bluuebunny/crossref_metadata_2025_split huggingface dataset:
Solvolysis of Organic Phosphates. V. Participation of the Neighboring Groups and Effects of Metal Ions in the Hydrolysis of 3-Hydroxy-2-pyridylmethyl Phosphate
Authors: Murakami Yukito , Sunamoto Junzo , Ishizu Hideyuki 
Published: July 2006

Abstract
The spontaneous hydrolysis of 3-hydroxy-2-pyridylmethyl phosphate was investigated at 60, 70, and 80°C over the–log[H+] range from 1 to 10 in aqueous media with an ionic strength of 0.10. The reactions followed apparent first-order kinetics with respect to the unreacted phosphate species, and the maximum rate was observed at–log[H+] 7–8. Reactive species in hydrolysis were neutral zwitterion, monoanion, and dianion species, the reactivity increasing in this order. This trend in reactivity order has not been observed previously. In a moderately acidic region (–log[H+]&lt;2.0), kinetic data were consistent with the acid catalysis acting on the zwitterion species. Activation parameters provide an evidence for the unimolecular nature of the transition state in spontaneous hydrolysis and suggest the Al process for the acid catalyzed reaction. The anomalously high reactivity of the dianion species was attributed to participation of the 3-hydroxy group in the reaction process: intramolecular transfer of the hydroxyl proton to the ester oxygen in a pre-equilibrium stage, followed by the P-O bond cleavage in the subsequent transition state to give the products. Hydrolysis was also carried out in the presence of copper(II), nickel(II), zinc(II), aluminum (III), iron(III), and thorium(IV) ions at 60°C and μ=0.10 in a relatively lower pH range. Introduction of the 3-hydroxyl group to 2-pyridylmethyl phosphate resulted in a change of catalytic status of various metal ions. Only iron(III) and thorium(IV) ions accelerated the rate to a significant extent. Validity of the two requirements originally proposed for the bivalent metal catalysis was extended to the polyvalent metal catalysis.
Metal Catalysts Supported on Zeolite. I. A Study on Platinum Particles Distribution
Authors: Kubo Toshihiko , Arai Hiromichi , Tominaga Hiroo , Kunugi Taiseki 
Published: July 2006

Abstract
Zeolite 13Y, loaded with platinum cations by ion exchange, was calcined in the air and subsequently reduced in a hydrogen stream. Hydrogen and carbon monoxide adsorption studies, together with an electron microscopic observation of the catalyst, revealed that the size distribution of platinum particles is controlled by the calcination temperature. The hydrogen chemisorption method gave the average particle diameters, which were in fairly good agreement with the observations made by means of an electron microscope on the catalyst with a platinum particle diameter larger than 20 Å, while trace amounts of hydrogen chemisorption were observed for platinum particles less than 20 Å.
The Abnormal Absorption Intensity of the C-H Stretching Vibration Band in Chloroform Vapor. I. The CNDO Calculation Involving the 3d Orbitals
Authors: Miyazaki Tomoo , Shigetani Tsunehisa , Yamamoto Hiroshi 
Published: July 2006

Abstract
By the CNDO calculation involving the 3d orbitals, the infrared absorption intensity of the C–H stretching vibration band in chloroform vapor has been discussed in comparison with those of methyl chloride and methylene chloride. The value of the 3d orbital exponent of the chlorine atom was estimated on the basis of calculations using different values of the 3d orbital exponent on methyl chloride. The absolute intensities of the fundamental and the first overtone bands were calculated from the values of the first and the second derivatives of dipole moments with respect to the normal coordinates. From the results of these calculations, it follows that the electrical properties of the vibrating bond are the most effective factors in bringing about the abnormal absorption intensity of the C–H stretching vibration band in chloroform vapor.
Excimer and Monomer Defect Emissions of Perylene and Pyrene Crystals as Studied by the Nanosecond Time-resolved Spectroscopy Technique
Authors: Inoue Akinori , Yoshihara Keitaro , Kasuya Takahiro , Nagakura Saburo 
Published: July 2006

Abstract
Nanosecond time-resolved fluorescence spectra were measured at 77°K for pyrene and perylene crystals, and anomalous emissions which have lifetimes of ∼ 8 nsec and are difficult to be found by the usual steady excitation, were observed at the higher-wave number sides of the usual excimer emissions. From the band position and the vibrational structure, the anomalous emission was interpreted as being due to monomer defects in each crystal. The analysis of the observed rise and decay curves of the monomer defect and excimer emissions shows that the excited states of both emissions are populated independently from the band level of each crystal excited by light irradiation. The temperature dependence of the emission indicates that a thermal activation of 0.035 eV is required for the excimer formation in a perylene single crystal, while no activation energy is required for the excitation of the monomer defect.
Mordant Blue 31 as a New Fluorometric Reagent for Aluminum, Gallium, and Scandium
Authors: Hiraki Keiz\={o} 
Published: July 2006

Abstract
A sensitive fluorometric determination of aluminum, gallium, and scandium with Mordant Blue 31 was worked out. The reagent reacts with aluminum, gallium, scandium, yttrium, lanthanum, lutetium, indium, and magnesium in acidic or basic medium to form complexes with reddish yellow fluorescence. The complexes of aluminum (pH: 5–7), gallium (pH: 4), and scandium (pH: 6) exhibit strong fluorescence with an emission maximum at 590, 600, and 610 nm, respectively. The effects of time, pH and the concentration of the reagent were investigated. In acidic medium, aluminum, gallium, and scandium were found to form 1:1 complex with Mordant Blue 31. Under the optimum conditions, 0.1–3μg of aluminum, 1–12μg of gallium, and scandium in 25 ml sample solution could be determined. Although the fluorescence intensity of aluminum and gallium complexes was a little lower than that of the lumogallion complexes, Mordant Blue 31 was also applicable as a fluorometric reagent for aluminum and gallium. Since scandium-Mordant Blue 31 complex exhibits the strongest fluorescence of all other scandium-azo dye complexes, the reagent was used as a fluorometric reagent for scandium.
Oxovanadium(IV) Complexes of Schiff Bases Obtained from Salicylaldehyde Derivatives and Arylamines
Authors: Kuge Yoshio , Yamada Shoichiro 
Published: July 2006

Abstract
Oxovanadium(IV) complexes of Schiff bases obtained from salicylaldehyde derivatives and arylamines (abbreviated as VO(X-SAL.R)2) have been synthesized, where X=H, 5,6-benzo, 5-Cl, and 5-Br, and R=Ph, CH3-Ph, 2,6-(CH3)2-Ph and 2,6-(C2H5)2-Ph, Ph being phenyl nucleus. Complexes of the type VO(5-X-SAL.Ph)2 in the solid state, X being Cl and Br, consist of the species having a different configuration from that of the other complexes. For the latter complexes, distortion from the square-pyramidal configuration is not apparent in the solid state or in non-donor solvents, but in pyridine they combine with one pyridine molecule to form six-coordinate vanadium(IV) complexes. Comparison shows that the tendency toward the distortion in the solid state is lower with R=aryl than with R=α-branched alkyl groups.
Stereochemical Studies of Metal Chelates. VI. The Separation and Stereochemistry of Isomers of Dichloro((3S,8S)-dimethyl triethylenetetramine)cobalt(III) Perchlorate
Authors: Saburi Masahiko , Yoshikawa Sadao 
Published: July 2006

Abstract
The cis-α and cis-β isomers of dichlorocobalt(III) complexes with (3S, 8S)-dimethyltriethylenetetramine were isolated. These isomers were stereospecifically formed in the Λ and Δ absolute configurations respectively. The cis-β isomerh as the Δ-β(RS) geometry, in which the configurations with respect to the coordinated secondary nitrogen centersof tetramine differ from one another. The difference between the Δ-β(RS) and Δ-β(RR) (and Λ-β(SS)) forms was noticed in the circular dichroism curves in the first absorption band region.
Synthetic Reactions by Complex Catalysts. XXV. The Copper-catalyzed Reaction of Allyl Isocyanide with Carbonyl Compounds and Olefins. Syntheses of 4-Vinyl-2-oxazoline and 5-Vinyl-1-pyrroline Derivatives
Authors: Saegusa Takeo , Murase Ichiki , Ito Yoshihiko 
Published: July 2006

Abstract
This paper describes two reactions of allyl isocyanide (AIC) by means of the Cu2O catalyst; these reactions produce heterocyclic compounds with vinyl substituents. First, the reactions of AIC with such carbonyl compounds as ketones and aldehydes produce 4-vinyl-2-oxazoline derivatives (1) in good yields. Second, AIC also reacts with the C=C double bond of α,β-unsaturated nitriles and esters to produce 5-vinyl-1-pyrroline derivatives (4,5, and 6). A mechanistic scheme involving an isocyanoallylcopper complex (11) has been assumed.
The Cope Rearrangement of Bridged Homotropilidenes Studied by MINDO Methods
Authors: Iwamura Hiizu , Morio Kazuhiko , Kunii Tosiyasu L 
Published: July 2006

Abstract
The theoretical structures and heats of formation of semibullvalene (1a), barbaralane (1b), and bullvalene (1c) have been investigated by the MINDO methods. The strain energies are estimated to be 19.7, 8.8, and 0.5 kcal/mol, respectively. The activation energies for the Cope rearrangement of these bridged homotropilidenes were obtained by a comparison of the results of a similar study on the biallylic transition states for the rearrangement. They are in good agreement with the experimental values. Extremely facile rearrangement in 1a is attributed to the partial release of strain energy through the formation of the transition state, and to the proximity (2.16 Å) of the non-bonded termini of the divinylcyclopropane unit in the ground state.
The Crystal Structure of 1-Ethyl-5-bromouracil. II. The Crystal Structure of the Form II Crystal of 1-Ethyl-5-bromouracil
Authors: Tsukihara Tomitake , Ashida Tamaichi , Kakudo Masao 
Published: July 2006

Abstract
Two crystalline forms of 1-ethyl-5-bromouracil were found. The crystal structure of the form II has been determined. The dimension of the tetragonal unit cell are a=b=17.13 Å, c=5.36 Å, and Z=8. The space group is P42⁄n. The final R is 0.064. The hydrogen bond scheme in this crystal, N(3)–H(3)···O(2), is the first finding in alkylated pyrimidine dimers. The carbon atom binding to the nitrogen atom of the pyrimidine ring deviates significantly from the pyrimidine ring plane.
Infrared Absorption Spectra of Aminobenzoic Acid Coordination Compounds
Authors: Inomata Tadaaki , Moriwaki Takao 
Published: July 2006

Abstract
Several divalent metal-aminobenzoic acid coordination compounds were prepared in aqueous solutions and their thermal analyses, magnetic moments, and infrared spectra were investigated. These coordination compounds have the structure of ML2 or ML2·nH2O and are coordinated with amino and carboxyl groups of the ligand. Metal-o-aminobenzoic acid chelates give approximately the same infrared spectra but metal-m- and p-aminobenzoic acid coordination compounds are classified into two groups by their infrared spectra. Detailed assignments for the infrared absorption bands of the metal-coordination compounds have been made by a comparison of the spectra with those of the ligand and its related compounds.
A Study of Silver(I) Complexes with Some π-Donors and n-Donors in Chloroform by the Solvent Extraction Method
Authors: Sekine Tatsuya , Takahashi Yoshihiro 
Published: July 2006

Abstract
The solvent extraction of silver(I) in a 0.1 M constant-ionic-strength solution into chloroform with 2-thenoyltrifluoroacetone(TTA) and with caproic acid was studied by means of radiometry. It was found that these extractions are enhanced by the addition of aliphatic and cyclic alkenes, of aromatic hydrocarbons, and of some n-donors. The enhancement of the extraction was explained in terms of the formation of molecular complexes of the silver(I)-TTA chelate or of silver(I) caproate in chloroform. By an analysis of the experimental data, the stability constant of the silver(I)-TTA chelate in the aqueous phase, and the stability constants of the molecular complexes in the chloroform phase with these donors, were determined. Some consideration was made of these results and of the possibility of the application of these extraction systems to analytical chemistry.
Arylation and Vinylation Reactions of Benzo[b]furan via Organopalladium Intermediates
Authors: Kasahara Akira , Izumi Taeko , Yodono Minoru , Saito Ryu-ichi , Takeda Toru , Sugawara Toshiaki 
Published: July 2006

Abstract
The Heck reaction of benzo[b]furan with arylpalladium chloride leads to the formation of 2-arylbenzo[b]-furan derivatives. In the presence of palladium acetate, benzo[b]furan reacts in benzene to give 2,2′-bibenzo[b]furyl, accompanied by 2-arylbenzo[b]furan. In the phenylation of [2-2H]benzo[b]furan with phenylpalladium salts, it was confirmed that no hydride shift takes place in the reaction. In the presence of palladium acetate, benzo[b]furan also reacts with olefin to produce benzo[b]furyl-substituted olefins, accompanied by a small amount of 2,2′-bibenzo[b]furyl, and from the reaction of [β,β-2H2]styrene and benzo[b]furan in the presence of palladium acetate it was confirmed that no hydride shift occurs in the reaction.
The Reduction of Triazolium and Tetrazolium Iodides with Sodium Borohydride
Authors: Isida Tyuzo , Akiyama Tetsuo , Mihara Nobutake , Kozima Sinpei , Sisido Keiiti 
Published: July 2006

Abstract
The sodium borohydride reduction of azolium iodides containing two, three, or four nitrogen atoms in the ring was studied. 1,4,5-Trisubstituted tetrazolium iodides gave Δ2-tetrazolines, whereas 1,3,5-trisubstituted tetrazolium iodide yielded no reduction product. 1,3,4,5-Tetrasubstituted 1,2,4-triazolium iodides and 1,2-disubstituted 1,2,3-triazolium fluorosulfonate were reduced to Δ2-1,2,4-triazolines and Δ2-1,2,3-triazoline respectively, but 1,3,4,5-tetrasubstituted 1,2,3-triazolium iodides were not reduced at all. Both pyrazolium and imidazolium salts gave the corresponding azolidines. These results can be explained in terms of the characteristics of sodium borohydride, which reduces selectively the immonium moiety in azolium salts.
The Optical and Electrical Properties of Metal Photodoped Chalcogenide Glasses
Authors: Shimizu Isamu , Sakuma Hiraku , Kokado Hiroshi , Inoue Eiichi 
Published: July 2006

Abstract
The optical and electrical properties of the metal photo-doped chalcogenide glasses were studied. The optical absorption of the chalcogenide glasses e.g., the As–S, As–S–Te, and As–S–Se systems) was increased by the photo-doping of such metals as Ag and Cu in the region of their absorption edges. The electrical conductivity of the glasses also increased with the photo-doping of the metals. The effective band gap obtained from the results of the temperature dependency of the electrical conductivity decreased with the increase in the amount of metal which was photo-doped in the glasses. The results obtained in this study suggest that the metals photo-doped in the chalcogenide glasses behaved as structural modifiers of the glasses, and that the state of density in the gap was increased by the metal photo-doping.
Thermal Decomposition Reactions of Metal Oxalato Complexes in the Solid State. II. Evolved Gas Analyses of Metal Oxalato Complexes
Authors: Nagase Kenzo 
Published: July 2006

Abstract
The thermal decomposition reactions of a number of metal oxalato complexes in the solid state were studied by an EGA method in a helium atmosphere. As regards the decomposition stage of an anhydrous complex, the complexes investigated could be divided into three groups: the complexes of Mn(III), Fe(III), Co(III), Rh(III), Cu(II), Pd(II), and Pt(II), this first group giving only CO2 as a gaseous product, decomposed by electron transfer from an oxalato ligand to a central metal ion; the complexes of Al(III) and Zn(II), this second group giving CO and CO2 in the molar ratio of 1:1, decomposed by C–O bond breaking to form a metal oxide with no change in the oxidation number of a central metal; and the complexes of V(III) and Cr(III), this third group giving CO2and a smaller amount of CO, decomposed through both the processes, electron transfer and C–O bond breaking. The subsequent decomposition reactions of the bivalent metal oxalato complexes formed upon heating the corresponding trivalent metal oxalato complexes were divided into two types: one is associated with further reduction of a central metal ion, while the other is associated with C–O bond breaking.
Binuclear Metal Complexes. VI. Syntheses and Properties of Binuclear Copper(II) Complexes of 2,6-Bis[N-(β-dialkylaminoethyl)iminomethyl]-4-methylphenol
Authors: Okawa Hisashi , Tokii Tadashi , Nonaka Yasuomi , Muto Yoneichiro , Kida Sigeo 
Published: July 2006

Abstract
A new series of binuclear copper(II) complexes, [Fsal(=NenNR2)2Cu2X]2+ (R=Me and Et, X=Cl, Br, and OH), were synthesized, where Fsal(=NenNR2)2 indicates the Schiff base prepared from 2,6-diformyl-4-methylphenol and N,N-dialkylethylenediamine (alkyl=methyl(Me) and ethyl(Et)). Two copper(II) ions are connected with the phenolic oxygen and X. The complexes obtained were characterized by elemental analyses, infrared and visible spectra, molar conductivities in methanol, ESR spectra and magnetic susceptibilities. It was found that the stability of the complexes decreases in the order X=OH&gt;&gt;Br&gt;Cl. It was concluded from cryomagnetic measurements that the effect of the bridging group X on spin-coupling decreases in the order OH&gt;&gt;Br&gt;Cl.
Photochemical Reaction of 1,2-Naphthoquinone and Its Derivatives with Xanthene
Authors: Maruyama Kazuhiro , Takuwa Akio 
Published: July 2006

Abstract
In contrast to other o-quinones, photochemical reaction of 1,2-naphthoquinone with xanthene gave a 1 : 1 adduct in which xanthene moiety is attached to position C4, i.e., 1,4-dihydro-2-hydroxy-4-xanthyl-1-ketonaphthalene (2a). The analogous photo-adducts, 2b, 2c, and 2d, were obtained by the photochemical reaction of 3-chloro-1,2-naphthoquinone, 3-bromo- 1,2-naphthoquinone, and 6-bromo-1,2-naphthoquinone with xanthene, respectively. The dynamic aspect of these reactions was also examined using the CIDNP technique and the reaction mechanism was discussed.
The Viscosities of Aqueous Solutions Containing Metal Complexes. III. Iminodiacetato and Methyliminodiacetato Complexes
Authors: Mizutani Kiyoshi , Yasuda Motoo 
Published: July 2006

Abstract
The viscosities of aqueous solutions containing a metal chelate formed with iminodiacetic acid (H2ida) or N-methyliminodiacetic acid (H2mida) were measured with Cannon-Fenske capillary viscometers. Measurements were made in a Shibata viscosity bath maintained at 25±0.01°C. The Jones-Dole viscosity B-coefficient of each bis-ida chelate is lower than that of the corresponding bis-mida chelate, as may be expected. The B-coefficients for the mono-ida and mono-mida chelates were not determined accurately and will not be reported here. The B-value of cisN-[Co(ida)2]− is higher than that of the trans-isomer. This is probably associated with the fact that the cis-isomer interacts with the solvent more strongly than the trans-isomer.
Apparent Molal Volumes of Some Organic Electrolytes in a Dilute Aqueous Solution at 5, 25, and 45°C
Authors: Sakurai Masao 
Published: July 2006

Abstract
The apparent molal volumes, φv, of five series of homologous organic salts of the H(CH2)nCOONa (n=0–6), (CH2)n(COONa)2 (n=0,2,3,4,6,8), H(CH2)nNH3Cl (n=0,2,6), (CH2)n(NH3Cl)2 (n=2,3,6), and H(CH2)n-SO3Na (n=1,2) types in a dilute aqueous solution have been measured by means of a float method as a function of the concentration and the temperature. The coefficients of the deviation of φv from the Debye-Hückel limiting law, bv, are negative for most organic electrolytes. The large positive bv values observed for the sodium oxalate and sodium succinate solutions at 5°C have been attributed to ion-pair formation. The partial molal expansibility of organic ions has been evaluated and interpreted on the basis of the multilayer hydration model proposed by Frank and Wen. The estimation of volume increments per CH2 group suggests that the influences of ammonium ions on the hydrophobic hydration around CH2 groups differ significantly from those of carboxylate ions. The volume change accompanying the substitution of a terminal hydrogen atom with an ionic group has been calculated, and discussed in connection with the overlapping effect of electrostriction in bolaform electrolytes.
The Atomic Absorption Spectrophotometric Determination of Arsenic and Selenium in Premixed Inert Gas(Entrained Air)-Hydrogen Flames with a “Multi-flame” Burner
Authors: Nakahara Taketoshi , Nishino Hirohito , Munemori Makoto , Musha Sôichirô 
Published: July 2006

Abstract
The determination of arsenic and selenium by atomic absorption spectropho tome try was established in premixed inert gas (entrained air)-hydrogen flames using a “multi-flame” burner. Arsenic and selenium electrodeless discharge lamps were used as the sources of radiation. The optimum operating conditions for the atomic absorption measurements for arsenic and selenium at 193.7 and 196.1 nm respectively were investigated. Under the optimum conditions, the sensitivities for 1% absorption were 0.17 and 0.15 ppm for arsenic and selenium respectively. Many other elements and acids interfered with the determination of arsenic and selenium in these low-temperature flames. Most of the interferences were found to be completely eliminated, in appearance, by adding a large amount (2000 ppm) of tin(II) chloride to the sample solutions. Furthermore, a gas-sampling technique for arsenic was studied in order to improve the arsenic sensitivity and in order to eliminate the interferences from other elements. The present method was applied to the determination of arsenic in sulfide ores and steels with satisfactory results.
Peroxo-, Oxo-, and catena-Oxo-Manganese Complexes with N,N′-Ethylenebis(salicylideneimine) Analogues
Authors: Matsushita Takayuki , Yarino Tatsuo , Masuda Isao , Shono Toshiyuki , Shinra Koichiro 
Published: July 2006

Abstract
By the reaction of MnII(salen) (salen=N,N′-ethylenebis(salicylideneiminato) dianion) and its analogues with molecular oxygen in organic solvents, three types of complexes including as structural units the MnIII–O2–MnIII,–(–MnIV–O–)–n, and MnIV=O bonds respectively, have been obtained, and characterized by means of their electronic and infrared spectra, by thermogravimetric analysis, and in terms of their magnetic properties. The lower magnetic moments for [MnIII(salen)]2O2 and –[–MnIV(salen)–O–]–n than those expected have been interpreted in terms of antiferromagnetic interactions. The oxo complex was found to give the catena-oxo complex quantitatively in a DMF, DMSO, or Py solution. The effects of the oxygen partial pressure and the nature of the substituent in the organic part on the complex formation were investigated. A lower partial pressure of oxygen has the advantage of yielding the μ-peroxo complex in a higher yield. A discussion of the reaction mechanism is also included.
The Hydrolysis of Y3+, La3+, Gd3+, and Er3+ Ions in an Aqueous Solution Containing 3 M (Li)ClO4 as an Ionic Medium
Authors: Amaya Toshihiko , Kakihana Hidetake , Maeda Masunobu 
Published: July 2006

Abstract
The hydrolysis equilibria of Y3+, La3+, Gd3+, and Er3+ ions have been studied at 25°C in 3 M (Li)ClO4 by measuring the hydrogen-ion concentration with a glass electrode. All the test solutions containing hydrolyzed species prepared by the addition of alkali were acidified by means of constant-current coulometry. The data, which indicate a slight hydrolysis of the relevant ions, can be explained by assuming the formation of the following complexes: Y(OH)2+, logβ2,1=−17.0±0.1; Y2(OH)24+, logβ2,2=−14.04±0.01; LaOH2+, logβ1,1=−10.04±0.01; GdOH2+, logβ1,1=−8.20±0.01; Er(OH)2+, logβ2,1=−17.4±0.1; Er2(OH)24+, logβ2,2=−13.72±0.01.