bluuebunny/crossref_metadata_2025_split huggingface dataset:
Charge-transfer Interaction and Chemical Reaction. IV. Reactions of para-Substituted Derivatives of Aniline with Chloranil
Authors: Nogami Takashi , Yoshihara Keitaro , Nagakura Saburo 
Published: July 2006

Abstract
Interactions of chloranil with p-phenyIenediamine, N,N-dimethyl-p-phenyIenediamine, and N,N,N′,N′-tetramethyl-p-phenylenediamine were studied by measuring visible and ultraviolet absorption spectra at various temperatures between 77°K and 300°K. In an ether-isopropyl alcohol (3:1) mixed solvent, the p-phenylenediamine- and N,N-dimethyl-p-phenylenediamine-chloranil systems were led to the substitution reaction through the outer complex and the ionic species as reaction intermediates. In ethyl ether, the p-phenylenediamine- and N,N-dimethyl-p-phenylenediamine-chloranil systems were found to yield the inner complex and the substituted species through the outer complex, respectively. In the N,N,N′,N′-tetramethyl-p-phenylenediamine-chloranil system, the inner complex was found to be formed via a clustering of the outer complexes.
The interactions between aromatic amines and chloranil were found to be classified into the following three types: (a) the charge-transfer (outer or inner) complex is formed between an electron donor and an acceptor and no further reaction proceeds; (b) the substitution reaction occurs through the outer and inner complexes; (c) the substitution reaction occurs through the outer complex and ionic species. The difference in the reactivities between mtfta-substituted derivatives of aniline and ortho- and para-substituted ones was explained by taking the π-electron density on the amino group into account.
Oxygen Exchange of Benzenesulfinic Acids in Water
Authors: Kobayashi Michio , Minato Hiroshi , Ogi Yoshikuni 
Published: July 2006

Abstract
When arenesulfinic acids were heated in water (H218O, 1.52 atom%) at 90–100°C for several hours, the 18O contents of the disproportionation products (thiolsulfonate and sulfonic acid) and the sulfinic acid recovered were approximately the same. The rate of oxygen exchange of p-toluenesulfinic acid was much faster than that of methyl phenyl sulfoxide, whereas the rate of oxygen exchange of benzoic acid was much slower than that of benzaldehyde. A mechanism consistent with the kinetic results is proposed for the oxygen-exchange reaction, involving the formation of the sulfinic anhydride (sulfinylsulfone) as an intermediate.
The Infrared Spectra and the Antiferroelectric Phase Transition of Copper Formate Tetrahydrate
Authors: Hiraishi Jiro 
Published: July 2006

Abstract
The infrared spectra of copper formate tetrahydrate are measured in the frequency region from 4000 to 24 cm−1 at various temperatures. This compound is known to undergo an antiferroelectric phase transition at −37.7°C. The bands due to the librational and translational modes of the crystalline water molecules in the antiferroelectric phase are quite different from those in the paraelectric phase, while no appreciable differences between the spectra in the two phases are observed for other bands. Those facts agree with the results obtained by the crystallographic study, which show that the ordering of the orientation of the water molecules occurs at the phase transition. The similarity of the librational and the translational modes of the water molecules to those of ice is also discussed.
The Catalytic Oxidation of Carbon Monoxide on Zirconium Dioxide
Authors: Hamamura Takuya , Onishi Yoshito , Iizuka Yasuo 
Published: July 2006

Abstract
The catalytic oxidation of carbon monoxide on zirconium dioxide was kinetically examined in order to compare with the results of titanium dioxide. The experiment was carried out under gas pressures of 10−2−100 mmHg at 400–550°C. The reaction rate was proportional to PCO and did not depend upon PO2, and there was no retarding effect by carbon dioxide. The rate constant of this oxidation reaction almost agreed with that of the reduction of zirconium dioxide by carbon monoxide. The reaction mechanism could be explained in the same manner as that on titanium dioxide. The catalytic activity of zirconium dioxide for this reaction was almost the same as that of rutile. The activation energy was about 12.5 kcal/mol, and this value was intermediate between those of anatase and rutile. The same relation was obtained in the activation energies of the thermal desorption of surface oxygen from these catalysts.
Molecular Structure of Propane
Authors: Iijima Takao 
Published: July 2006

Abstract
The structure of propane has been investigated by gas electron diffraction. The thermal average distances rg and rα-angles determined with the estimated limits of error were: C—C=1.532±0.003 Å, C–H=1.107±0.005 Å, ∠CCC=112±1°, and ∠HCH(CH3)=107±3°. By combining the diffraction results with the microwave data, the zero-point average structure has also been determined.
Ionization Energies and Rydberg States of Tetraaminoethylenes
Authors: Nakato Yoshihiro , Ozaki Masaru , Tsubomura Hiroshi 
Published: July 2006

Abstract
Absorption spectra and photo-ionization curves of tetrakis (dimethylamino) ethylene, (TMAE), and 1,1′,3,3′-tetramethyl-Δ2,2′-bi(imidazolidine), (TMBI), have been studied. It has been found that these compounds have very low ionization potentials (about 5.4 eV), which are even comparable with that of the lithium atom. The first ionization potentials of these compounds are nearly the same, although both their absorption spectra and their photo-ionization curves are considerably different from each other. These results can be explained semi-quantitatively by use of the results of simple, semi-empirical molecular orbital calculation with inclusion of direct interaction between four lone-pair orbitals on the N atoms, which was found to be important at the “perpendicular” structure. The first absorption bands of these molecules are assigned to the Rydberg bands, lying quite unusually near the visible region. The quantum defect δ is found to be 0.7 for the lowest Rydberg state of TMAE. The size of the Rydberg orbital for this state is estimated to be 2.9 Å from the maximum radial density, which is comparable with the core size. Higher Rydberg series are also observed for TMBI.
The Effects of Pre-irradiation Treatments on the Chemical Behavior of 64Cu Recoil Atoms in Neutronirradiated Copper Phthalocyanine
Authors: Kudo Hiroshi 
Published: July 2006

Abstract
The chemical behavior of 64Cu recoil atoms was studied in copper phthalocyanine which had been quenched from an elevated temperature or exposed to 60Co γ-rays before the neutron irradiation. In the quenched β-crystal, the initial retention was found to increase with an increase in the temperature of pre-irradiation heating, while the plateau retention of the post-neutron annealing reaction decreased. These results were compared with those for cadmium phthalocyanine and were understood in terms of “dislocation” in the crystal, the recoil atoms being assumed to be trapped and stabilized in the “dislocation.” Although the variations were small, the irradiation with 60Co γ-rays caused a change in the chemical behavior of the recoil atom. The role of some radiation-induced species were discussed.
Polarographic Investigation of Biopolymers. II. Cu (II)-poly (α,l-Glutamic Acid) in the Helix-Coil Transition Region
Authors: Inoue Senkichi , Yamaoka Kiwamu , Miura Masaji 
Published: July 2006

Abstract
The pH-induced helix-coil transition of the complex of Cu(II)-poly(α,l-glutamic acid) was studied with polarographic method. The diffusion current was found to change very sharply in a narrow range of pH and this change depended on the amount of Cu(II) ions. The half-wave potential of the complex was also dependent on pH and mixing ratio. The effect of Cu(II) ions on the secondary structure of the polymer was discussed from the viewpoint that the helix-coil transition of PGA is responsible for the change of the mode of binding interaction between Cu(II) ions and PGA sites. Based on the data of diffusion currents versus mixing ratios, the helical fractions of the complex at pH 3.4 and 4.0 were evaluated to be 0.37 and 0.11, respectively. From a value of the diffusion coefficient of the complex at pH 5.0, the molecular size in a random-coil form was calculated to be approximately 70 Å in diameter. The coordination number of the complex in the coiled form depended on the mixing ratio; the number was 3.4 in excess of polymer and 0.2–0.3 for the mixing ratio between 3.2 and 13. These values were discussed in terms of the possible mechanism of coordination. Finally, the activation energy of diffusion was obtained for complexes in helical and random-coil forms.
An MO-theoretical Study of the Nucleophilic Bimolecular Ring-opening of Ethylene Oxide
Authors: Fujimoto Hiroshi , Katata Motohiro , Yamabe Shinichi , Fukui Kenichi 
Published: July 2006

Abstract
The results of an approximate molecular orbital (MO) calculation of the interaction energy of the ring-opening of ethylene oxide by a hydride ion are presented. The method of calculation is based upon the isolated-molecule approximation. The interaction energy was divided into the Coulomb, exchange, delocalization, and polarization interaction terms, and the changes in these four terms with the progress of the reaction were investigated. The wave function of the combined system of ethylene oxide and a hydride ion was obtained by the configuration interaction (CI) procedure. The changes in the electron populations of ethylene oxide and the hydride ion were calculated from the ground-state CI wave function. Among the unoccupied MO’s of ethylene oxide, two low-lying unoccupied MO’s were shown to be of special importance in the electron transfer from the attacking anion to ethylene oxide. The effect of the deformation of the molecular shape upon the interaction energy and the intermolecular bond formation is also discussed.
A Study on the Nature of the Electronic Absorption Bands of Formylpyrroles and Acetylpyrroles
Authors: Matsuo Taku , Shosenji Hideto 
Published: July 2006

Abstract
The electronic spectra of formyl- and acetylpyrroles were studied from both experimental and theoretical viewpoints. On the basis of the solvent effect and pH-dependence of the absorption spectra, the lowest energy transitions of 2- and 3-acetylpyrroles and the corresponding formylpyrroles, as well as the second lowest energy transitions of 3-acylpyrroles, were suggested to be accompanied by the electron-transfer from the pyrryl to carbonyl group. As to 1-acetylpyrrole (or 1-formylpyrrole), the longest wavelength absorption bands disappeared when the conjugation between the pyrryl and carbonyl groups were inhibited by steric hindrance. Solvent effects on the absorption band, however, were so small that the extent of electron-transfer was considered to change little during the transition. The results of VESCF MO calculations also supported the above suggestion based on experimental observations. The behaviors of the second lowest energy transitions of 1- and 2-acylpyrroles were too complicated to be accounted for straightforwardly.
Intermolecular Hydrogen Transfer Reactions in the Excited States of EDA-Complexes of Benzophenone with Aromatic Amines at Low Temperature
Authors: Arimitsu Satoshi , Tsubomura Hiroshi 
Published: July 2006

Abstract
Electronic absorption and emission spectra of the mixtures of benzophenone and aromatic amines have been studied in rigid solutions. From absorption spectral measurements, it has been concluded that benzophenone as an acceptor forms the molecular complexes with various aromatic amines as donors. Emission spectra different from those of the component molecules were observed at longer wavelengths in the same systems. The maxima of the anomalous emission spectra of these systems were found to shift slightly to lower frequencies with the decrease in the ionization potentials of donor molecules. On account of their decay times, the emissions may be ascribed to the phosphorescence of benzophenone-aromatic amine complexes. Photolysis of benzophenone-aromatic amine complexes in rigid matrices always resulted in the appearance of the visible absorption spectrum of benzoketyl radical, together with ESR spectra, the analysis of which indicated that there is an interacting pair of radicals which is in the combined triplet (S=1) state. From the evaluation of the zero field splitting constants, the average distances between the interacting radicals were estimated. These results suggest that intermolecular hydrogen atom transfer from aromatic amines to benzophenone occurs, yielding the ketyl and aromatic amine radicals which lie close to each other. The reaction was found to proceed by way of the lowest excited triplet state of benzophenone.
Thermodynamic Properties of an Aqueous Solution of Tetraethylene Glycol Diethyl Ether
Authors: Nakayama Haruo 
Published: July 2006

Abstract
The excess Gibbs energy of mixing, GE; the excess enthalpy of mixing, HE, and the excess volume of the mixing, VE, of the tetraethylene glycol diethyl ether+water system have been measured as functions of the composition at 25°C. The GE, which has been determined through the isopiestic measurement of the water activity, is positive over the entire range of composition and has its maximum at 40 mol% ether. As has been found for analogous systems, the s-curve of HE is again found; that is, HE is large and negative (exothermic) in the water-rich region and positive (endothermic) in the ether-rich region. The VE is negative over the whole range of composition and has a minimum at 23 mol% ether. These results are discussed in the light of the structural modifications of water in the immediate neighborhood of the ether molecule.
A Dilatometric Study of Compatible Polymer Mixtures
Authors: Akiyama Saburo 
Published: July 2006

Abstract
Polymer mixtures of poly(vinyl nitrate) (PVONO2), and poly(vinyl acetate) (PVOAc), which had previously been concluded to be compatible with each other, were investigated by the dilatometric method. As a result, a characteristic behavior of the mixtures was observed. Each mixture showed a single glass-transition temperature (Tg) over the whole range of composition; this temperature was higher than those of pure polymers in the middle region of composition. The transition temperatures of the mixtures obeyed a modified Gordon-Taylor expression. The thermal expansion coefficients of the mixtures are discussed in relation to the effect of blending.
Trace Analysis of Metals by ESR. I. Microdetermination of Copper by Means of Solvent Extraction of Copper(II) Diethyldithiocarbamate
Authors: Yamamoto Daijiro , Fukumoto Tuneo , Ikawa Noriaki 
Published: July 2006

Abstract
A new method was developed for the direct determination of copper using ESR. Cupric diethyldithiocarbamate complex dissolved in benzene shows a unique ESR spectrum. The bivalent complex in benzene gave a very strong ESR signal with intensity sensitive to 0.005 ppm of Cu(II)-ion. Thus the ESR signal can be utilized for the trace analysis of Cu(II)-ion. The ESR signal intensity was linear in the ranges 1.0–0.1 γ/ml and 0.1–0.01 γ/ml of Cu(II)-ion. Mg2+, Fe2+, Ba2+, Mn2+, Zn2+, Co2+, Pb2+, Ni2+, I−, Br−, and NO3− did not interfere with the determination, while Hg2+ and CN− did. Comparing this method with photometric determination, we see that a very low content of Cu(II)-ion can be determined with a very small amount of sample.
Nickel(II) Complexes of 1,5-Dialkyl-2,4-pentanediones
Authors: Yoshida Isao , Kobayashi Hiroshi , Ueno Keihei 
Published: July 2006

Abstract
Bis(heptane-3,5-dionato)nickel(II) monohydrate [Ni(DNPM)2·H2O], bis(nonane-4,6-dionato)nickel(II) monohydrate [Ni(DNBM)2·H2O], bis(2,6-dimethylheptane-3,5-dionato)nickel(II) monohydrate [Ni(DIBM)2·H2O], bis(2,8-dimethylnonane-4,6-dionato)nickel(II) monohydrate [Ni(DIVM)2·H2O] and bis(tridecane-6,8-dionato)nickel(II) monohydrate [Ni(DNCM)2·H2O] were prepared, and a dimeric octahedral structure was proposed for each of them by means of spectroscopic studies. These dimeric chelates, (NiL2·H2O)2 were stable in solid state, however they disproportionated in non-coordinating solvents to afford dimeric monohydrates, Ni2L4·H2O, and monomeric dihydrates, NiL2·2H2O. DTA studies show that these monohydrates dehydrate in two steps and that the temperature of dehydration decreases in the order of the ligands, DNPM, DNBM, DIBM, DIVM, and DNCM. The dehydrated chelates are green in the neighborhood of room temperature while they changed into red at an elevated temperature. This thermochromism indicates that the chelates are in the trimeric octahedral form at low temperature and in monomeric tetra-coordinated square planar form at high temperature. On the other hand a nickel(II) chelate of 2,2,6,6-tetramethylheptane-3,5-dione (DPVM) was obtained as a pentacoordinated monodioxane adduct from aqueous dioxane. The coordinated dioxane was readily released to afford a monomeric tetra-coordinate square planar, red colored complex, Ni(DPVM)2.
Reaction Rates and Mechanisms of the Formation of Gallium(III), Indium(III), and Thallium(III) Complexes with Semi-Xylenol Orange in Aqueous Solutions
Authors: Kawai Yoichi , Takahashi Tetsuro , Hayashi Katsuyuki , Imamura Taira , Nakayama Hiroaki , Fujimoto Masatoshi 
Published: July 2006

Abstract
The kinetics for the complex formation of Ga(III), In(III), and Tl(III) with Semi-Xylenol Orange (SXO) in acid solutions were studied by stopped-flow technique. Kinetic results are interpreted in terms of a two-step mechanism involving pre-equilibrium. The increase in the reaction rate with decreasing hydrogen ion concentration is interpreted as the sum of several parallel pathways including monohydroxo metal ions and a few charge types of the ligand. The mechanisms and the rates of the three different d10-system metal ions are discussed. The phenomena of the slower increase in absorbance of Ga(III)-SXO complex after the rapid increase and the slow color fading of Tl(III)-SXO complex are also discussed.
The Electrochemical Behavior of the Low-valent Transititon-metal Complexes. I. Nickel-2,2′-Dipyridyl Complexes.
Authors: Misono Akira , Uchida Yasuzo , Yamagishi Takamichi , Kageyama Hironori 
Published: July 2006

Abstract
The electrochemical behavior of zero-valent nickel-2,2′-dipyridyl complexes (Ni(dipy)2, Ni(CH2CHCN)2-(dipy), and Ni(NCCHCHCN)2(dipy)) was examined in a hexamethylphosphoric triamide solution by polarographic and ESR measurements. In the polarography, these complexes were first reduced at a very anodic potential (E1⁄2: about −0.6–−0.8 V vs. Ag wire). At this reduction step, the anion radical of the complex was observed for all the complexes by means of ESR analysis. The spectra of the anion radicals and their g-values suggested the localization of an unpaired electron on the ligand side. The addition of 2,2′-dipyridyl to the solution increased the height of the second wave, the half-wave potential of which was also more anodic than that of free 2,2′-dipyridyl, and the anion radical of 2,2′-dipyridyl was observed at this reduction step. It was concluded that the dianion species formed at the second reduction step dissociated to give the 2,2′-dipyridyl anion radical, and that the anion radical of the complex was reproduced in the presence of excess 2,2′-dipyridyl.
Stereochemical Studies of Metal Chelates. IX. The Preparation and Stereochemistry of Cobalt(III) Complexes Coordinated with the meso-Form of 3,6-Diaza-2,7-dimethyl-1,8-diaminooctane
Authors: Saburi Masahiko , Yoshikawa Sadao 
Published: July 2006

Abstract
The meso-form of 3,6-diaza-2,7-dimethyl-1,8-diaminooctane (meso-3,8-dimetrien), one of the triethylenetetramine derivatives, was prepared. Dinitro- and dichlorocobalt(III) complexes with this ligand were also prepared and characterized. The Λ-cis-β(SS) and/or the Δ-cis-β(RR) configuration were assigned to these complexes. The trans-dichlorocobalt(III) complex of meso-3,8-dimetrien derived from the cis-β-dichloro complex was determined to have the meso-trans configuration (the absolute configurations of the coordinated secondary nitrogen atoms were antimeric to each other, namely, R and S), on the basis of proton magnetic resonance measurements.
Chlorination of Olefins with Thallium(III) Chloride Tetrahydrate
Authors: Uemura Sakae , Sasaki Osamu , Okano Masaya 
Published: July 2006

Abstract
In CCl4, TlCl3·4H2O reacted with mono- and diolefins to give vic-dichlorinated compounds (I) in 20–41% yields together with monochlorinated ones (II). The yields of I were intensely increased by adding CuCl2·2H2O or FeCl3 and bubbling oxygen into the reaction system, although such additives alone gave none of I in CCl4. In acetic acid, the reaction gave diacetoxylated compound. As to the vic-dichlorination, it was proposed that the reacting species was a polarized form of dimeric TlCl3 and not free chlorine evolved from TlCl3·4H2O.
The Base-catalyzed Condensation of o-Nitropropiophenone
Authors: Sakan Takeo , Hayashi Shoji , Miwa Toshio 
Published: July 2006

Abstract
Treatment of o-nitropropiophenone with sodium acetylide in liquid ammonia at −70°C gave a yellow phenol, C18H18O3N2, as a major product. The permanganate oxidation of the phenol gave 2-(1-carbamoylethyl)-2-methyl-3-indolinone, which was synthesized independently. From this result and the spectral data, the structure of the phenol was postulated to be 1-(o-hydroxyphenyl) derivative of the above indolinone. The neutral fraction of the reaction mixture gave three new compounds: 3-(o-Nitrophenyl)-1-pentyn-3-ol, 2-methyl-2-(2-methyl-3-indolinon-2-yl)-3(2H)-benzofuranone, and 3,3a-dihydro-2-hydroxy-3,3a-dimethyl-2-(o-nitrophenyl)-4(2H)-isoxazolo[2,3-a]indolone. Their structures were assigned from their spectral data. A mechanism for the formation of these products as well as for the base-catalyzed condensation of o-nitroacetophenone is discussed.
Reactions of Aryloxycopper(I) with Organic Halides
Authors: Kawaki Takao , Hashimoto Harukichi 
Published: July 2006

Abstract
Some aryloxycoppers were synthesized by the interaction of phenylcopper with phenols and then characterized. The reaction of aryloxycopper and organic halide in diglyme generally gave the corresponding ether. From these and other results, it is suggested that aryloxycopper (I) is an intermediate in the Ullmann condensation, etc.
Oxidation by Transition Metal Complexes. III. Oxidation of Cinnamaldehyde Catalyzed by Rhodium Compounds
Authors: Takao Kiyotomi , Wayaku Masami , Fujiwara Yuzo , Imanaka Toshinobu , Teranishi Shiichiro 
Published: July 2006

Abstract
The catalytic activity of RhCl(PPh3)3 and RhCl(CO)(PPh3)2 for oxidations of styrene and cinnamaldehyde has been studied. Under oxygen atmosphere, these complexes can cause catalytically oxidation of cinnamaldehyde to give benzaldehyde, glyoxal, benzene and styrene. The reaction is complicated because decarbonylation reaction takes place with oxidation, and the carbonyl complex formed plays a catalytic role for the oxidation.
Mercaptoacetate Derivatives. I. Reaction of Thiocyanatoacetic Esters with Aldehydes
Authors: Hayashi Toshio 
Published: July 2006

Abstract
An equimolar reaction of thiocyanatoacetic esters with aromatic aldehydes in the presence of sodium hydride, followed by treatment with hydrogen chloride, led to a mixture of 4-alkoxycarbonyl-5-aryl-2-imino-1,3-oxathiolane hydrochloride (3) and α-(S-carbamoylthio)-βchlorodihydrocinnamic ester (4). When excess aldehyde was used in the reaction, a small amount of 2,10-bis(α-chlorobenzyl)-4,8-dioxo-6-phenyl-5,7-diaza-3,9-dithiaundecanedioate (5) was obtained, together with the products 3 and 4. The NMR studies revealed that product 3 isolated exists all in one isomer which has the 4-ester and 5-aryl groups cis about a single bond in the ring. It was suggested that product 4 was formed by rearrangement of the trans isomer of 3.