bluuebunny/crossref_metadata_2025_split huggingface dataset:
Faraday Parameters of the Magnetic Circular Dichroism of Praseodymium Trichloride and Thulium Trichloride in Poly (vinyl alcohol) Film
Authors: Kato Yoshifumi , Nishioka Kyusaku 
Published: July 2006

Abstract
The magnetic circular dichroism and absorption spectra of PrCl3 and TmCl3 in polyvinylalcohol film are measured in the range of 300–700 nm. The absorption bands observed are five for PrCl3, the transitions from the ground state, 3H4, to the excited states, 1D2, 3P0, 3P1, 1I6, and 3P2, of Pr3+, and four for TmCl3, the transitions from the ground state, 3H6, to the excited states, 3F3, 3F2, 1G4, and 1D2, of Tm3+. In order to separate the C term of the Faraday parameters, the temperature variation of the spectra is carried out at room temperature to 77 K. The Faraday parameters are derived from the experiment by the use of three methods; the method of moments, the graphical method, and curve fitting. The characteristics of these methods are discussed, and the uncertainty of the parameters obtained is estimated to be 30% or more. A group-theoretical consideration is applied for the interpretation of the results; this consideration fairly well explains the sign of the C terms obtained for PrCl3, but not for TmCl3.
Properties of Ampholytic Surfactant, N-Alkyl-β-alanine
Authors: Okumura Takeo , Tajima Kazuo , Sasaki Tsunetaka 
Published: July 2006

Abstract
Ampholytic surfactant, N-alkyl-β-alanine, was synthesized and its infrared absorption spectra, surface tension, isoelectric points and critical micelle concentrations of aqueous solutions were measured at various electrolyte concentrations, pH and temperature. The measurements of isoelectric points and infrared spectra confirmed a zwitterionic sructure of N-alkyl-β-alanine. The critical micelle concentrations determined by surface tension measurements are 1.3×10−2 and 9×10−4mol/l respectively for the decyl and dodecyl homologs at 30 °C, the values decreasing with the increase in pH, electrolyte concentration and temperature.
The Crystal Structure of (±)-1-Benzyl-5-phenyl-1-azacycloheptan-4-one Hydrochloride, C19H21NO·HCl
Authors: Fukuyama Keiichi , Shimizu Shozo , Kashino Setsuo , Haisa Masao 
Published: July 2006

Abstract
The crystal structure of (±)-1-benzyl-5-phenyl-1-azacycloheptan-4-one hydrochloride has been determined by the heavy-atom method from three-dimensional X-ray data. The crystals are monoclinic, space group P21⁄c, with four formula units in a unit cell of dimensions: a=5.967(8), b=11.20(1), c=25.96(2) Å, and β=93.8(3)°. The structure was refined by the block-diagonal least-squares method to an R index of 0.076 for 1299 independent observed reflections. The benzyl and phenyl groups are bonded equatorially to the azacycloheptanone ring which takes a chair-like conformation. The chloride ion is hydrogen-bonded to the ring nitrogen atom at a distance of 3.075(4) Å.
Counterion Effect on the Titration Behavior of Poly(itaconic acid)
Authors: Muto Nobuhiko 
Published: July 2006

Abstract
The effect of counterions on the titration behavior of poly(itaconic acid) (PIA) was studied by titrating PIA in aqueous solutions containing alkali metal salts and a tetramethylammonium salt at 25°C. The acidity of the primary carboxylic groups of PIA increases in the order (CH3)4N+&lt;Li+&lt;Na+&lt;K+, whereas that of the secondary carboxylic groups increases with the decrease in the crystallographical radii of the counterions, in the order (CH3)4N+K+&lt;Na+&lt;Li+, in agreement with the results for ordinary polycarboxylic acids. The order K+&gt;Na+&gt;Li+ on the binding strength to the primary carboxylate groups in the first dissociation step is interpreted in terms of the radii of the hydrated cations; it can be ascribed to the stable ring structure of the monoanion of the itaconic acid residue, resulting from the hydrogen bonding between two adjacent carboxylate groups. In apparent complete dissociation, about 80, 60, and 40% of the itaconate residues bind to Li+, Na+, and K+ ions, respectively, when it is assumed that no (CH3)4N+ ions are bound to the carboxylate groups.
Vibration-Rotation Spectrum of Methyl Fluoride II. Analysis of ν3+ν6 Band
Authors: Nakagawa Jim , Suzuki Isao , Shimanouchi Takehiko , Fujiyama Tsunetake 
Published: July 2006

Abstract
The ν2+ν6 band of methyl fluoride has been measured with a high-resolution infrared spectrometer. The molecular constants are obtained with the least-squares method. The effect of the x,y-type Coriolis interaction is discussed and the theoretical spectra are compared with the observed spectrum.
The Decomposition of Hydrogen Peroxide with Metal Complexes. I. The Catalytic Decomposition of Hydrogen Peroxide by the Ammine-Copper(II) Complex Ions in an Aqueous Solution
Authors: Hayakawa Katumitu , Nakamura Sumio 
Published: July 2006

Abstract
The catalytic decomposition of hydrogen peroxide by the ammine-copper(II) complex ions has been studied using kinetic measurements, UV and visible spectroscopy, electron-spin resonance spectroscopy, and polarography. It was found that there were two reaction paths in the catalytic decomposition of hydrogen peroxide. In the first case, a linear part was observed in the plot of the amount of oxygen evolved vs. time. In this case, a brown intermediate was formed which was later found to be a diamagnetic peroxo-copper complex and to contain some of the stable oxygen anion radical just after the mixing of the reactants. The activation energy of the reaction was found to be 23±1 kcal mol−1. In the second case, no linear part was observed in the kinetic curve. In this case, the reaction had a reaction order in hydrogen peroxide varying from the first- to the second-order depending on the initial concentrations of the reactants. The nature of the brown compound and the active species of the reaction is discussed.
Stereochemical Studies of N-Methyl-(S)-alaninatocobalt(III) Complexes with Chiral Tetramines. II. Cobalt(III)-N-Methyl-(S)- and (R)-alaninate-N,N′-Bis(β-aminoethyl)-1), 2(R)-diaminocyclohexane Systems
Authors: Saburi Masahiko , Yoshikawa Sadao 
Published: July 2006

Abstract
The preparation and structural assignments of N-methyl-(S)- and -(R)-alaninatocobalt(III) complexes with N,N′-bis(β-aminoethyl)-1(R),2(R)-diaminocyclohexane (abbreviated as (R)-baetchxn) are described. The Λ-β2-(SSR) isomer has been obtained for Co(N-Me-(S)-ala)((R)-baetchxn)2+ ion. The two isomers, which have been found for the Co(N-Me-(R)-ala)((R)-baetchxn)2+ ion under equilibrium condition at pH 7, are assigned as the Λ-β2(SSR) and Λ-β2(SSS) configurations, taking into account the stereospecific coordination of the (R)-baetchxn. The stereoisomerism of Δ-β2-Co(N-Me-(S)-ala)(trien)2+ ion is also discussed. The structures of two species observed in the PMR measurements of Co(N-Me-(R)-ala)((R)-baetchxn)2+ ion and assigned to Λ-β2(SSR) and Λ-β-(SSS) configurations, respectively, are determined, based on the chemical shifts of α-methine protons of N-methylalaninate moieties.
Aminosugars. XXII. Syntheses and Properties of 6-Deoxy-6-and 3-Deoxy-3-guanidino-d-hexoses
Authors: Yoshimura Juji , Sekiya Tetsuo , Ogura Yoshio 
Published: July 2006

Abstract
Methyl 6-deoxy-6-guanidino-α-d-glucopyranoside, 6-deoxy-6-guanidino-d-galactose, 3-deoxy-3-guanidino-d-allose (7), and 3-deoxy-3-guanidino-d-glucose were synthesized by guanidination of the corresponding amino-sugars. The acetate of 7 was proved to exist in a bicyclic structure; 2′,4′,6′-tri-O-acetyl-d-allopyrano[l′,2′,3′;4,5,6]-2-acetylimino-1,3-diacetyl-perhydropyrimidine, whereas others exist as the usual pyranoses. Properties of the new compounds and the synthetic methods were examined.
A Macrocyclic Enzyme Model System. Acyl Transfer from p-Nitrophenyl Carboxylates to Paracyclophane Oxime
Authors: Murakami Yukito , Sunamoto Junzo , Kano Koji 
Published: July 2006

Abstract
The deacylation reactions of p-nitrophenyl carboxylates by 10-hydroxy-11-hydroxyimino[20]paracyclophane (Oxime-I) have been investigated in an alkaline aqueous acetone. Oxime-I was acylated by p-nitrophenyl laurate (PNPL) and decanoate (PNPD), but was not affected by p-nitrophenyl acetate (PNPA) and hexanoate (PNPH). Meanwhile, 2-hydroxycyclodecanone oxime (Oxime-II) and acetoxime (Oxime-III) did not undergo any reaction with all of the present carboxylic esters under the same conditions. These results suggest that the acylation reactions of Oxime-I with PNPD and PNPL proceed primarily through incorporation of the substrates into the cyclic oxime cavity. The formation of an intra-complex was also suggested by an evidence that the copper(II) ion markedly retarded the reaction rate of PNPL with Oxime-I below the catalyst-absence level. The binding constant for PNPL with Oxime-I was considerably large in comparison with the usual micelle-substrate or synthetic polymer-substrate complexes. On the basis of thermodynamic parameters for the binding and the subsequent acylation, the driving force for the incorporation and the geometry of the intra-complex have been discussed.
Perkin Synthesis of Bromobenzalphthalides. Their Reactions with Amines and Hydrazine
Authors: Islam A M , Khalil A M , El-Maghraby A A 
Published: July 2006

Abstract
The isomeric 5-bromo- and 6-bromo-3-benzalphthalides were prepared by condensation of 4-bromophthalic anhydride with phenylacetic acids. The reaction of such isomeric bromobenzalphthalides with primary aromatic amines give the corresponding bromobenzalphthalimidines. Bromophthalazinone derivatives were obtained in good yields by the reatcion of bromobenzalphthalides with hydrazine hydrate.
Gel Filtration of Starch–Iodine System
Authors: Kodama Makoto , Sasaki Tsunetaka 
Published: July 2006

Abstract
The well-known starch-iodine reaction was taken up to study the applicability of gel filtration to the problem of physical chemistry. Gel filtration by the frontal analysis was carried out, the following results being obtained. (1) Soluble starch- and amylose–iodine systems give elution volumes of iodine containing constituents (Vsi and Vai, respectively) distinctly smaller than that of iodine, which decrease with increasing concentration of iodine, C, and starch, approaching the elution volume of starch. This is a direct experimental evidence of starch–iodine complex formation. (2) An equation derived for Vsi vs. C and Vai vs. C relations holds satisfactorily. The concentration of free iodine in equilibrium with the complex is calculated by the equation. (3) Presence of iodide ion facilitates the complex formation, but its decomposition is instantaneous when it is isolated from free iodine. (4) Some iodide ions are found to be incorporated in the complex. (5) Amylopectin also forms a complex with iodine, but the amount of iodide incorporated is not large. (6) Potentiometric titration of starch with iodine exhibits a similar behavior to the gel filtration measurement.
The Crystal Structure of the Cupric Complex with Succinimide. II. Potassium Tetrakis(succinimidato)copper(II) Hexahydrate and Lithium Tetrakis(succinimidato)copper(II) Monohydrate
Authors: Tsukihara Tomitake , Katsube Yukiteru , Fujimori Kumiko , Kawashima Kiyoshi , Kan-Nan Yoshiaki 
Published: July 2006

Abstract
As part of a program for the study of the crystal structure of copper(II)-complex with succinimide, the crystal structures of potassium tetrakis(succinimidato) copper(II) hexahydrate and lithium tetrakis(succinimidato) copper(II) monohydrate have been determined by means of X-ray analysis. In the potassium-salt, the copper atom has a square planar coordination and the potassium ion has a trigonal prismatic environment formed by six oxygen atoms. In the lithium-salt, the copper atom has a flattened tetrahedral coordination, and each lithiun ion is tetrahedrally surrounded by four oxygen atoms. The conformational difference between the complex anion of the potassium-salt and that of the lithium-salt seems to result from the different sizes of the alkali-metal ions.
Studies of the π–π* Absorption Bands of p-Quinones and o-Benzoquinone
Authors: Kuboyama Akira , Matsuzaki Sanae , Takagi Hiroshi , Arano Hiroshi 
Published: July 2006

Abstract
The π–π* absorption spectra of p-benzoquinone, α-naphthoquinone, anthraquinone, and their derivatives, mainly in n-heptane up to the vacuum UV region, were obtained. On the other hand, MO calculations of the n-electronic systems of these p-quinones and o-benzoquinone were carried out by means of the P-P-P method. The π–π* absorption bands of these quinones could be favorably assigned on the basis of the calculated results.
Effect of Cesium Counterion on the ESR Spectrum of Tetracyanoethylene Anion Radicals
Authors: Ogasawara Masaaki , Inaba Seizo , Yoshida Hiroshi , Hayashi Koichiro 
Published: July 2006

Abstract
Evidence was obtained by ESR for the ion-pair formation between the tetracyanoethylene anion radical and the cesium counterion in tetrahydrofuran. The hyperfine lines of the ESR spectrum of cesium tetracyanoethylenide were exceptionally broad at high salt concentrations in tetrahydrofuran, while they were remarkably narrowed by the addition of a small amount of DMF or triglyme (cation-solvating agents) or by replacing the counterion with the tetra-n-butylammonium ion. This indicates that the broad linewidth is due to the unresolved hyperfine splitting of the cesium counterion. In addition, the concentration dependence of the ESR spectrum indicates that the line broadening is to be interpreted not only in terms of the Heisenberg spin exchange, but also in terms of the equilibrium between the ion-pair and the free ion. The cesium hyperfine coupling constant was estimated by simulating the line shape to be 40 m Gauss in the ion-pair state between the tetracyanoethylene anion radical and the cesium ion in the tetrahydrofuran solution.
Molecular Orbital Study on the H2O–HCl System
Authors: Shibata Shuzo , Hirota Fumihiko , Ota Yukio 
Published: July 2006

Abstract
The hydrogen bonded system of H2O–HCl was studied by the CNDO/2 method. Calculation of the potential energy for the system showed that the complex of H2O–HCl is considerably stable. The equilibrium structure of the complex and its charge distribution were also investigated.
The Solvent Extraction of the Copper–Pyrocatechol Violet Chelate with Tridodecylethylammonium Bromide
Authors: Shijo Yoshio 
Published: July 2006

Abstract
The solvent extraction of the copper–Pyrocatechol Violet chelate with tridodecylethylammonium bromide (abbreviated TDEA) in benzene as an ion-association system has been investigated by the spectrophotometric method. The copper–PV–TDEA complex can be extracted into such aromatic hydrocarbons as benzene, toluene, and xylene, but not into such polar solvents as n-butanol, ethyl acetate, methylisobutylketone, and nitrobenzene. When a sample solution containing copper and PV, the pH of which has been adjusted to 7.5–8.5, is shaken with TDEA in benzene for 10 s, the maximum extraction of the ternary complex is obtained. The extractability of the complex from 50 ml of an aqueous solution into 10 ml of benzene is 98.3% under the optimum conditions. The absorbance and stability of the complex increase upon the addition of a small amount of ethanol to the extracted layer. Beer’s law is obeyed up to 6.5 μg copper per 10 ml of benzene, and the molar absorptivity of the complex is 7.9×104 cm−1·mol−1·l at 663 nm. The composition of the complex is confirmed to be Cu:PV: TDEA=1: 2: 2 by the continuous variation method. A structure for the complex is proposed.
The Novel Synthesis of l-Hydroxyproline from d-Glutamic Acid
Authors: Eguchi Chikahiko , Kakuta Akio 
Published: July 2006

Abstract
l-Hydroxyproline (1) and d-allo-hydroxyproline (2) were synthesized from d-glutamic acid (3) using the asymmetric center of 3 as that at C4 of 4-hydroxyproline. When the aqueous solution of 1 or 2 was heated at 200 °C for 2 hr, a solution in the equilibrium state, containing 55% of 1 and 45% of 2, was obtained. From this mixture, 1 was obtained by fractional crystallization.
Oxidation by Iron(III) Complexes. VIII. The Reactions of Iron(III) Chloride with Toluene and Substituted Toluenes
Authors: Inoue Hiroo , Izumi Megumu , Imoto Eiji 
Published: July 2006

Abstract
The thermal and photochemical reactions of toluene with anhydrous iron(III) chloride in the solid state result in nuclear chlorination. In a homogeneous system, a side-chain reaction occurs under irradiation with light, although no product is obtained in the thermal reaction. The addition of water to the iron(III) chloride–toluene system in the range of the molar ratio of 1–5 changes the course of the photochemical reaction; in the water/iron(III) chloride molar ratios of 1–1.7, 3, and 4–5, the main products are the diphenylmethane-type compound, o- or p-chlorotoluene (o&gt;p), and benzyl chloride respectively. Pyridine as a ligand acts to give benzyl chloride selectively. The Mössbauer data of the FeCl3/nH2O solid show that the arrangement of the Cl− ion around the Fe(III) ion changes upon the addition of water. The thermal and photochemical reactions of p-methoxytoluene with anhydrous iron(III) chloride give 2,2′-dimethoxy-4,4′-dimethylbiphenyl by oxidative aryl coupling. Water inhibits the aryl coupling reaction.
Reaction of 2-BenzoyIamino-2-methylpropionamidine and 2-Benzoylaminoacetamidine with Bifunctional Compounds
Authors: Uchida Hiroaki , Chinone Akiko , Ohta Masaki 
Published: July 2006

Abstract
The reaction of 2-benzoylamino-2-methylpropionamidine (III) with 1,3-bifunctional compounds was investigated in connection with studies on 2-benzoylaminoacetamidine(I). In case of the reaction of III an appreciable amount of 5,5-dimethyl-2-phenylimidazolin-4-imide (VIII) was formed, the yield of 2-(1-benzoylamino-1-methylethyl)-4,6-dimethylpyrimidine (VI) being low. On the other hand, III reacted with ethyl acetoacetate to give 2-(1-benzoylamino-1-methylethyl)-4-hydroxy-6-methylpyrimidine (IX) in about 50% yield besides VIII. Both III and I were made to react with ethoxymethyleneacetylacetone to yield 5-acetyl-2-(1-benzoylamino-1-methylethyl)-4-methylpyrimidine (X) and 5-acetyl-2-(N-benzoylaminomethyl)-4-methylpyrimidine (XI), respectively. Reaction of I with ethoxymethylenemalononitrile gave 4-amino-2-(N-benzoylaminomethyl)-5-cyanopyrimidine (XII), but did not proceed with benzoin, malondialdehyde, tetraethoxypropane or phenacyl bromide.
Studies of the Equilibria between Tetraarylallyl-type Radicals and Their Dimers
Authors: Watanabe Kohji , Yamaughi Jun , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo 
Published: July 2006

Abstract
Tetraarylallyl-type radicals are stable radicals. In these series, TPA is obtained as radical crystals. However, BDA, BDAA and DDA are obtained as diamagnetic dimerized substances. These are partially dissociated in solution. These can be detected in solution by ESR and optical spectra measurements of these radicals about the equilibrium between the radical monomer and its dimer. The equilibrium constants and the energy of the formation of the dimer are thus determined. The order of the magnitudes of the dimer’s formation energies can be explained in terms of the frontier electron densities of the bond-forming positions of radicals.
The Fractionation of Tritiated Water in an Equilibrium between Organic Hydrates and Their Aqueous Solutions
Authors: Tanaka Haruhiko , Kado Tsutomu , Negita Hisao 
Published: July 2006

Abstract
The fractionation of the tritiated water (HTO) was examined during the crystallization of hydrates, such as (COOH)2·2H2O, (COOK)2·H2O, Cu(HCOO)2·4H2O, and Sr(HCOO)2·2H2O. The dilution of HTO in the organic salts was found to be comparable to that in inorganic salts observed previously. The fractionation of HTO was explained on the basis of an ionic process in an aqueous solution, and the crystal growth mechanism, in a way similar to that described in a previous paper. On the contrary, a considerable dilution was observed for oxalic acid dihydrate. The proton effect on the fractionation in both the ionic and dehydration processes was also discussed.
The Kinetics and Mechanisms of the Reactions of Nitric and Nitrous Acids with Hexaaquochromium(II) Ions
Authors: Ogino Hiroshi , Tsukahara Keiichi , Tanaka Nobuyuki 
Published: July 2006

Abstract
Stoichiometric and kinetic investigations of reactions of the nitric and nitrous acids with hexaaquochromium(II) ions have been carried out in acidic media. The stoichiometries of these reactions found in this work were consistent with the mechanisms proposed by Swaddle,1) in which one mole of nitric acid reacts with four moles of chromium(II) and one mole of nitrous acid reacts with two moles of chromium(II). For the former reaction, it was found that the two-electron reduction of nitric acid by chromium(II) is rate-determining and that the rate constant was 2.2×102 M−1 s−1 at 25 °C and at an ionic strength of 1.0 (NaClO4). For the latter reaction, it was found that the one-electron reduction of nitrous acid by chromium(II) is rate-determining and that the rate constant was 4.5×10−3 M−1 s−1 at 25 °C and at an ionic strength of 1.0 (NaClO4). The rates of the reactions of chromium(II) with anionic species of the parent acids, NO3− and NO2−, were too slow to be detected under the present experimental conditions.
Fundamental Studies on Palladium Catalysts. IX. Characteristics of Hydrogen Sorption and Hydrogenation Activity of Supported Palladium Catalysts
Authors: Yamabe Tsunekichi , Shirono Katsuhiro , Uehara Masaru , Suzuki Sadao 
Published: July 2006

Abstract
The sorption of hydrogen and the hydrogenation of ethylene on palladium/silica–alumina catalysts with palladium contents of 0.58–4.5 wt% were investigated. It was found that Vx (the amount of molecularly-adsorbed hydrogen) and Vz (that of dissociatively-adsorbed hydrogen) increase, while Vy (that of dissolved hydrogen) decreases, with the increase in the specific surface area of palladium, and that the saturated value of Vz is proportional to the amount of chemisorbed carbon monoxide. It was also shown that the increase in the palladium content results in a growth of the palladium crystallites, their number staying approximately constant. The rate of ethylene hydrogenation was found to be first-order with respect to hydrogen and zero-order with respect to ethylene over the temperature range of −20–20 °C. The activity was proportional to the surface area of palladium, and the activation energy was almost constant for these catalysts.
Polymerization of Vinyl Compounds with Hydridodinitrogentris(triphenylphosphine)cobalt(I)
Authors: Kubo Yoichiro , Yamamoto Akio , Ikeda Sakuji 
Published: July 2006

Abstract
The kinetics of polymerization of vinyl compounds (acrylonitrile, methacrylonitrile, and methyl methacrylate) with hydridodinitrogentris(triphenylphosphine) cobalt(I), CoH(N2)(PPh3)3 1 (PPh3: triphenylphosphine) was studied. By comparison with previous studies on the decomposition of 1 in the presence of vinyl compound a polymerization mechanism involving slow initiation followed by rapid propagation and unimolecular termination was proposed. The effects of concentration of monomer and of added triphenylphosphine on the molecular weight of the polymer were studied. The result of copolymerization was explained by the competitive coordination between the monomers involved. Poly(methyl methacrylate)s obtained by 1 in bulk and the solvent were all rich syndiotactic fraction.