bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photochemical Reactions of Some Thioparabanates
Authors: Yonezawa Teijiro , Matsumoto Masakatsu , Matsumura Yoichi , Kato Hiroshi 
Published: July 2006

Abstract
1,3-Disubstituted thioparabanates (I) were reduced with ethanol under the action of light to yield 2-mercaptoimidazolidine-4,5-diones (II) with or without 2-(1-hydroxyethyl)-2-mercapto-imidazolidine-4,5-dione (III). It seems that these reactions may be initiated by the n–π* transition of the lone pair in the 2-thiocarbonyl group. When dimethylthioparabanate (Ic) was irradiated with a high-pressure mercury arc in a chloroform solution of amylene, a photocycloaddition product, a trimethylene sulfide (IVa), was obtained.
Studies of the Transient Intermediates of a Thiopyronine Aqueous Solution under Flash Excitation
Authors: Morita Masaharu , Kato Shunji 
Published: July 2006

Abstract
Flash photolytic studies of the transient intermediates produced in the flash excitation of an aqueous buffered solution of the photosensitizing dye “thiopyronine” were undertaken in order to obtain direct insight into the reaction mechanism of the photosensitizing action of the dye. As had been expected from the structural similarity to a well-known photosensitizer, methylene blue, previously reported on, the flash excitation of thiopyronine, in a deaerated buffered solution at pH 7.4 without any substrate, produced three transient intermediates: a triplet-state (Dt), a half-oxidized form (Oxd), and a half-reduced form or semiquinone (Red) of the dye. Red and Oxd were generated simultaneously through electron tansfer reactions, i.e., Dt+Dt→Red+Oxd and Dt+D→Red+Oxd, where D is the dye in the ground state. Thiopyronine solutions containing some reducing and oxidizing agents were studied in order to identify the intermediates. The absorption spectra of these intermediates were identified, and their reaction mechanism studied. The rate constants of some elementary processes obtained are:
Dt→k1=2.36×103sec−1
Dt+Dt→k′=7.69×108m−1sec−1
Dt+D→k″=7.69×108m−1sec−1
Red+Red→k6=(1–2)×109m−1sec−1
Oxd→k7=(1–3)×103sec−1
Dt+EDTA→k8=1.6×107m−1sec−1
Dt+ATU→k9≈small
Oxd+ATU→k10(2–5)×106m−1small
The high efficieny of thiopyrinine in its Photodynamic effect was discussed in connection with the high quantum yield of triplet-state production and the high reversibility of the high reversibility of the photochemical redox reaction of the dye.
Catalytic Vapor-Phase Ammoxidation of Substituted Toluenes over Chromium Oxide
Authors: Sakanishi Katsumasa , Ogata Yoshiro 
Published: July 2006

Abstract
Ammoxidation of substituted toluenes over a chromium oxide catalyst has been studied in a flow system at atmospheric pressure. The reactions give satisfactory yields (ca.70%) of corresponding nitriles at high conversion of toluenes. The rate constant for the reaction of substrate adsorbed on the catalyst surface, kT0, is independent of the substituent of substrate, while the adsorption equilibrium constant of gaseous substrate, KT depends on the substituent, affording Hammett’s ρ of −0.9 for σ+. These results support our mechanism reported previously for the analogous oxidation of toluene and ethylbenzene over Cr2O3, which involves an electron transfer from adsorbed hydrocarbons to dissociated oxygen.
The Bond Character of the Sn–Cl Bonds in the Hydrates of Tin (IV) Chloride
Authors: Negita Hisao , Okuda Tsutomu , Mishima Mitsuo 
Published: July 2006

Abstract
Several hydrates of tin(IV) chloride, e.g., SnCl4·xH2O (x=2, 3, 4 and 5) and SnCl4·yD2O (y=3, 4 and 5), were investigated by means of the nuclear quadrupole resonance (NQR) due to 35Cl and the Mössbauer effect due to 119Sn. The NQR-frequencies were observed at the temperature of liquid nitrogen and room temperature; they were found to range from 17.656 to 21.439 MHz. The Mössbauer effect was investigated only at the temperature of liquid nitrogen; it resulted in isomer shifts ranging from 0.275 to 0.350 mm/sec. The NQR-frequency and the isomer shift decreased with an increase in the number of water molecules in the hydrates, and the relationship between the NQR-frequency and the isomer shift was nearly linear. This relation was interpreted in terms of the transfer of the s-electrons of the tin atom to the chlorine atoms. Furthermore, it was revealed that there was a significant difference between the Sn-Cl bond of the hydrates and that of ammonium chlorostannate.
Palladium (II) Complexes of N-Substituted Salicylideneimines
Authors: Yamada Shoichiro , Yamanouchi Kuniko 
Published: July 2006

Abstract
Many new palladium(II) complexes (abbreviated as M(X-SAL·R)2) of Schiff bases obtained from substituted salicylaldehydes and alkyl and aryl amines were prepared as yellow-orange or red crystals, where X denotes H, 3-CH3O and 5,6-benzo. For R=n-alkyl and aryl groups, the complexes Pd(X-SAL·R)2 in non-donor solvents consist of square-planar molecules. The complexes of the type Pd(X-SAL·t-C4H9)2 show electronic spectra which are different from those of the complexes of the type Pd(X-SAL·n-alkyl)2, but all these complexes are diamagnetic. This difference between the two kinds of complexes is discussed in connection with the bonding in, and the structure of, the complexes on the basis of the spectral and magnetic properties. The results for the palladium(II) complexes are compared with those for the corresponding nickel(II) complexes.
The Syntheses and the Structure of Triethanolamine Complexes with Cobalt (II) and Nickel (II)
Authors: Kuge Yoshio , Yamada Shoichiro 
Published: July 2006

Abstract
Triethanolamine complexes with cobalt(II) and nickel(II) have been synthesized as crystals and examined on the basis of analytical data, electronic absorption spectra, and magnetic moments. A complex, Ni{N(CH2CH2OH)3}(ClO4)2, which is formed with Ni(ClO4)2, is concluded to have a six-coordinated configuration, similar to that previously reported for the corresponding chloride, bromide, and nitrate complexes. In cobalt(II) complexes, Co{N(CH2CH2OH)2(CH2CH2O)}X, which are formed with CoX2 (X=Cl−, Br−, or NCS−), the cobalt(II) ion is concluded to take a five-coordinated configuration.
The Cobalt Carbonyl-catalyzed Hydroesterification of 3-(β-Cyano-ethoxy)propene with Carbon Monoxide and Methanol
Authors: Matsuda Akio 
Published: July 2006

Abstract
The cobalt carbonyl-catalyzed hydroesterification of 3-(β-cyanoethoxy)propene with carbon monoxide and methanol occurred in the presence of a small amount of hydrogen at a moderate temperature, methyl 4-(β-cyanoethoxy)butyrate being produced in a much larger amount than methyl 2-methyl-3-(β-cyanoethoxy)propionate. The double-bond isomerization leading to the formation of propionaldehyde dimethylacetal and ethylene cyanohydrin occurred simultaneously. The selectivity to the double-bond isomerization was very large at a low pressure; it decreased as the pressure was increased, with a corresponding increase in selectivity to the hydroesterification. The reaction rate was not increased by the addition of pyridine, but it was increased about tenfold by the addition of palladium chloride. Thus, the reaction could be carried out at a lower temperature in the presence of palladium chloride. The selectivity to the hydroesterification, however, did not increase upon the addition of palladium chloride, as the double-bond isomerization was also accelerated by its addition.
Structure Proof of Diarylmethanes Formed in the Jacobsen Reaction of Monochlorotetramethylbenzenes
Authors: Suzuki Hitomi 
Published: July 2006

Abstract
The Jacobsen reaction of monochlorotetramethylbenzenes was found to yield dichloroheptamethyldiphenylmethanes as by-product. Their indefinite structure proof was made on spectroscopy and synthesis. 1H NMR spectra for a variety of polymethyldiphenylmethanes and their chlorine derivatives were determined.
Aminocyclitols. XX. Bromination of Dl-epi-Inositol
Authors: Suami Tetsuo , Suzuki Akira , Uchida Masaru , Yanagida Shin-ichi 
Published: July 2006

Abstract
Bromination of Dl-epi-inositol yielded two hitherto unknown dibromo-dideoxyinositols, along with two known bromo-deoxyinositols (Dl-5-bromo-5-deoxy-allo-inositol and Dl-1-bromo-l-deoxy-neo-inositol). The proton magnetic resonance spectroscopic studies of the dibromo-dideoxyinositols with the aid of spin decoupling technique established their configurations to be Dl-2,4-dibromo-2,4-didoxy-chiro-inositol and Dl-1,4-dibromo-1,4-dideoxy-chiro-inositol.
Preparation and Properties of the Mixed Dinitro Complexes of Cobalt(III) with the Carbonato or Oxalato Ligand
Authors: Ichikawa Hiroyasu , Shibata Muraji 
Published: July 2006

Abstract
Three new tervalent dinitro complexes of cobalt(III) have been prepared by the use of a tricarbonatocobaltate(III) solution or a similar solution as the starting material. These complexes, [Co(NO2)2(CO3)3]3−, [Co(NO2)2(OX)2]3− and [Co(NO2)2CO3OX]3− are characterized by their absorption spectra in solution. The geometrical structures of these complexes have been determined as of the cis-form on the basis of their IR spectra. The compounds were not stable against decomposition in aqueous solutions: the bis(oxalato) compound was most unstable against the decomposition to the Co(II) state. The stability has been discussed in connection with the specific absorption band of the coordinated NO2− ligand.
Reaction of p-Nitrophenyl Benzenesulfonates with Thiophenoxides
Authors: Tagaki Waichiro , Kurusu Takehiko , Oae Shigeru 
Published: July 2006

Abstract
The reaction of p-nitrophenyl benzenesulfonates has been investigated in dioxane-water solvent. The overall rate constant, kA, was separated into two composite rate constants, kAr, and kSO2, corresponding to the cleavage of C–O and S–O bonds respectively. The reactivities of hydroxide and thiophenoxide in this reaction were compared. The overall rate constant was found to be several times larger with OH− than with PhS−. The reactivity of OH− was largely due to its higher reactivity toward sulfur, while its reactivity toward carbon atom was comparable to that of PhS−. Substituent effect of the nucleophile, thiophenoxide and of the substrate shed some light on the mechanism of this reaction.
Reactive Species in the Explosion of Silver Acetylide. I. Reaction with Saturated Hydrocarbon
Authors: Taki Ko 
Published: July 2006

Abstract
The reactive species produced by the explosion of silver acetylide were found to react with hydrocarbon and to give acetylene and ethylene as the main products. The reactive species must be carbon oligomers. Since, in the reactions with higher hydrocarbons, acetylene and ethylene are also produced, their formation process may be the decomposition of the adduct of the reactive species. From the product distributions, the phase dependence of the ratio of ethylene to acetylene, and the effect of such moderator as carbon dioxide and inert gas, the reactive species are considered to be not only the monoatomic carbon (C1) but also the diatomic carbon (C2). The effect of a NO radical scavenger in the reactions of both ethane and propane is also described.
A Structural Study of the Catalytic Activity in Formaldehyde Polymerization in Liquid Carbon Dioxide
Authors: Kagiya Tsutomu , Narita K\={o}z\={o} 
Published: July 2006

Abstract
The catalytic activities of various acids, bases, and salts in formaldehyde polymerization in a liquid carbon dioxide solution were studied in connection with the structures of the catalysts. The activity of the catalysts increased with decreases in the pKa of Brönsted acids and in the ion-dissociation energy of alkyl acetates, and with increases in the pKa′ of organic compounds containing a nitrogen or oxygen atom, such as triethylamine or diethyl ether, and in the pKa of the conjugated acids of sodium salts. The activity of the salts obtained from a strong acid with various bases increased with a decrease in the pKa′ of the bases, while that of the salts from weak acids with weak bases decreased with an increase in the summation of the pKa values of acids and the pKa′ values of bases, reaching a minimum point and then increasing. The activity of various salts decreased with an increase in the pH in an aqueous solution, reached a minimum point at pH 6, then increased.
Photoinduced Reactions. XXXIV. Photosensitized Oxygenation of 2,4,5-Triphenylthiazole
Authors: Matsuura Teruo , Saito Isao 
Published: July 2006

Abstract
In connection with the photodynamic action of the biological systems, photosensitized oxygenation of a thiazole was investigated. Photooxidation of 2,4,5-triphenylthiazole in methanol in the presence of rose bengal resulted in the formation of benzil and benzamide. On the other hand, photooxidation of 2,4,5-triphenylthiazole in chloroform containing methylene blue as a sensitizer gave N,N-dibenzoylthiobenzamide in good yield. Possible mechanisms for these reactions, involving an endo-peroxide or a zwitterionic peroxide, are discussed.
Reactions of Diarylphosphines, Their Oxides and Sulfides with Isothiocyanates and Thiocyanic Acid
Authors: Ojima Iwao , Akiba Kin-ya , Inamoto Naoki 
Published: July 2006

Abstract
N-Substituted thiocarbamoyldiarylphosphine oxides and sulfides were prepared by the addition reaction of diarylphosphine oxides and diphenylphosphine sulfide with isothiocyanates. Diarylphosphine oxides and diphenylphosphine reacted with ammonium thiocyanate under hydrogen chloride stream to produce diarylphosphinyl- and diarylthiophosphinyl-substituted bis(iminomethyl) sulfides, which are a new type of sulfide. Diphenylphosphine also reacted with thiocyanic acid in ether to give thiocarbamoyldiphenylphosphine and bis(diphenylphosphinyliminomethyl) sulfide. Mechanisms for formation of these bis(iminomethyl) sulfides have been discussed.
The Structure Theory of Water. I. Two State Theory
Authors: Arakawa Kiyoshi , Sasaki Katsutaka 
Published: July 2006

Abstract
A statistical thermodynamic theory was successfully applied to liquid water, based on the two state model which consists of an ice-like structure (class I) and unbonded monomers (class II). The resulting partition function was formulated and calculated using the two quantities, the energy difference between class I and class II, ε, and the free volume per molecule, vf, as the adjustable parameters which were varied within the physically-reasonable range. The magnitudes of ε and vf were estimated to be 3 kcal/mol and 4.0×10−25 cm3 respectively to give the best fit of calculated values to the experimental data. From the partition function obtained, the Helmholtz energy, the internal energy, the entropy, and the specific heat were calculated. The agreement between the calculated values and the experimental data was found to be satisfactory. From the obtained result it may be concluded that the simple two state model is adequate to explain the thermodynamical data for liquid water.
Measurement of Negative Ions Formed by Electron Impact. V. Negative Ion Mass Spectra and Ionization Efficiency Curves of Negative Ions of m⁄e 16, 25 and 41 from Tetrahydrofuran
Authors: Tsuda Satoru , Yokohata Akira , Kawai Michihiro 
Published: July 2006

Abstract
The negative ion mass spectra of tetrahydrofuran, with an emphasis on their relative abundances to the positive ions under 80 eV and 40 eV electron energies, and the ionization efficiency (IE) curves of m⁄e 16(O−),m⁄e 25(C2H−) and m⁄e 41(C2HO−) ions to the extent of 40 eV electron energies were measured. The electron impacts of 80 eV and 40 eV gave almost the same distribution of m⁄e for negative ion mass spectra. The relatively strong peaks were observed at m⁄e 24(C2−) ions for 80 eV and m⁄e 14(CH2−) ions for 40 eV, besides the commonly strong peaks of m⁄e 25(C2H−), m⁄e 16(O−) and m⁄e 41(C2HO−) ions. The comparison of the yield of C2H− ions with that of C3H6+ gave the values 9.4×103 and 2.7×104 for C3H6+/C2H− at 80 eV and 40 eV electron energies, respectively. The reaction schemes expected to occur at each onset observed in the IE curves were also discussed. It is of interest to note that C2H− ions are not obtained in the range of low energy of electrons, but become observable at ∼23.5 eV.
The Catalytic Activity of Onium Compounds in the Homogeneous Liquid Phase Oxidation of Cumene and α-Pinene
Authors: Fukui Kenichi , Ohkubo Katsutoshi , Yamabe Tokio 
Published: July 2006

Abstract
The catalytic activity of onium compounds was studied in the homogeneous liquid phase oxidation of cumene and α-pinene. The onium salts, particularly sulfonium, phosphonium, selenonium, arsonium and telluronium were found effective. This result is connected to the fact that the central atom in these onium has vacant d orbitals. Among the anions of the onium salts tested, phosphate and sulfate were most effective. The aryl substituents in the central sulfur in sulfonium lessened the activity, while alkyl substituents made it greater. These facts were attributed to charge migration from the substituents and the anionic part to the central atom.
On the Viscosity of Liquid Oligotrifluorochloroethylene
Authors: Yoshida Naosato , Hamada Shuichi , Shirai Toshiaki 
Published: July 2006

Abstract
The viscosities and densities of liquid oligotrifluorochloroethylene were measured over a molecular-weight range from 820 to 1090 at temperatures from 40°C to 100°C. The temperature dependences of the viscosities did not show an Arrhenius-type variation, but were extremely adaptable in the WLF equation; i. e., a viscoelastic behavior was shown under the present experimental conditions. The apparent activation energies, ΔHa, for the viscous flow of the liquid samples were comparatively large and increased with an increase in the number-average molecular weight. The logarithm of the viscosity, logη, varied linearly with the logarithm of the number-average molecular weight, logη=AlogMn+B. The slopes, A, of the linear relationships were estimated to be 11.0, 10.4, 9.3, and 8.4 at 50, 60, 70, and 80°C respectively. The values of the slopes, A, were very much larger than unity in the case of usual organic polymers below the critical values of the molecular weight, and they decreased with an increase in the temperature.
Infrared Study of Rotational Isomers of meso- and racemic-2,3-Dibromobutane
Authors: Iimura Kazuyoshi 
Published: July 2006

Abstract
The infrared spectra of meso- and racemic-2,3-dibromobutanes in solution and in gaseous states were obtained in the study of the rotational isomers. The occurrence of three rotational isomers was confirmed for both meso- and racemic-isomers. The quantitative estimation of the equilibrium concentrations of the rotational isomers was also made in various solvents. The energy difference between the rotational isomers was determined by measuring the temperature-dependence of the absorption intensities of v(C–Br) vibrations.
Polarographic Study of Metal Complexes. VIII. Dicyanobis-(ethylenediamine) cobalt(III) Complex with a cis-Configuration
Authors: Maki Nobufumi , Yamamoto Kouei , Sunahara Hiroshi , Sakuraba Shukichi 
Published: July 2006

Abstract
In an aqueous solution containing an excess of ethylenediamine, i. e., under the conditions where the aquation is prevented, the dicyano-cobalt(III) complex, cis-[Co(CN)2en2]NO3, has been found to be reduced in three steps at the dropping mercury electrode (DME). The first step, corresponding to the acceptance of one electron, represents the reduction from the cobalt(III) to the cobalt(II) state, while the second and the third step were interpreted as being due to the reduction of two kinds of the cobalt(II) species formed by the overall rearrangement of ligands in solution. One such kind of cobalt species is the binuclear tetracyanocobaltate(II) complex, [Co(CN)4-en-Co(CN)4]4−, which is reduced to the metal through the cobaltate(I) complex, while the other is the cobalt(II) complexes with ethylenediamines in an equilibrium state, which are reduced directly to the metal at the DME. Namely, the second step represents the reduction from the cobalt(II) complex of the former to the cobalt(I) state, while the third step, denoting the reduction to the metal, was observed only on the dE⁄dt-E curve of the oscillopolarogram, but not on the current-potential curve due to the maximum wave. In the non-aqueous solution of dimethyl sulfoxide, the dicyano-cobalt(III) complex, cis-[Co(CN)2en2]ClO4, undergoes the step-by-step reduction of Co(III)→Co(II)→Co(I)→Co(0), as it were, at the DME. Neither aquation nor rearrangements of ligands take place throughout reductions under these experimental conditions, that is, even in lower oxidation states of the cobalt.
On the Oxidation of Guaiazulene
Authors: Kohara Kazuko 
Published: July 2006

Abstract
Guaiazulene was oxidized with potassium permanganate and with selenium dioxide according to the Treibs procedure. An acidic and a neutral crystalline compounds obtained from the permanganate oxidation in acetone were identified by means of UV, IR, and NMR spectrum measurements as 4-methyl-7-isopropylazulene-1-carboxylic acid and 1-formyl-4-methyl-7-isopropylazulene respectively. It was also confirmed that the selenium dioxide oxidation of guaiazulene in acetone gave 3-formylguaiazulene and 3,3′-diguaiazulenylacetone, the chemical structure of which had already been established by Treibs.
Homolytic Chlorination of Aliphatic Compounds. II. Photochlorination of Aliphatic Nitriles
Authors: Kosugi Masanori , Takeuchi Kohji , Migita Toshihiko 
Published: July 2006

Abstract
Acetonitrile, propionitrile, n-butyronitrile and pivalonitrile were photochlorinated competitively at 40°C in the presence of an appropriate chlorinated ethane, and relative amounts of the chlorinated products were determined by v.p.c. From the results the relative reactivities of C-H bonds toward hydrogen abstraction by chlorine atom were estimated. A linear free energy relationship was observed between σ* value of X and the reactivity of CH3–X toward chlorination (X: –CN, –CH2CN, –CH2CH2CN, –CMe2CN). This indicates that cyano group will affect the reactivities of these C-H bond through its inductive effect.
Energy Transfer from the Triplet Excited States of Aromatic Molecules to Chromium(III) Complexes
Authors: Ohno Takeshi , Kato Shunji 
Published: July 2006

Abstract
The quenching efficiencies of five tervalent chromium complexes on the phosphorescence of erythrosin and benzil have been compared at the temperatures of dry ice and liquid nitrogen. The results were well explained in terms of the collisional energy transfer. It was observed that aromatic ligands enhanced the rate of the energy transfer even if the triplet energy of the donor was lower than that of the ligands.
Effect of γ-Preirradiation on Catalytic Activity of Nickel Oxide for the Oxidation of Carbon Monoxide
Authors: Tezuka Yoshisato , Takeuchi Toyosaburo 
Published: July 2006

Abstract
The change in NiO catalytic activity upon the variation in the irradiation of γ-rays in the presence of O2 gas was studied. Activities were determined for the reaction of CO with NiO and for the oxidation reaction of CO on NiO. The results showed a decrease in the CO-NiO reaction rate with an increase in the irradiation of NiO, particularly in the absence of oxygen; if the irradiation was more than 7×107R, the reaction rate increased as both the irradiation in the presence of oxygen and the oxygen partial pressure increased. The activity change in NiO was explained by assuming the migration of the specially-active oxygen into the oxide bulk by means of the irradiation of γ-rays.