bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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(&lt;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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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%.
Electronic States of Diphenylamine and Its Related Compounds
Authors: Hinohara Tadao , Cho Seikichi , Morita Toshifumi 
Published: July 2006

Abstract
For the analysis of the characteristic nature of the first absorption band of diphenylamine (DPA), calculations of the electronic states of DPA and its analogous compounds, diphenylether (DPE) and diphenylmethane (DPM), were carried out and the solvent effects on the fluorescence spectra of these compounds were investigated. The calculated results show that the first excited states of these three compounds are mainly benzene B2u. However, in DPA, the ionic state (CTs−) is located very closely to the B2u state. It seems reasonable to say, therefore, that, in solution, the ionic state lowers its energy down to the position of the B2u state and that the first absorption band observed in the solution is a superposed band of two transitions, G→B2u and G→CTs−. To confirm this assumption, the value of Δμ, which is the dipole-moment change between the ground and excited states, is estimated from the solvent effect on the fluorescence spectrum. The observed value of Δμ for DPA is intermediate between the theoretical values for the lowest (B2u) and the second excited state (CTs−) ; from this fact it may be inferred that the mixing of CTs− to the lowest excited state (B2u) is increased in the excited equilibrium state.
Studies on Salt Solution Aerosols. IV. Droplet Size Determination of Aqueous Sodium Chloride Solution Aerosols by Chemical Spot Method
Authors: Ueno Yasuo , Sano Isamu 
Published: July 2006

Abstract
Droplets of aqueous NaCl solution aerosols generated by atomization were collected on an AgNO3 containing film, by measuring microscopically the sizes of the AgCl spots formed on the film, the diameters of the droplets were determined with the aid of the calibration curve between the spot and droplet diameters. It was found that the calibration curve can be expressed by a relation Dd3=Kds2, where Dd is the volume average diameter of the droplets, ds the surface average diameter of the spots and K a constant. The meaning of K was considered.
Photosensitive Ionomer. I. Preparation of Mercurous Acrylate and Photosensitive Plates
Authors: Suzuki Shin , Sugita Kazuyuki 
Published: July 2006

Abstract
Photographic plates were prepared by coating an emulsion consisting of mercurous acrylate, polyvinyl alcohol and water on glass plates. They were found to be sensitive to light ranging from 250 nm to 340 nm. A dark brown image with density ca. 0.6 above the fog was formed by a printing-out process. The latent image could be amplified with the reducing developers such as hydroquinone or metol. Image formation was ascribed to metallic mercury which was isolated by photoreduction and/or reduction of mercurous ion.
Intermolecular Forces and Rotational Phase Transition in the C2H2 Crystal
Authors: Hashimoto Masao , Hashimoto Michiko , Isobe Taro 
Published: July 2006

Abstract
The potential energy of the acetylene crystal was calculated as a function of the rotational molecular orientations. The potential energy of this crystal has two kinds of minima, not a double minima; one arises from the quadrupole-quadrupole interaction, to which the high-temperature is due, while the other arises from the overlap repulsion interaction with which the low temperature structure is coincident. It was suggested that the mechanism of the phase transition in this crystal is a rotational transition between the two molecular orientations.
The Crystal and Molecular Structure of π-Cyclooctenyl-π-cycloocta-1,5-dienecobalt, Co(C8H13) (C8H12)
Authors: Koda Shigetaka , Takenaka Akio , Watanabé Tokunosuké 
Published: July 2006

Abstract
The crystal structure of π-cyclooctenyl-π-cycloocta-1,5-dienecobalt, Co(C8H13)(C8H12), has been established by successive Fourier analyses. The atomic parameters were refined by least-squares techniques using three-dimensional X-ray data to an R factor of 0.125. The complex molecule crystallizes in the space group P21⁄c with four molecules in the unit cell of dimensions: a=10.78, b=7.30, c=17.81 Å, β=104.2°. The four cobalt atoms lie nearly on the face-centered positions in the unit cell and are sandwiched between the two ligands, cyclooctenyl C8H13 and cyclooctadiene C8H12. The seven nearest Co···C distances range from 2.02 Å to 2.09 Å. Atoms Co, C(1), C(3) and the respective centers of the two double bonds, C(9)–C(16) and C(12)–C(13), in C8H12 ring are coplanar to within 0.08 Å. The conformation of C8H13 is of the tub form and C8H12 of the boat form. The two lengths of the double bonds in C8H12 are 1.41 Å and 1.39 Å, while those in the allyl part in C8H13 are 1.35 Å and 1.46 Å, respectively. The average distance of the remaining twelve C–C bonds is 1.54 Å.
The Primary Process of the Photochemical Dimerization of Carbostyril
Authors: Yamamuro Tetsu , Tanaka Ikuzo , Hata Norisuke 
Published: July 2006

Abstract
Carbostyril dimerizes photochemically in ethanol to yield its dimer. In order to clarify the primary process of this photochemical dimerization, studies by means of steady-light irradiation and flash spectroscopy and measurements of the absorption spectrum of the intermediate and of the phosphorescence spectrum at 77°K were carried out under various conditions. The transient absorption was observed around 430 mμ, it was identified as being due to a T–T transition of carbostyril. Experiments on both the decay kinetics of the triplet species and the quantum yield of the carbostyril disappearance under various conditions revealed that the photochemical dimerization of carbostyril proceeded through a bimolecular interaction between the triplet and the unexcited molecules.
Absorption Spectra of Crystals of Cytosine and Its Derivatives
Authors: Tanaka Masashi , Tanaka Jiro 
Published: July 2006

Abstract
The electronic spectra of cytosine, one of DNA bases, have been studied. The absorption spectra of single crystals of cytosine and its derivatives are presented, and the direction of the transition moment of the first π→π* band is determined to be inclined at about +100° from the N1–C4 line toward the C5 atom. The second π→π* band is shown to have polarization direction at +30° inclined to the reference axis.
Spreadability of Ovalbumin Monolayers at Air-water Interface. Effects of Additives to Spreading Solutions
Authors: Ishii Toshio , Muramatsu Mitsuo 
Published: July 2006

Abstract
The effect of additives (urea, potassium chloride, butanol, and thioglycol) to spreading solutions upon spread-ability of ovalbumin monolayers has been studied in terms of the rate constants and the limiting areas for intermediate (fast) and final (slow) processes of uncoiling of the protein molecule. It has been found that the addition results in the disappearance of the first (fast) process, which appeared upon spreading without additives. In the second (slow) process, the rate constant is found to be the same as that for the case without additives regardless of the type of the additives. Sodium dodecyl sulfate (SDS) added to the spreading solution is showed a peculiar behavior, which is explained in relation to the interaction between the protein and SDS molecules.