi Yoshihito
Published: July 2006

On chlorine gas and several oxysalts of chlorine, the values of the wavelength shift of ClKα1,2 lines and the spectra of ClKβ lines were measured. We thus verified our assumption that the Kβ′ line results from the bias of valence electrons from the atom of the third-period element to the oxygen atom in the oxyanion; this can be explained in terms of the relationship between the chemical structure and the ClKβ spectrum of the hypochlorite ion. The relationship between the relative intensity of the Kβ′ line and the wavelength shift of the Kα1,2 lines was linear, just as in the cases of oxygen-sulfur compounds.
Electronic Structure of Lone Pairs. IV. The Transannular Interaction of Several Meso-cycles
Authors: Yamabe Hiroko , Kato Hiroshi , Yonezawa Teijiro
Published: July 2006

The MO calculation of the transannular interaction of eight-membered model systems, containing S,O,N, or C atoms in the position opposed to the C atom of the C=O group, are made by the extended Hückel method and the semi-empirical ASMO SCF method. The relation between the bond order (Prs value or EAB value) and the infrared absorption frequency, νC=O, is discussed. The electronic absorption maxima in the 221 mμ–235 mμ region are assigned to π–π* type transitions of intramolecular charge transfer from the interacting atom, X, to the C=O group. The absorptions in the region from 217 mμ to about 190 mμ are n–σ* type transitions. In the model calculation of the NH3 and HCHO system, it is shown that the interaction is large, the lone pair being directed to the C atom.
On the Effects of Doubly Excited Configurations in Semi-Empirical Molecular Orbital Calculations on Non-Alternant Hydrocarbons
Authors: Kashiwagi Hiroshi
Published: July 2006

Effects of inclusion of doubly excited configurations in semi-empirical SCF-CI calculations are studied for the π-electrons of the four non-alternant hydrocarbons, fulvene, heptafulvene, vinylfulvene, and fulvalene. Transition energies to lower excited states are little affected by inclusion of doubly excited configurations. However, oscillator strengths change substantially and a good agreement with experiment is obtained. Dipole moments of ground states are affected by about 20%.