bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Crystal Structure and Magnetic Property of the Alkoxo-Oxygen Bridged Tetranuclear Copper(II) Complex, Cu4{(n-C3H7)2N(CH2)2O}4Cl4
Authors: Matsumoto Naohide , Ueda Ikuhiko , Nishida Yuzo , Kida Sigeo 
Published: July 2006

Abstract
The crystal structure of the alkoxo-oxygen bridged tetranuclear copper(II) complex, Cu4{(n-C3H7)2N(CH2)2O}4Cl4, has been determined from the three-dimensional X-ray diffraction method. The crystals are orthorhombic with the space group Pbcn. The cell dimensions are α=15.965 (4), b=14.941 (1), c=19.305 (2) Å. The structure has been determined from the heavy atom method and refined by the block-diagonal least-squares method to give R=7.52%. The complex is of a cubane type structure formed by four copper and four alkoxide oxygen atoms. Each copper atom has a distorted square pyramidal environment. The correlation between the magnetic property and the structure was discussed on some homologous compounds of cubane structure.
The Oxidation Activity and Acid-base Properties of Mixed Oxide Catalysts Containing Titania. I. The TiO2–MoO3 and TiO2–V2O5 Systems
Authors: Ai Mamoru 
Published: July 2006

Abstract
The amounts of both the acidic and basic sites of two series of catalysts, TiO2–MoO3 and TiO2–V2O5, with different compositions were measured by studying the adsorption of the basic and acidic molecules in the gas phase, using both the static and pulse methods. The acidity of TiO2–MoO3 catalysts is very high at Mo=40–60 atom%, though those of the TiO2-rich (Mo&lt;30 atom%) and MoO3-rich (Mo&gt;80 atom%) catalysts are fairly low. The acidity of the TiO2–V2O5 increases steadily with the V2O5 content. The basicity of the catalysts is remarkably enhanced by the introduction of a small amount of MoO3 or V2O5. It can be said that the catalysts are basic at Mo&lt;20 atom% or V&lt;10 atom%, while the MoO3-rich or V2O5-rich catalysts are acidic. The vapor-phase oxidation of 1-butene, butadiene,and acetic acid, the dehydration and dehydrogenation of isopropyl alcohol (IRA), and the isomerization of 1-butene were carried out in the presence of an excess of air, and the relationship between the catalytic behavior and the acid-base properties was investigated. It was concluded that the activities and selectivities can be relatively well explained by the acid-base properties between the catalyst and the reactant.
Aldol Condensation of Aldehydes with Ketones Promoted by the Copper(II) Ion. Orientation to the Chemical Model for Metalloaldolases
Authors: Iwata Masaaki , Emoto Sakae 
Published: July 2006

Abstract
The aldol condensation reactions of aromatic aldehydes such as 1 through 4 and 7 through 13, and aliphatic aldehydes such as 5 and 6, with a number of ketones promoted by the copper(II) ion were examined. The reactions were specifically promoted by the copper(II) ion, while such metal ions as zinc, cobalt(II), manganese(II), and magnesium were quite inactive as catalysts. All the aldehydes but 7 and 8 reacted with all the aliphatic ketones except ethyl acetoacetate, acetonitrile, and nitromethane to varying degrees in the Claisen-Schmidt type of reaction. Acetylacetone gave a condensation product of the Knoevenagel type. In the reaction of aldehydes with 2-butanone, aldehydes regiospecifically attacked the methylene group at C3 of 2-butanone. Amines inhibited the reaction, while the coexistence effect of zinc or cobalt(II) was observed. It was shown that there existed a substrate selectivity depending greatly on the kinds of ketones in the reaction promoted by the copper(II) ion. As a consequence, possible intermediates in the reaction were proposed and the relationship of the aldol condensation reaction promoted by the copper(II) ion with the metalloaldolases was discussed, particularly in the light of the role of the metal ions in both catalytic mechanisms.
The Reductive N-Methylation of Amines with Tetracarbonyl-hydridoferrate-Formaldehyde
Authors: Watanabe Yoshihisa , Shim Sang Chul , Mitsudo Take-aki , Yamashita Masakazu , Takegami Yoshinobu 
Published: July 2006

Abstract
Alcoholic tetracarbonylhydridoferrate combined with formaldehyde is an excellent reagent for reductive N-methylation of amines. The effects of reaction conditions such as temperature, atmosphere, and molar ratio (ferrate/formaldehyde/amine) on the reaction have been examined. The optimum condition for N,N-dimethylation of aniline is at 60 °C, under carbon monoxide, and at 1.0/2.2/1.0 for the molar ratio.
A MINDO/2′-MO Study of the Inversion Barriers of Some Molecules Involving First-Row Atoms
Authors: Ohkubo Katsutoshi , Azuma Yutaka , Okada Masahide 
Published: July 2006

Abstract
The inversion barriers of CH3−, NH3, CH3NH2, (CH3)2NH, (CH3)3N, NH2OH, NH2CHO, and OH3+ were investigated by means of the MINDO/2′ method. Although the calculated bond lengths are in satisfactory agreement with the experimental values, the calculated bond angles are too large and resulted in relatively low inversion barriers in comparison with the observed values.
N-Allylprazole as a Ligand. III. The Crystal and Molecular Structure of (1-Allyl-3,5-dimethylpyrazole)copper(I) Chloride
Authors: Fukushima Kazuo , Kobayashi Akiko , Miyamoto Takeshi , Sasaki Yukiyoshi 
Published: July 2006

Abstract
The crystal structure of (1-allyl-3,5-dimethylpyrazole) copper (I) chloride, CuCl(C8H12N2), has been determined by the three-dimensional X-ray analysis. The crystal is triclinic, space group P\bar1; a=8.442(4), b=8.873(6), c=8.112(3) Å, α=103.44(3), β=116.42(3), γ=63.37(3)° and Z=2. The structure was refined to an R value of 0.056 for 1196 collected reflections. The complex has a dimeric structure in which the copper(I) ion is surrounded quasi-tetrahedrally by two bridging chlorines, a pyrazole-nitrogen and the olefinic part of the allyl group. The C=C bond distance (1.34 Å) scarcely shows any increase upon coordination to the metal. The olefin plane is almost perpendicular to the Cu-olefin bond axis and shows no significant bendings of the olefinic atoms out of the plane.
Reduction and Oxidation Potentials of Metal-free and Cobalt Tetra(p-substituted phenyl)porphyrins
Authors: Tezuka Meguru , Ohkatsu Yasukazu , Osa Tetsuo 
Published: July 2006

Abstract
Both reduction and oxidation potentials of metal-free and cobalt tetra(p-substituted phenyl)porphyrins were determined by means of cyclic voltammetry. They are correlated with Hammett σ values of the substituents when the electron transfer occurs at the porphin ring, but not in the electron transfer step in which the cobalt atom participates.
The Chlorination of 1,3- and 1,5-Cyclooctadienes with Various Chlorinating Agents
Authors: Uemura Sakae , Onoe Akira , Okazaki Hajime , Okano Masaya , Ichikawa Katsuhiko 
Published: July 2006

Abstract
The chlorination of 1,3-cyclooctadiene with various chlorinating agents gave an isomeric mixture of trans-3,4-, cis-3,4-, trans-3,8-, and cis-3,8-dichlorocyclooctene. From 1,5-cyclooctadiene an isomeric mixture of trans- and cis-5,6-dichlorocyclooctene was obtained. The isomer distribution depended a great deal on chlorinating agents in both cases.
Catalytic Oxidation of Mercaptans by Iodine-Hydrogen Iodide System in Dimethyl Sulfoxide
Authors: Aida Tetsuo , Akasaka Takeshi , Furukawa Naomichi , Oae Shigeru 
Published: July 2006

Abstract
Mercaptans were oxidized readily by a catalytic amount of iodine or hydrogen iodide (i.e., aq. HI-solution) in the presence of dimethyl sulfoxide to afford the corresponding disulfides nearly quantitatively.
Extrinsic Carrier Photogeneration in Poly(N-vinylcarbazole) Films Doped with Dimethyl Terephthalate
Authors: Yokoyama Masaaki , Endo Yoshihiro , Mikawa Hiroshi 
Published: July 2006

Abstract
Based upon the previously reported experimental results that the exciplex fluorescence of poly (N-vinylcarbazole) films doped with dimethyl terephthalate is partly quenched by an electric field, a model is proposed for the extrinsic carrier photogeneration mechanism. Interaction between a migrating singlet exciton and an electron acceptor (“encounter complex”) produces an electron-hole ion pair having a rather large separation through a charge-transfer process between the components and a thermalization process of the excess energy. This ion pair dissociates into free carriers with Onsager’s probability of escaping the geminate recombination which gives a “relaxed fluorescent exciplex state”. The field dependence of the initial separation of the ion pair is also discussed.
Kinetics of the Proton-Transfer Reactions of Some ortho-Hydroxy Derivatives of Azo and Azomethine Compounds in Dioxane-Water Medium
Authors: Yoshida Noboru , Fujimoto Masatoshi 
Published: July 2006

Abstract
The kinetics of the proton-transfer reactions between hydroxide ion and o-hydroxy azo and o-hydroxy azomethine compounds having a strong O–H···N or an O–H···π intramolecular hydrogen-bond are studied in 50% (v/v) dioxane-water by means of temperature-jump method. The forward and the backward rate constant kf and kr for the overall reactions OH−+HA\oversetkf\undersetkr\ightleftharpoonsH2O+A− are evaluated to be in the range between 4.4×104 and 6.1×108 M−1 s−1 and between 1.5×103 and 6.2×104 s−1 respectively. The values of the kf for the azomethines are by several orders of magnitude higher than those of the corresponding azo compounds. The values of kf and kr in dioxane-water are found to be smaller than those in aqueous medium.
Circular Dichroism of Cobalt(III) Complexes of the Type cis-[CoN2O4] and cis-[CoN4O2] Containing Acetylacetonate Ion, 2,2′-Bipyridine and 1,10-Phenanthroline
Authors: Kashiwabara (nee Konya) Kazuo , Igi Kozo , Douglas Bodie E 
Published: July 2006

Abstract
Two new cobalt(III) complexes, [Co(acac)(bpy)2]2+ and [Co(acac)(phen)2]2+ (acac=acetylacetonate ion, bpy=2,2′-bipyridine and phen=1,10-phenanthroline) were prepared from the reaction of [Co(CO3)(bpy)2]+ and [Co(CO3)(phen)2]+, respectively, with acetylacetone, and converted to the partially resolved optically active forms using a SP-Sephadex ion-exchange column. [Co(acac)2(bpy)]+ was also resolved partially with a SP-Sephadex column. [Co(acac)2(phen)]+ was resolved with a combination of silver dibenzoyl-d-tartrate and dibenzoyl-d-tartaric acid. The circular dichroism (CD) spectra for these four complexes and for [Co(acac)2(en)]+ and [Co(acac)2(tn)]+ (en=ethylenediamine, tn=trimethylenediamine) were measured. A marked solvent effect was observed in the d-d transition region for the CD spectra of the [Co(acac)2L]+ complexes. The absolute configurations for all these complexes were assigned on the basis of their CD spectra.
Spectral Properties of Mixed Ligand Copper(II) Complexes Containing l-α-Amino Acids
Authors: Sakurai Takeshi , Yamauchi Osamu , Nakahara Akitsugu 
Published: July 2006

Abstract
Absorption and circular dichroism (CD) spectral behaviors of ternary copper(II) complexes containing two l-α-amino acids or an l-α-amino acid and iminodiacetate (ida), 2,2′-bipyridine (bpy), 2-pyridinecarboxylate (pea), or 2,6-pyridinedicarboxylate (pdea), have been studied comparatively, and synthetic studies have given as crystals the mixed ligand complexes, [Cu(ida)(l-arg)]·2H2O, [Cu(ida)(l-orn)]·2H2O, [Cu(ida)(l-lys)]·1/4H2O, [Cu(pdca)(l-arg)]·H2O, and [Cu(pdca)(l-orn)]·2.5H2O, where l-arg, l-orn, and l-lys denote l-arginine, l-ornithine, and l-lysine, respectively. The CD magnitudes of the systems Cu(ida)(l-arg), Cu(ida)(l-orn), and Cu(ida)(l-lys) were found to be enhanced appreciably as compared with the magnitudes estimated from the values for the corresponding binary systems. These ternary systems showed further magnitude enhancements in 50% aqueous ethanol. The enhanced magnitudes observed for Cu(l-glu)(l-arg), where l-glu is l-glutamate, were also intensified in 10, 20, and 50% aqueous ethanol, whereas they were weakened nearly to the estimated values in aqueous solutions with higher ionic strengths (μ=0.1 and 0.5(NaClO4)). These observations support the view that the pairs of ligands constituting the above ternary complexes are fixed around copper(II) by electrostatic ligand-ligand interactions between the oppositely charged side chains. Pyridine-containing ligands, bpy, pea, and pdea, in the ternary systems with l-α-amino acids affected the signs and the magnitudes of the CD spectra.
Syntheses and Reactions of Fluorine-containing Aromatic Ketones
Authors: Kimoto Hiroshi , Muramatsu Hiroshige , Inukai Kan 
Published: July 2006

Abstract
Phenyl 1,1,2,3,3,3-hexafluoropropyl ketone(I) and 2,2,3-trifluoro-3-(trifluoromethyl)indanone(II) were synthesized by the radical-addition reaction of benzaldehyde to hexafluoropropene. The reduction with NaBH4 and the Grignard reaction with methylmagnesium iodide of these ketones gave the corresponding secondary and tertiary alcohols respectively. A Clemmensen reduction, alkaline hydrolyses, and reactions with hydroxylamine and with diazomethane were also carried out.
A Facile Method for the Oxidation of Alcohols
Authors: Saigo Kazuhiko , Morikawa Anri , Mukaiyama Teruaki 
Published: July 2006

Abstract
Trialkyltin alkoxides, prepared from alcohols and trialkyltin methoxide by azeotropical removal of methanol, are easily oxidized by bromine in the presence of trialkyltin methoxide, a hydrogen bromide captor, to give the corresponding aldehydes or ketones in good yields. Alcohols are oxidized directly in one step to the corresponding carbonyl compounds by utilizing bis(tributyltin) oxide and bromine.
Branched-chain Sugars. VIII. On the Configuration of Branched-chain Sugars from Methyl 3-O-Benzoyl-4,6-O-benzylidene-α-d-arabino-hexopyranosid-2-ulose
Authors: Yoshimura Juji , Mikami Kazutoshi , Sato Ken-ichi , Shin Chung-gi 
Published: July 2006

Abstract
Stereoselectivities in the Grignard, diazomethane and nitromethane reaction of methyl 3-O-benzoyl-4,6-O-benzylidene-α-d-arabino-hexopyranosid-2-ulose (1) were examined. In contrast to the Grignard reaction of 1 using methylmagnesium iodide to give a single 2-C-methyl derivative (4), the diazomethane reaction followed by reduction afforded another epimer (6). The nitromethan condensation product (10) of 1 was converted into the corresponding 2-C-acetaminomethyl derivative (13). The NMR spectrum of 2-O-acetate of 4 and comparison of the optical rotations of 4, 6, 10 and 13 in cupraramonium solution indicated that 4 and others have d-gluco-and d-manno-configuration, respectively. Discussions were made on the stereoselectivties of these reactions.
A Study of the Removal of Oily Soil by Rolling up in Detergency
Authors: Ogino Keizo , Agui Wataru 
Published: July 2006

Abstract
The removal of simply constituted oily soil from a low-energy surface such as polypropylene (PP) has been examined in aqueous solutions of sodium dodecylbenzenesulfonate and its builders. Oleic acid, olive oil, lauryl alcohol, oleyl alcohol, and liquid paraffin were used as model oily soils. Rolling-up was observed in all the soils except oleyl alcohol and liquid paraffin. The rolling-up of the soil occurred in the contact angle range of 0°&lt;θ&lt;90°(θ is contact angle) when the soil was removed incompletely from PP. Apparent activation energies for rolling-up were derived, i.e., 8 kcal/mol for oleic acid and 11.9 kcal/mol for olive oil. Complexes were formed for oleic acid, lauryl alcohol, and oleyl alcohol. The effects of the surfactant in various concentrations at various temperature, and with various builders were studied in view of the interfacial tension and the contact angle.
The Estimation of the G-Values for Ionization and Excitation of Ten-Electron Molecules: Methane, Ammonia, and Water Irradiated by 100 keV Electrons
Authors: Okazaki Kiyoshi , Sato Shin , Ohno Shin-ichi 
Published: July 2006

Abstract
The binary-encounter collision theory is applied to calculate the G-values for the ionization and excitation of methane, ammonia, and water irradiated by 100 keV electrons. Double collision of the incident electron in a molecule is also taken into account. On the assumption of the occurrence of certain reactions in the systems, the G-values for electrons, various radicals, and several final products were estimated. Some of the results are as follows: the G-values for electrons were 3.60 for methane, 3.56 for ammonia, and 3.00 for water. These values are in fair agreement with the experimental values: 3.6 for methane, 3.8 for ammonia, and 3.3 for water. The calculated G-value for hot hydrogen atoms was about 1.0 for all three compounds. The ratios of the G-value for excitation to that for electrons are 1.1 for methane, 1.5 for ammonia, and 1.7 for water. An estimation was also made of the G-value for the emission of highly-excited hydrogen atoms using reported cross sections. The G-values are 0.1 for methane and ammonia, and 0.2 for water.
Chromium(III) Complexes with Amino Acids. I. Chromium(III) Complexes with Glycine and dl-α-Amino Acids
Authors: Oki Hisaya , Otsuka Kiyoe 
Published: July 2006

Abstract
A comparison has been made between the synthesis carried out by the isothermal matrix method in solid state and that by the usual method in solution for chromium(III) complexes with glycine and dl-α-amino acids (alanine, aminobutyric acid, norvaline, norleucine, valine, isoleucine and leucine). The effect of the length of the skeletal carbon chain or the presence of the side chain in α-amino acids on the formation of complexes was investigated. The complexes with α-amino acids which have a normal chain were obtained in fac-structure except for norleucine complexes, whereas the complexes with α-amino acids which have a side chain were obtained only in dimertype by the matrix method in solid state. The chromium(III) complexes with dl-α-amino acids were all prepared as tris-type structure, except for α-aminobutyric acid and valine, whereas all the complexes of dimer-type structure were prepared in solution, except for alanine and norleucine.
Chemistry of Nitrosoimines. XV. Reactions of 3-Substituted 2-Nitrosoimino-2,3-dihydrobenzothiazoles with Lithium Aluminum Hydride and Diazo Compounds
Authors: Akiba Kin-ya , Kawamura Takayuki , Ochiumi Masahide , Inamoto Naoki 
Published: July 2006

Abstract
3-Substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) were reduced with lithium aluminum hydride to give the corresponding thiazolone azines and bis[o-(N-substituted N-formylamino)phenyl] disulfides as major products. Reactions of 1 with some substituted diazomethanes gave the corresponding unsymmetrical azine N-monoxides (16) or azines (17) depending on the structure of the diazomethane.
Nickel-Phosphine Complex-Catalyzed Grignard Coupling. I. Cross-Coupling of Alkyl, Aryl, and Alkenyl Grignard Reagents with Aryl and Alkenyl Halides: General Scope and Limitations
Authors: Tamao Kohei , Sumitani Koji , Kiso Yoshihisa , Zembayashi Michio , Fujioka Akira , Kodama Shun-ichi , Nakajima Isao , Minato Akio , Kumada Makoto 
Published: July 2006

Abstract
It has been established that dihalodiphosphinenickel(II) complexes exhibit extremely high catalytic activity for selective cross-coupling of Grignard reagents with aryl and alkenyl halides. This catalytic reaction can be employed in synthetic practice for reasons of simple procedures, mild reaction conditions, high yields and high purity of the coupling products, and the wide applicability to reactions involving primary and secondary alkyl (regardless of the presence or absence of β-hydrogen (s)), aryl, and alkenyl Grignard reagents and nonfused, fused, and substituted aromatic halides and haloolefins. Limitations lie in sluggish reactions between alkyl Grignard reagents and dihaloethylenes. The most effective catalysts are [Ni{(C6H5)2P(CH2)3P(C6H5)2}Cl2] for alkyl and simple aryl Grignard reagents, [Ni{(CH3)2P(CH2)2P(CH3)2}Cl2] for alkenyl and allylic Grignard reagents and [Ni{P(C6H5)3}2-Cl2] for sterically hindered aryl Grignard reagents and halides. Great stabilizing effects of phosphine ligands on the catalytic species are demonstrated by no effect observed after aging the catalyst. Organic chlorides are generally the most suitable halide in view of the reasonable reactivities and limited side reactions. Ether is favored over tetrahydrofuran as solvent. About sixty experimental results are presented and several features are discussed.
The Electronic Spectra of α,ω-Di-1-anthrylpolyenes in Solution and in Solid State
Authors: Mandal Krishnagopal , Misra T N 
Published: July 2006

Abstract
The electronic absorption spectra of a number of α,ω-Di-1-anthrylpolyenes have been studied in solution and in crystals. Three intense and two weak band systems have been observed. The plots of λ2–n and ε–n result in a good straight line in lower members. These results suggest that long anthrylpolyenes are not in all-trans form. Highest energy emission and lowest energy absorption bands show good overlap and identical solvent behavior. It has been concluded that in anthrylpolyenes the lowest excited state is an allowed 1Bu type. The terminal anthrylgroup interaction effect is such that 1Ag is not lowered relative to 1Bu in these polyenes. The absorption bands of anthrylpolyenes in the crystalline state could be explained in terms of factor group split components.
Infrared Studies of the Isocyanate Species Formed in the Reaction of NO with CO over Pt and Rh
Authors: Niiyama Hiroo , Tanaka Motoo , Iida Hiroshi , Echigoya Etsuro 
Published: July 2006

Abstract
The behavior of isocyanates formed on the surface of Rh and Pt in the reaction of nitrogen oxide with carbon monoxide was studied by means of IR spectroscopy using a flow reactor. The isocyanate species readily reacted with N2O or H2O, however, it did not decompose when dosed with NO or CO. The catalytic activity of Pt–Al2O3 in the reaction of NO+CO declined quickly with an increase in the amount of the surface isocyanate (–NCO). Accordingly, it is concluded that –NCO is not a reaction intermediate but an inhibitor of the reaction.
Emission Spectra of the Vinyl Polymers with Pendant Carbazolyl Groups
Authors: Itaya Akira , Okamoto Ken-ichi , Kusabayashi Shigekazu 
Published: July 2006

Abstract
The emission properties of poly(N-vinylcarbazole) (PVCz) prepared by radical and cationic polymerization (PVCz(r) and PVCz(c) respectively), the oligomers of N-vinylcarbazole, and poly[2-(N-carbazolyl)ethyl vinyl ether] (PCzEVE) were investigated in solutions. The fluorescence spectrum of PVCz(r) was different from that of PVCz(c). This seems to be attributable to the difference in the tacticity between them. On the basis of this result, the structure of the second excimer site is discussed. PCzEVE, in which the carbazolyl chromophores are widely spaced on the skeletal chains by –O–CH2–CH2– bonds, showed an interesting, new, structureless emission band with a peak at 27000 cm−1. This was different from both the monomeric structured fluorescence and the sandwich-like excimer one which were observed for the model compounds and the polymers. The emission properties of PCzEVE were unique among the vinyl polymers with aromatic chromophores widely spaced on the skeletal chain.
Synthesis and Characterization of Aluminium(III) Complexes with Schiff Bases Obtained from Salicylaldehyde Derivatives and Alkylamines
Authors: Kuma Hiro , Yamada Shoichiro 
Published: July 2006

Abstract
Aluminium(III) complexes with Schiff bases (abbreviated as X–sal–R) obtained from salicylaldehyde derivatives and amines (RNH2) have been synthesized by a method starting from aluminium(III) isopropoxide. Complexes of the type Al(X–sal–n-alkyl)3 have been isolated, but any attempt to obtain complexes of the types Al(X–sal–i-C3H7)3 and Al(X–sal–aryl)3 has not been successful. The tris-complexes obtained show similar electronic absorption spectra, regardless of R. Proton magnetic resonance spectra indicate that the aluminium(III) complexes may have a fac-configuration.