bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Preparation and Stereochemistry of Optically Active Cobalt(III) Complexes with 3,3′-Dimethyl-2,2′-bipyridine and Bis(diamines) or Tetramines
Authors: Suzuki Toshishige M , Kimura Tetsuo 
Published: July 2006

Abstract
Bis(en), trien, tren and bis(R,R-chxn) cobalt(III) complexes of 3,3′-dimethyl-2,2′-bipyridine (dmbpy) have been prepared and resolved. The dissymmetric conformation of dmbpy arising from the non-coplanarity of the two pyridine rings is maintained in the inert complexes. 3,3′-Dimethyl-2,2′-bipyridine coordinates to the cobalt(III) ion with a stereospecific conformation depending on the configuration. The absorption and circular dichroism (CD) spectra of the dmbpy complexes were compared with those of the corresponding 2,2′-bipyridine (bpy) complexes.
Spectral Studies on the Interaction between Oxovanadium(IV) β-Diketonates and Organic Solvents
Authors: Adachi Natumi , Fukuda Yutaka , Sone Kozo 
Published: July 2006

Abstract
The effect of temperature on the visible absorption spectra of oxovanadium(IV) β-diketonates [VO (β-dik)2] (β-dik=aca, bza, tfa, and dpm*) were studied in organic solvents. The results together with the spectral and thermogravimetric data of the pyridine and dioxane adducts of these chelates lead to the conclusion that the ease of taking up a solvent molecule to form a six-coordinate solvated chelate in solution increases in the order: VO(tfa)2&gt;VO(bza)2≈VO(aca)2&gt;VO(dpm)2. Various proofs for the existence of a polymeric structure of VO(tfa)2, which was formerly indicated on the basis of its IR spectrum, were found.
12,13-Epoxy-C-nor-D-homosteroids. III. The Synthesis and Stereochemistry of 17-Oxygenated 12,13-Epoxyetiojervanes
Authors: Murai Akio , Iwasa Noriaki , Takeda Masami , Sasamori Hiroshi , Masamune Tadashi 
Published: July 2006

Abstract
The synthesis of several 17-oxygenated 12,13-epoxyetiojervanes is described. Jervine (1) was degraded by a known procedure into trienone (10), which on hydride reduction afforded 11α- and 11β- alcohols (11 and 12). The respective alcohols were submitted to the Lemieux-Johnson oxidation to give Δ12-17-oxo-11-alcohols (13 and 14), which were reduced under the Birch conditions to yield Δ12-17-ketone (15). Epoxidation of these alcohols and ketone produced the aimed epoxides (18–24). The structure and configuration of these epoxides and the synthetic intermediates were determined on the basis of the chemical and spectral evidence.
Fluorination with Substituted (Difluoroiodo)arenes
Authors: Gregorcic Ana , Zupan Marko 
Published: July 2006

Abstract
The reaction of substituted (difluoroiodo)arenes with 1-phenyl-1-(m-chlorophenyl)ethylene results in 1,1-difluoro-1-(m-chlorophenyl)2-phenylethane, with 1-phenyl-1-(p-methoxyphenyl)ethylene in 1,1-difluoro-1-phenyl-2-(p-methoxyphenyl) ethane, and with 1-phenylcyclopentene and 1-phenylcyclohexene in rearranged gem-difluoro compounds. The reaction with norbornene results in three products: fluoronortricyclane (9–12%), 2-exo-7-syn-difluoronorbornane (75–86%), and 2-exo-7-anti-difluoronorbornane (5–15%) depending upon the substituent on the phenyl ring in (difluoroiodo)arenes.
The Reactions of β-Amino Enones with Hydroxylamine
Authors: Kashima Choji , Yamamoto Yasuhiro , Omote Yoshimori , Tsuda Yoshihiko 
Published: July 2006

Abstract
The reactions of N-substituted β-amino enones with hydroxylamine give two isoxazole isomers. The ratio of these isomers changes with the electron-withdrawing effect of the N-substituents.
The Palladium-catalyzed Phenylation of Enol Esters with Iodobenzene
Authors: Kasahara Akira , Izumi Taeko , Fukuda Naoki 
Published: July 2006

Abstract
The palladium-catalyzed phenylation of olefins with iodobenzene has been extended to enol esters. In the presence of triethylamine and a catalytic amount of palladium acetate, vinyl acetate is phenylated with iodobenzene to produce, mainly, stilbene, accopanied by small amounts of (E)- and (Z)-styryl acetates.
Magnetic Properties of Oxovanadium(IV) Complexes with Bidentate ON Donor Schiff Bases
Authors: Syamal A 
Published: July 2006

Abstract
The magnetic properties of oxovanadium(IV) complexes of Schiff bases(I) are reported. Contrary to an earlier report that these complexes are involved in magnetic exchange, the complexes are found to be magnetically dilute. The complexes display μeff in the range 1.68–1.71 B. M. at 78–297 K with θ=2–4 K, and exhibit 8 line ESR spectra.
Statistical Thermodynamic Theory of Liquid Water
Authors: Arakawa Kiyoshi , Tokiwano Kazuo , Kojima Kazumitsu 
Published: July 2006

Abstract
A new statistical thermodynamic theory is presented for a model of liquid water, which consists of two components, i.e., tetrahedrally-coordinated pentamers and non-hydrogen-bonded monomers. In the model the two components are assumed to be immersed in a uniform background potential which results from electrostatic, induction, and dispersion forces between water molecules. A partition function is given without assuming any specified lattice. A translational partition function is written into a simple and explicit expression which is derived from the Lebowitz solution of the Percus-Yevick equation for hard sphere mixtures. The mole fraction of each component and the density are determined by solving two equations, i.e., the condition of free energy minimization and the equation of state derived from the partition function, simultaneously. Various thermodynamic quantities are calculated and the values determined are compared with those observed. Some discussions are carried out, together with the criticism of the earlier theories.
The Liquid-phase Oxidation of Acetaldehyde with Metal Polyphthalocyanines. Solvent Effect
Authors: Ohkatsu Yasukazu , Hara Takao , Osa Tetsuo 
Published: July 2006

Abstract
Acetaldehyde was oxidized using metal polyphthalocyanines as catalysts. Metal polyphthalocyanines, especially Fe,Cu–polyphthalocyanine, were found to be useful oxidation catalysts for the selective formation of peracetic acid from acetaldehyde. The rate of oxidation was much affected by the nature of the solvents. The solvent is considered to take part in the initiation oxidation reaction in two ways: one is based on the prevention of the oxygen molecule from coordination with a metal polyphthalocyanine and subsequent activation, and the other is due to the solvation with the activated oxygen molecules on the catalyst. Preferable solvents were ethyl acetate, bromobenzene, benzene, and acetone.
The Reaction of 4-Thiazoline-2-thione with Methyl Iodide. Solvent Effects and Pressure Effects
Authors: Kondo Yasuhiko , Shinzawa Masayuki , Tokura Niichiro 
Published: July 2006

Abstract
Rate constants for the reaction of 3-isopropyl-4-methyl-4-thiazoline-2-thione with methyl iodide have been determined in several solvents at 1 atm. In acetonitrile and propylene carbonate, the reaction was studied at pressures up to 1500 atm by a conductivity method. A comparison of the activation volume and overall volume change of reaction, obtained from density measurements, suggests that the charge development at the transition state is only fractional. The results of CNDO/2 calculations support the argument.
Photoelectrochemical Behavior of n-Type TiO2 and Other Semiconductor Electrodes in Acetonitrile Solutions Containing Various Aromatic Amines
Authors: Nakatani Kenji , Tsubomura Hiroshi 
Published: July 2006

Abstract
The electrode behavior of n-type TiO2 in acetonitrile solutions containing one of a variety of aromatic amines under illumination has been investigated. The onset potential of the anodic photocurrent leading to the oxidation of the amines changed from the most negative −0.51 V vs. SCE for N,N,N′,N′-tetramethyl-p-phenylenediamine to the least negative −0.27 V for aniline. These values parallel the change of the flat band potential by the amine and become more negative as the ionization potential of the amine decreases. The influence of the amine on the flat band potentials of ZnO, CdS, and GaP was also studied and found to be much less than in the case of TiO2. From these results, the reason for the change of the flat band potential in the case of TiO2 is attributed to a specific charge transfer interaction between the semiconductor and the amine.
The Distribution of Higher Alcohols in Aqueous Micellar Solutions
Authors: Hayase Kohji , Hayano Shigeo 
Published: July 2006

Abstract
The distribution coefficients, K, for 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol between the sodium dodecyl sulfate (SDS) micellar and aqueous phases were measured directly, with the gas chromatographic technique was used to measure the vapor pressure of the alcohols. The standard free energy change of penetration, ΔGp°, of the alcohol from the aqueous to the micellar phase was obtained using the equation: ΔGp°=−RTlnK. There is a linear relation between ΔGp° and the carbon number of the alcohol.
Intersystem Crossing Processes of Acridine
Authors: Kikuchi Koichi , Uji-ie Koji , Miyashita Yoshikatsu , Kokubun Hiroshi 
Published: July 2006

Abstract
The T1(π, π*)→T3(π, π*) absorption of acridine has first been observed at about 985 nm in ethanol. Temperature dependences of the fluorescence lifetime and the triplet yield of acridine were investigated in poly(vinyl alcohol) film, and it was found that the intersystem crossing from the first excited singlet state S1(π, π*) to T1(π, π*) occurs through both temperature dependent and independent processes. The activation energy of the temperature dependent process corresponds substantially to the energy difference between T3(π, π*) and S1(π, π*). The intersystem crossing from S1(π, π*) to T2(n, π*) followed by the internal conversion to T1(π, π*) was assigned to the temperature independent process.
Thermal Analysis and NMR Observation of 66-Nylon
Authors: Ito Masayoshi , Kanamoto Tetsuo , Tanaka Koji 
Published: July 2006

Abstract
The effects of morphology on γ-relaxation in 66-Nylon is investigated. The morphology of the samples was characterized mainly by thermal analysis. Information about the molecular motion of 66-Nylon is obtained from the temperature dependence of the spin-lattice relaxation times (T1). In order to compare the relaxation behavior of 66-Nylon with that of other semicrystalline polymers, the T1 of polyoxymethylene (POM) was also measured as a function of temperature. It was found that in 66-Nylon, both solution-grown crystals and bulk samples are composed of folded chain lamellae with fairly large amounts of less perfect crystalline regions. Both the magnitude and the temperature of the T1 minimum at about 30 °C (γ-region) for 66-Nylon are not sensitive to the sample history, in contrast to those for POM. In addition, the T1-temperature curve in the γ-region for 66-Nylon is much broader than that for POM. These NMR results for 66-Nylon are interpreted in terms of a rather wide variety of structural heterogeneities from the usual amorphous regions to fairly restricted regions, such as the less-perfect crystalline regions at the lamellar surface.
The Molecular-Symmetry Reduction in Open-Shell Conjugated Hydrocarbons
Authors: Toyota Azumao , Nakajima Takeshi 
Published: July 2006

Abstract
On the basis of the second-order Jahn-Teller theorem, we propose a criterion for predicting the stable groundstate geometrical structures of open-shell conjugated hydrocarbons. It is found that in contrast with the cases of the parent closed-shell hydrocarbons no molecular symmetry reduction occurs in the ion radicals of the CmHm–2 catacondensed nonalternant hydrocarbons, such as pentalene and heptalene. On the other hand, it is revealed that the ion radicals of fulvalene systems suffer the molecular symmetry reduction from D2h to C2v. In addition, the electronic spectra were calculated using the stable geometrical structures obtained by use of the semiempirical open-shell SCF MO method.
Reaction of Carbon Dioxide with Tetraphenylporphinatoaluminium Ethyl in Visible Light
Authors: Inoue Shohei , Takeda Norikazu 
Published: July 2006

Abstract
Tetraphenylporphinatoaluminium ethyl reacts with carbon dioxide in the presence of 1-methylimidazole to produce tetraphenylporphinatoaluminium propionate in the presence of visible light but not in the dark.
A Molecular Orbital Calculation of Chemically Interacting Systems. Interaction between Two Radicals
Authors: Minato Tsutomu , Yamabe Shinichi , Fujimoto Hiroshi , Fukui Kenichi 
Published: July 2006

Abstract
The reaction path of radical-radical recombination and disproportionation has been studied by means of a perturbational method with a clear orbital interaction concept, and the mechanism of these reactions has been elucidated theoretically. It has been confirmed that these termination reactions do not have a common transition state. The recombination is found to take the path which gives the maximum interaction between the singly occupied molecular orbitals (SOMO’s) of two radical species, whereas the disproportionation is shown to take the route which gives the significant charge transfer interaction from the particular doubly occupied (DO) MO of one radical to the SOMO of the other radical. The DOMO localized at the C–H bond donates electrons to the SOMO to cause the hydrogen abstraction. In the process of disproportionation, one radical which abstracts a hydrogen atom acts as an electron-acceptor and the other radical with the hydrogen atom to be abstracted as an electron-donor. The difference between the mechanism of the recombination and that of the disproportionation is clarified in terms of the mode of the orbital interaction.
Structural Studies of the Interaction between Indole Derivatives and Biologically Important Aromatic Compounds. II. The Crystal and Molecular Structure of the Tryptamine–Phenylacetic Acid (1:1) Complex
Authors: Inoue Masatoshi , Sakaki Toshimasa , Fujiwara Takaji , Tomita Ken-ichi 
Published: July 2006

Abstract
The title complex crystallizes in the monoclinic space group of P21/c. The unit-cell dimensions are a=6.673(4), b=19.017(8), c=13.394(7) Å, and β=110.54(2)°. The crystal structure was solved by a direct method. By block-diagonal least-squares refinements, the R-value converged to 0.062. In this complex, a salt bridge is found between the anionic carboxyl group of phenylacetic acid (PAA) and the cationic amino group of tryptamine (TPA). All the hydrogen atoms attached to the nitrogen atoms participate in the hydrogen bonding. The two complex molecules are hydrogen-bonded around a center of symmetry to form one unit, which is held together by van der Waals contacts in the b- and c-directions. Each unit is also stabilized by forming a hydrogen bond with the unit of the neighboring cell translated in the a-direction.
Vibrational Spectra of Dimethylaminosulfonyl Chloride and Its C-Deuterated Derivative
Authors: Tanaka Yukiko , Tanaka Yoshimasa , Saito Yutaka , Machida Katsunosuke 
Published: July 2006

Abstract
The infrared and Raman spectra of dimethylaminosulfonyl chloride and its C-deuterated derivative have been recorded in the liquid state. The fundamental frequencies have been assigned by referring to the band intensities, Raman depolarization ratios and isotopic frequency shifts. A normal coordinate analysis based on a planar Cs molecular model has been carried out by using a simple Urey-Bradley force field for stretching and bending coordinates and a valence force field for torsional coordinates. The calculated frequencies based on a refined set of force constants agree well with the observed ones.
The Crystal Structure of Monoaquabis(1,10-phenanthroline)copper(II) Tetrafluoroborate [Cu(H2O)(phen)2](BF4)2
Authors: Nakai Hisayoshi , Noda Yukinao 
Published: July 2006

Abstract
The crystal of the title compound is monoclinic, with a=19.099(6), b=8.100(3), c=16.177(5) Å, β=100.54(5)°, the space group of C2/c, and Z=4. The structure was determined from the counter data and was refined to R=0.083 for 1736 non-zero reflections. The coordination geometry of the copper atom is best described as a distorted trigonal bipyramid, in which the equatorial plane is composed of Cu, two N, and water O atoms, and the axial positions are occupied by two N atoms. The complex has a crystallographically imposed twofold axis which passes through the copper and the water oxygen atoms at the equatorial plane. The two phenanthroline ligands are related with each other by this axis.
Heterofulvalenes. I. 5-Aza- and 6-Aza-1,4-dithiafulvalenes
Authors: Nakayama Jyuzo , Watabe Yukie , Hoshino Masamatsu 
Published: July 2006

Abstract
5-Aza, 2,3-benzo-5-aza-, 6-aza-, and 2,3-benzo-6-aza-1,4-dithiafulvalenes were synthesized and their spectroscopic properties are described. For example, the reaction of 2-methylthio-1,3-dithiolylium iodide with pyrrole gave 2-(2-pyrrolyl)-1,3-dithiolylium iodide in a 92% yield, which was treated with DBU, giving rise to 5-aza-1,4-dithiafulvalene as thermally-stable orange crystals in an 82% yield. Several reactions found during the course of these synthetic studies are also reported.
Photoreaction of 1-(1-Cycloalkenyl)-4-phenyl-1-butanone under Neutral and Acidic Conditions
Authors: Tada Masaru , Maeda Tetsuro , Saiki Hiroshi 
Published: July 2006

Abstract
UV irradiation of 1-(1-cycloalkenyl)-4-phenyl-1-butanones gives differing products depending on the reaction conditions, neutral or acidic. In benzene 1-(1-cyclopentenyl)-4-phenyl-1-butanone gives 4-phenylspiro[4,4]-nonan-1-one, formed by the intramolecular abstraction of hydrogen, and 4-cyclopentylidene-4-phenylbutanal, formed by Norrish type I fission of the spiro ketone. 1-(1-Cyclohexenyl)-4-phenyl-1-butanone does not exibit this behavior. Both ketones give the reduction products, 1-cyclopentyl-4-phenyl-1 -butanone and 1-cyclohexyl-4-phenyl-1-butanone, under the action of trifluoroacetic acid, and cyclized products, 7-phenylperhydro-4-indenone and 4-phenylperhydro-1-naphthelenone, under the action of boron trifluoride etherate. The reaction processes under acidic conditions have both an ionic and a free radical nature. The results have lead to the proposition of the mechanism involving electron transfer, proton transfer, and hydrogen abstraction.
A Localized Molecular Orbital Calculation of Chemically Interacting Systems. Interaction between Amines and Carbonyls
Authors: Minato Tsutomu , Fujimoto Hiroshi , Fukui Kenichi 
Published: July 2006

Abstract
The bond interchange in the course of the addition of amine to carbonyl has been studied by means of a localized molecular orbital method with a clear chemical-bond concept, and the mechanism of the addition has been elucidated theoretically. It is ascertained by the present calculation that the charge transfer interaction from the highest occupied molecular orbital of amine to the lowest unoccupied molecular orbital of carbonyl is of importance to form a new nitrogen-carbon bond. Furthermore, the stereospecificity of the nucleophilic addition to a double or triple bond has been studied. When an intermediate is created by the addition of a nucleophile to the unsaturated bond, it is suggested that the intermediate is reactive for the electrophilic attack on the side trans to the new bond formed by the first attack. This is reasoned in terms of the mode of orbital interaction.
Synthesis of Ylide Complexes of Cobalt and the Crystal Structure of [Benzoyl(1-pyridinio)methanide]chlorobis(dimethylglyoximato)cobalt(III) Toluene Solvate
Authors: Saito Taro 
Published: July 2006

Abstract
Bis(dimethylglyoximato)halogenocobalt(III) complexes of benzoyl(1-pyridinio)methanide were synthesized by a new kind of oxidative addition reaction of N-phenacylpyridinium halides to diaquabis(dimethylglyoximato)cobalt(II) in air. The crystal structure of the [benzoyl(1-pyridinio)methanide]chlorobis (dimethylglyoximato) cobalt(III) toluene solvate was solved by single-crystal X-ray diffraction techniques. The crystals are monoclinic (space group P21/c), with cell dimensions of a=11.41(1), b=10.28(1), c=27.50(3) Å, β=116.3(1)°, and Z=4. The final R was 0.068. The ylide ligand coordinates to cobalt through the ylide carbon, with a Co–C distance of 2.07(1) Å, and the chlorine atom is bonded to cobalt with a Co–Cl distance of 2.285(4) Å and with a C(ylide)–Co–Cl bond angle of 175.5(3)°. The dimethylglyoxime ligands and cobalt atom are co-planar to within 0.04 Å.
Acidic Property and Catalytic Activity of Tungsten Oxide
Authors: Hattori Hideshi , Asada Noriyoshi , Tanabe Kozo 
Published: July 2006

Abstract
A maximum activity of tungsten oxide for the isomerization of 1-butene was observed when the catalyst was evacuated at 600 °C, the ratio of cis-2-butene to trans-2-butene being 1.4. The activity was lost by the addition of NH3, but not affected by the addition of CO2 or H2O. The oxidation states of tungsten oxide treated with hydrogen at 550 and 650 °C were WO2.89 and WO2, respectively. The activity of WO2.89 for the double bond isomerization of 1-butene was almost the same as that of WO3 but the activity of WO2 for the double bond and skeletal isomerization of 1-butene and the dehydration of isopropanol was higher than that of WO3 or WO2.89· The coisomerization of cis-2-butene-d0/d8 revealed that the double bond isomerization of butenes proceeds by an intermolecular hydrogen transfer mechanism. When cis-2-butene-d8 was introduced to the catalyst on which cis-2-butene-d0 had been preadsorbed, the reactant and the product containing much of H were obtained, no d0-species being observed. It was concluded that the active sites for the isomerization of butenes are protons of polymerized butene formed by the adsorption on Lewis acid sites of tungsten oxide surface and the isomerization takes place via carbenium ion intermediates.
The Crystal and Molecular Structure of Oxydi(carboxymethyl)bis-(triphenylphosphine)palladium(II), [Pd(C4H4O3)(PPh3)2]
Authors: Zenitani Yukio , Tokunan Haruo , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami 
Published: July 2006

Abstract
The molecular structure of oxydi(carboxymethyl)bis(triphenylphosphine)palladium(II), [Pd(C4H4O3)(PPh3)2] has been determined by means of X-ray diffraction. The crystal belongs to the orthorhombic system, space group P212121, with four formula units in a cell with dimensions of a=16.320(2), b=20.104(2), and c=10.271(2) Å. R=0.058 for 4732 non-zero relfections. The feature of the structure is that the palladium atom is chelated by an acetic anhydride to form a six-membered ring [Pd–C=2.141(13) and 2.124(11) Å], and the palladium atom has a square-planar geometry.
Photochemical Reactions of Aromatic Compunds. XXXI. Exciplex Quenching by Pyridine, Methylated Pyridines, and Methylated Imidazoles and Termolecular Interaction in the Excited Singlet State
Authors: Majima Tetsuro , Pac Chyongjin , Sakurai Hiroshi 
Published: July 2006

Abstract
Pyridine, methylated pyridines, and methylated imidazoles quenched the exciplexes of aromatic nitrile–2,5-dimethylfuran or 2,5-dimethyl-2,4-hexadiene, and the rate constants for the exciplex quenching were obtained. The exciplex quenching by 2-methyl- and 2,6-dimethylpyridines was much less efficient than that by the other quenchers. The exciplex quenching was discussed in terms of the interaction of the n-orbital of the quenchers with the positive charge developed on the electron-donor side of the exciplexes. Curved Stern-Volmer plots were obtained in the quenching of aromatic nitrile fluorescence by 1-methylimidazole and/or 1,2-dimethylimidazole. On the basis of the kinetic results, the mechanism was discussed in terms of a termolecular interaction between excited singlet aromatic nitrile, the methylated imidazole as the π-donor, and the second one as the n-donor.