bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intensities of the T←S Transitions in Oxalyl Chloride and Bromide
Authors: Shimada Hiroko , Kanda Yoshiya 
Published: July 2006

Abstract
The matrix elements of the spin-orbit interaction and the intensities of the T←S transitions resulting from possible perturbing processes in glyoxal and its halogen substituted derivatives are examined. The calculated results show that the T←S transitions in these molecules borrow their intensities predominantly from the 1Bu(π,π*)←1Ag and 3Bg(n,π*)←3Au transitions by means of the first-order spin-orbit interaction. An experimental study of the T←S absorptions of haloderivatives of glyoxal shows that the intensity increases with an increase in the atomic number of the halogen atom. This intensification due to halosubstitution can be interpreted in terms of two factors; (1) the halosubstitutional effects on the transition energies and on the intensities of these two perturbing transitions, and also on the transition energy of the T←S transition, and (2) the halosubstitutional effect on the matrix element of the spin-orbit interaction, which comes to involve the one-center term on the halogen atom if slight delocalizations of the n-orbital as well as of the π-orbital over the halogen atom are taken into account.
Semi-Empirical SCF MO Treatment for Valence Electron Systems. Electronic Structures of trans- and cis-Isomers of Butadiene, Acrolein, and Glyoxal
Authors: Kato Hiroshi , Konishi Hideyuki , Yamabe Hiroko , Yonezawa Teijiro 
Published: July 2006

Abstract
Using a semi-empirical ASMO SGF method for all valence electron systems, but a method modified to include one-center exchange integrals and an off-diagonal core integral as estimated by the approximation in our previous treatment, the electronic structures of trans- and cis-isomers of butadiene, acrolein, and glyoxal are calculated. The energy sequence of the molecular orbitals, the charge distributions in lone-pair orbitals and π MO’s, and the charge distribution in these compounds are investigated. The n–π* and π–π* transition energies are also presented; the agreement between the calculated and observed values is almost entirely satisfactory. Further, the singlet-triplet oscillator strength in the trans-glyoxal is estimated by means of the obtained results.
The Measurement of Surface Excess Oxygen of Nickel Oxide Catalysts by Reduction with Hydrazine
Authors: Uchijima Toshio , Takahashi Masamichi , Yoneda Yukio 
Published: July 2006

Abstract
The method for the determination of the surface excess oxygen of oxides has been provided by using aqueous hydrazine solution as a reducing reagent and applied to several pure and lithium doped nickel oxide catalysts, calcined at various temperatures from 350 to 900°C. Two different kinds of procedures, i. e., titration of the amount of hydrazine consumed and volumetric measurement of gaseous nitrogen evolved, have been employed. A satisfactory agreement is obtained between both methods, which affirms that the following reaction is taking place.
N2H4+2O(S)→N2+2H2O
The amount of the surface excess oxygen decreases monotonously with increasing calcination temperature and also with increasing concentration of the lithium oxide additives. From comparison of these results with those due to acidic chloride and iodide methods, most of the excess oxygen is concluded to exist on the surface of the oxides and, furthermore, a certain distribution in the oxidation power of the excess oxygen is suggested to exist.
The C-C Bond Rupture in the Radiolysis of Liquid n-Hexane
Authors: Shinsaka Kyoji , Shida Shoji 
Published: July 2006

Abstract
The effects of added N2O, NO, N2O-NO mixture and NH3 on the yields of fragment products of n-hexane in the γ-radiolysis of liquid n-hexane at 40°C have been investigated. All of these additives decrease to a certain extent the G-values of fragment products. The decreases of the G-values at sufficiently high N2O concentration (∼0.3 mol/l) are approximately the same as those in the presence of NH3. The degrees of contribution of neutralization process and other processes to the C-C bond rupture have been separately estimated from the decreases at sufficiently high concentration of N2O, NO and N2O-NO mixture. It is shown that processes other than neutralization may play rather an important role than neutralization in the C-C bond rupture. The effect of added NH3 on the yields of fragment products of n-hexane may be attributable to either the proton transfer from n-C6H14+ to NH3 or the charge transfer from n-C6H14+ to NH3.
A Spectrophotometric Study of the Thorium Complex of 2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-mandelic Acid
Authors: Miyata Haruo 
Published: July 2006

Abstract
2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-mandelic acid forms a stable violet complex with thorium ion at 1:1 molar ratio in an acidic solution. The acid dissociation constants of the reagent and the apparent stability constant of its thorium complex were estimated spectrophotometrically at 25°C and μ=0.1. It was found that the thorium complex formed by the present reagent was more stable than those of the other phenyl-azo-chromotropic acid derivatives reported in the preceding papers.
Studies of Mixed Cyano Cobalt(III) Complexes. III. Some Cis Isomers of Monocyanobisethylenediamine Series
Authors: Ohkawa Kuwako , Hidaka Jinsai , Shimura Yoichi 
Published: July 2006

Abstract
Five new cis isomers of the [Co(X)(CN)en2]n+ complexes, namely, those of X=NH3, OH2, OH−, I− and NO2−, have been prepared and resolved into their optically active isomers. A new trans isomer of X=NO2− has also been prepared. The splitting of the d→d absorption bands of the geometrical isomers of the [Co(X)(CN)en2]n+ complexes have been discussed in reference to their visible and ultraviolet absorption spectra, rotatory dispersion and circular dichroism spectra.
Synthetic Studies Starting from β-Cyanopropionaldehyde. IV. Reactions of β-Cyanoacrolein
Authors: Satsumabayashi Sadayoshi , Motoki Shinichi 
Published: July 2006

Abstract
The reactions of β-cyanoacrolein or its dimethyl acetal were investigated. Various new compounds were prepared by the application of several basic reactions, namely, oxidation, reduction, addition, and others. Moreover, β-cyanoacrolein was found to react as a dienophile or as a diene in Diels-Alder reactions. In the reaction with butadiene, isoprene, and 1, 3-pentadiene, cyanotetrahydrobenzaldehyde derivatives were obtained. When ethyl vinyl ether or butyl vinyl ether was used as a dienophile, dihydropyran derivatives were prepared; this pyran was hydrolyzed with dilute hydrochloric acid to 2-cyanoglutar aldehyde.
On the Formation of Benzonitrile from Benzaldehyde and Ammonia. II. Iodine as an Oxidant
Authors: Misono Akira , Osa Tetsuo , Koda Seiichiro 
Published: July 2006

Abstract
The present authors previously reported a method of synthesizing nitriles from aldehydes by using iodine as an oxidant (Bull. Chem. Soc. Japan, 39, 854 (1966)). The possible route and detailed conditions of this reaction have now been investigated in the case of benzaldehyde; the results will be described in this paper. Benzaldehyde, ammonia, and iodine in methanol react to form benzonitrile and methyl benzoate as the main products. A possible reaction mechanism is suggested by a consideration of the effect of the temperature and of the concentrations of the reactants, and of the effect of the addition of ammonium iodide and water, as well as by a consideration of the results of the reaction starting from hydrobenzamide. The mechanism may be as follows. Iodamine, which is in equilibrium with iodine and ammonia, oxidizes benzilideneimine, which arises from the reaction between benzaldehyde and ammonia to give hydrobenzamide, to produce benzonitrile. Methyl benzoate is produced by the oxidation of the hemiacetal which arises from the reaction between benzaldehyde and methanol. Gyaphenin (2, 4, 6-triphenyl-1, 3, 5-triazine) is found as a by-product, but it is shown not to be produced by the trimerization of benzonitrile.
Kinetic Studies of the Photoreaction of Benzophenone with Furan
Authors: Toki Susumu , Sakurai Hiroshi 
Published: July 2006

Abstract
The photoreaction of benzophenone with furan was studied kinetically in a benzene solution. A reaction mechanism was proposed, and the rate constants of elementary reactions were determined. Benzophenone gives primarily oxetane with furan through the n-π* lowest triplet state. Benzophenone reacts with the oxetane initially formed to afford a 2 : 1-adduct or to decompose that to the starting materials. The ratio of the addition to the decomposition is 1 : 4. The simplest scheme for the direct cycloaddition of a benzophenone triplet and an alternate scheme involving a biradical intermediate are discussed; the second scheme is more acceptable. The rate of the formation of the intermediate is considerably slower in a benzophenone-furan system than in a benzophenone-ketenimine system (ca. 1/10). The formation of oxetane is greatly dependent on the ratio of the bond-forming to the bond-breaking of the biradical intermediates, which are efficiently formed (4.2×107 m−1 sec−1 for furan and 4.0×107 m−1 sec−1 for oxetane).
Über die Darstellung einiger 5-Oxo-2-methyl-4, 4-dialkyl-3-äthoxycarbonyl-4, 5-dihydroindol und deren Reduktionen
Authors: Suehiro Tadashi , Sugimori Shigeru 
Published: July 2006

Abstract
Direkte 4-Alkylierung von 5-Hydroxy-2-methyl-3-äthoxycarbonylindol (I) verläuft mit Cinnamylchlorid ausser mit Benzyl- und Allyl-chlorid, aber nicht mit Benzyloxymethylchlorid, Chloracetonitril, Bromessigester und Bromacetal. 4-Allylindol-Derivat IIb lässt sich auch durch Claisen-Umlagerung von 5-Allyloxyindol-Derivat IIIa herstellen. In Kombination der C-Benzylierung, C-Allylierung und der katalytischen Hydrierung mit der Claisen-Umlagerung kann man einige 5-Oxo-2-methyl-4, 4-dialkyl-3-äthoxycarbonyl-4, 5-dihydroindole IV darstellen. Beim Erhitzen von 5-Oxo-4, 4-diallyl-Verbindung IVb findet eine Umlagerung in 5-Hydroxy4, 6-diallyl-Derivat IIe statt, dessen Struktur synthetisch festgestellt wurde, während beim 5-Oxo-4,4-dibenzyl-Derivat IVa eine Benzyl-Gruppe unter Aromatisierung abgespaltet wird. Katalytische Hydrierung und Natriumborhydrid Reduktion von IV wurden mit einander vergleichend untersucht.
Silent Discharge Reactions in Aqueous Solutions. IV. Systems of Ferrous-Cupric Ions and Ceric-Thallous Ions Acidified with 0.8 n Sulfuric Acid in Helium and Argon Atmospheres
Authors: Yokohata Akira , Tsuda Satoru 
Published: July 2006

Abstract
In this series of studies of silent discharge reactions, the G values of the hydrogen atom,, the hydroxyl radical and hydrogen peroxide have successfully been determined in terms of the radiolysis of water by slow electrons: G(H)=1.1, G(OH)=1.6, and G(H2O2)=1.0 in helium, and G(H)=0.6, G(OH)=0.7 and G(H2O2)=1.5 in argon. Also, the absorbed dose has been estimated. In order to obtain further information regarding the nature of these radicals and the adequacy of these G values, the ferrous-cupric ions system and ceric-thallous ions system in atmospheres of helium and argon have now been investigated. The experimental results show that Gobs(Fe3+) in a ferrous-cupric ion system and Gobs(Ce3+) in a ceric-thallous ion system almost coincide with Gcalc(Fe3+) (=2G(H2O2)+G(OH)–G(H)) and Gcalc(Ce3+) (=2G(H2O2)+G(OH)+G(H)), as was to be expected from the previously determined G values. These findings suggest that the silent discharge reaction in these systems can be well interpreted in terms of the scavenging effect of cupric ions and thallous ions on the hydrogen atom and the hydroxyl radical, as in the case of radiation chemistry. Further, the present study has confirmed that the G values determined in the earlier experiment are reliable.
An ESR Study of the Aromatic-compounds-photosensitized Decomposition of Alcohol by the Two-photon Process
Authors: Shimokoshi Kazuo , Mori Yuji , Tanaka Ikuzo 
Published: July 2006

Abstract
ESR techniques were used to examine the photosensitized decomposition of solvents in a system composed of α-naphthol and its derivatives, diphenylamine, tetraphenyl hydrazine, and diphenyl methane in methanol, EPA, and ethanol at 77°K. The effects of intermittent irradiation and incident light intensity were investigated mainly in the system composed of α-naphthol in methanol at 77°K. The lifetime of the lowest triplet state of α-naphthol was determined by the intermittent irradiation, with some kinetic considerations; it agreed reasonably well with the values obtained by the direct measurement of the phosphorescence. The rate of the radical formation was found to be nearly proportional to the square of the light intensity. From these results, it was concluded that T-T* absorption in these sensitizers played an important role in forming the radicals from alcohols. The inter-molecular triplet-triplet energy transfer process was also confirmed in a system composed of a mixed alcoholic solution of phenanthrene and naphthalene at 77°K.
The Electronic and ESR Spectra of Triphenylmethane Adsorbed on Solid Acid Catalysts
Authors: Arai Hiromichi , Saito Yasukazu , Yoneda Yukio 
Published: July 2006

Abstract
The electronic spectra of adsorbed triphenylmethane have been observed through a study of disk samples made by the compression method from ordinary powder catalysts. Three kinds of adsorbed species of triphenylmethane were obtained for silica-alumina. The band at 265 mμ was due to a physically adsorbed species (Ph3CH). A new band at 340 mμ was assigned to the triphenylmethyl radical (Ph3C·), formed in the absence of air, with a sharp spectrum (g=2.004) observed in the electron spin resonance. The species of the bands at 408 and 435mμ was identified as triphenylcarbonium ion (Ph3C+), the amount of which increased with the light and temperature exposure period. Types of acid present on silica-alumina, alumina, silica, and other catalysts were discussed.
Electric Conductivity and Viscosity Studies of Aqueous Solutions of Nitroamminecobalt(III) Complexes
Authors: Tamamushi Reita , Isono Toshiaki , Katayama Shunzo 
Published: July 2006

Abstract
The ionic equivalent conductivities at infinite dilution, viscosity B-coefficients, partial molal volumes, and ionic radii of nitroamminecobalt(III) complex ions have been determined in aqueous solutions at 25 °C. From the conductivity data, the thermodynarnic association constants of the polyvalent complex cations with chloride ions have been calculated. The log K values at 25°C are 1.5 for [Co(NH3)6]3+–Cl− and 1.3 for [Co(NO2)(NH3)5]2+–Cl− respectively. Some factors, which will determine the B-coefficients of complex ions, have been briefly discussed.
The Oxidation of the Methyl Group at C-5 in Friedelin and Shionone
Authors: Fukuda Toshio , Tsuyuki Takahiko , Tanahashi Yoshiaki , Takahashi Takeyoshi 
Published: July 2006

Abstract
3β-Friedelanol (V, R=H) and 3β-shionanol (VIII, R=H) have been converted into γ-lactones, (VI) and (IX) respectively, either by lead tetraacetate-iodine oxidation followed by Jones’ oxidation or by photolysis of their nitrites (V, R=NO and VIII, R=NO) followed by Jones’ oxidation. These results confirm the presence of an axial methyl group at C-5 in friedelin (II) and shionone (I).
α-Pyrone-6-carboxylic Acid Derivatives. IV. Optical Resolution and Configuration of Stizolobic Acid, Stizolobinic Acid and β-(6-Carboxy-α′-pyron-5-yl)alanine Lactam
Authors: Senoh Siro , Maeno Yoshiko , Imamoto Shoji , Komamine Atsushi , Hattori Shizuo , Yamashita Kyohei , Matsui Masanao 
Published: July 2006

Abstract
The optical resolution of three isomers of Dl-β-(6-carboxy-α′-pyronyl)alanine was carried out by chemical as well as enzymatic methods and six optically active isomers were obtained. The configuration of each aspartic acid, derived from the ozonolysis of these optical isomers in aqueous solution, was analyzed enzymatically using glutamic-oxaloacetic transaminase and malate dehydrogenase. By the same procedure, the configuration of the two natural amino acids, stizolobic acid and stizolobinic acid, was confirmed and both were assigned the L-form. Thus the absolute configuration of six optical active isomers of β-(6-carboxy-α′-pyronyl)alanine and the two natural amino acids is assigned unequivocally, and the relationship between the synthetic and the natural amino acids is established.
The Photo-Ionization of Molecules in Solutions. IV. Electron Capture and Charge Transfer Fluorescence Phenomena Occurring between N, N, N′, N′-Tetramethyl-p-phenylenediamine and Electron Acceptors in Organic Solvents
Authors: Yamamoto Naoto , Nakato Yoshihiro , Tsubomura Hiroshi 
Published: July 2006

Abstract
A mixture of N, N, N′, N′,-tetramethyl-p-phenylenediamine (TMPD) and pyrene in some rigid matrices was illuminated at a low temperature in the near ultraviolet region. It was found that TMPD+, pyrene anion, and solvated electrons are formed in the medium. The ratio of the formation of pyrene anion and TMPD+ has been studied at various concentrations of pyrene. The behavior of the photo-ejected electron, particularly its extent of migration has then been discussed on the basis of the experimental results. The thermoluminescence spectrum of the UV-irradiated matrix containing TMPD and pyrene was measured after it had been illuminated in the infrared region. The luminescence may tentatively be assigned to the charge transfer fluorescence. The emission spectra were investigated for a mixture containing TMPD and α-methylnaphthalene in several solvents by exciting the TMPD. It was found that a new emission band appeared at 480 mμ. It was assigned to the charge transfer fluorescence.
Electronic Structures and Reactivities of Aliphatic Small-Membered-Ring Compounds. I
Authors: Yonezawa Teijiro , Shimizu Kiyoshi , Kato Hiroshi 
Published: July 2006

Abstract
Extended LCAO MO investigations into the physico-chemical properties of cycloalkanes and their derivatives are carried out. The bond natures of C–C and C–H in cycloalkanes, the electronic distributions of the lowest vacant orbital, the electron-attracting powers of the ring, and the relative reactivity of the ring cleavage are successfully explained. Further, their ionization potentials and electron affinities are discussed. In addition, the electronic distributions on the equatorial and axial forms of monosubstituted cyclobutane and cyclohexane are made explicit.
Studies of the Photochemistry of Aromatic Diazo Compounds. I. Electronic Structure and Photodecomposition of Benzenediazonium Salt
Authors: Sukigara Mitsunori , Kikuchi Shin-ichi 
Published: July 2006

Abstract
The electronic states of benzene diazonium cation were calculated by a method similar to that of Pariser and Parr. On the basis of the calculations, the 259 mμ and 295 mμ absorption bands were attributed to 1A1–1A1 and 1A1-1B1 transitions respectively. When the sample was irradiated in an alcoholic solution by a 295 mμ light, no ESR signal was detected, but fluorescence and phosphorescence were observed; the fluorescence and the absorption spectrum of 1A1–1B1 transition have the correlation of a mirror image to each other. On the other hand, upon irradiation by a 259 mμ light, this sample showed an ESR spectrum which was attributed to the phenyl σ-radical, but no fluorescence or phosphorescence was observed. From the above experimental results and theoretical considerations, it was concluded that the electronically-excited benzenediazonium salt releases its excess energy by the following processes: (1) From the excited 1B1 state, there occur radiative transition to the ground state and intersystem crossing to the phosphorescent state, though it is as yet uncertain whether 3B1 or any other triplet states are involved. The photodecomposition does not proceed from the excited 1B1 state. (2) From the excited 1A1 state, neither the radiative transition to the ground state nor a nonradiative transition to any fluorescent or phosphorescent states occurs. The molecule decomposes rapidly to give phenyl σ-radical after excitation to this electronic state.
Phase Transitions in Poly-n-Alkyl Methacrylate Monolayers
Authors: Nakahara Tatsuo , Motomura Kinsi , Matuura Ryohei 
Published: July 2006

Abstract
The effects of temperature on the surface pressure of monolayers of polymethacrylates with n-alkyl groups containing from 9 to 18 carbon atoms have been studied. Two kinds of phase transitions have been observed in the surface pressure-area isotherms. On the basis of the bulk properties of the polymers, these phase changes have been interpreted as the transition of the monolayer to a three-dimensional fluid state and as side-chain crystallization.
Chlorine Nuclear Quadrupole Resonance Study of the Molecular and the Ionic Crystals of Phosphorus Pentachloride and the Phase Transitions in and between the Two Crystalline Modifications
Authors: Chihara Hideaki , Nakamura Nobuo , Seki Syûzô 
Published: July 2006

Abstract
The 35Cl quadrupole resonance (NQR) spectra in both the molecular (PCl5) and the ionic (PCl4+·PCl6-) solid modifications were measured and assigned, and their temperature dependences (20 to 250°K) were interpreted by a modified Bayer theory. A phase transition of higher order occurs in the ionic solid at 102.3°K which was also revealed by a preliminary heat capacity measurement: There are seven resonance lines below 102.3°K and four above it. An anisotropy in the librational motion is suggested. The molecular solid modification is metastable and transformation into the ionic solid occurs over a range of temperature. This was observed both in the quadrupole resonance spectrum and in the differential thermal analysis; the latter was used to derive the apparent activation energy for the disproportionation reaction. A phase transition occurs also in the molecular solid at 183°K. The partial ionic character of the P-Cl bonds in the two modifications was estimated from the NQR results and could account for the observed chemical shift in the nuclear magnetic resonance of 31P. The 35Cl resonance frequencies in a family of compounds PXn were correlated.
The Crystal Structure of trans-Diaquo-bis(pyridine-2-carboxamide)-nickel(II) Chloride, [Ni(H2O)2(piaH)2]Cl2
Authors: Masuko Akiyoshi , Nomura Teruo , Saito Yoshihiko 
Published: July 2006

Abstract
The crystal structure of trans-diaquo-bis(pyridine-2-carboxamide)nickel(II) chloride, [Ni-(H2O)2(piaH)2]Cl2, was determined by X-ray diffraction and refined by three-dimensional least-squares method. The crystals are monoclinic with space group P21⁄a, a=13.567, b=10.067, c=6.355 Å and β=113.73°. There are two formula units in the unit cell. The structure is built up of centrosymmetric complex ions and chloride ions. Two ligand molecules are coordinated to the nickel atom in trans position with amide oxygen atoms and ring nitrogen atoms. (Ni–N, 2.02 Å, Ni–O, 2.05 Å). The ligand molecules are nearly planar and they are approximately in one plane with the nickel atom. Two water molecules are coordinated at a distance of 2.14 Å and complete the octahedral arrangement around the nickel atom.
The Changes in the Secondary Properties of Zinc Oxide in the Process of Mechanical Treatment
Authors: Takahashi Hiroshi , Tsutsumi Kazuo 
Published: July 2006

Abstract
The changes in the secondary properties of zinc oxide upon mechanical treatment were studied. In the process of the mechanical treatment of zinc oxide, the Blaine specific surface area, the sedimentation volume, and the particle size distribution changed periodically with the treatment time. Such periodical changes are characteristic of the state of association of the particles, and can be interpreted as the changes in the total energy content of the solid.