bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reaction Kinetics of the Redox Decomposition of Hydroxymercurated Propylene in Aqueous Solution Followed by Time-Sequential NMR Spectroscopy
Authors: Matsuo Masashi , Saito Yasukazu 
Published: July 2006

Abstract
The redox decomposition process of hydroxymercurated propylene in aqueous solution yielding acetone has been followed by time-sequential NMR spectroscopy in situ. No reaction intermediates and reaction products other than acetone were observed. Stoichiometric relationship holds between the reactant and the product during the reaction, which was verified by NMR spectra. The reaction rate was confirmed to be of first order with respect to mercurial. Although the rate was accelerated at higher acidity in solution, a similar rate enhancement took place by addition of neutral salts. At a certain ionic strength, no close linear correlation between the apparent rate constants and proton concentration was observed. In contrast, excellent linear dependence was obtained by the thermodynamic activities of the added electrolytes including acid. Since the apparent rate constant was independent of the concentration of free mercuric ion, a monomolecular mechanism is proposed. Taking into account the rate dependence upon added electrolytes, the redox decomposition of the hydroxymercurated olefins to give carbonyl compounds seems to proceed only when an aquo ligand is removed from the carbon-bonded mercuric ion.
Studies on Microcapsules. XI. Electrophoretic Behavior of Polyphthalamide Microcapsules Containing Aqueous Solution of Bovine Serum Albumin
Authors: Shiba Motoharu , Kawano Yasuaki , Tomioka Suiichi , Koishi Masumi , Kondo Tamotsu 
Published: July 2006

Abstract
Electrophoretic measurements were made on polyphthalamide microcapsules containing aqueous solution of bovine serum albumin and their membrane at various hydrogen ion concentrations. The microcapsules moved toward the anode at any pH, while the membrane migrated to the anode above pH 3.5 and to the cathode below this pH. These results were explained on the assumption that a fraction of albumin molecules is chemically incorporated into the microcapsule membrane through the microencapsulation and that the net electrical charge of the microcapsules is highly dependent on the charge of the outer surface of their membrane.
Photochemical Reactions of Uranyl Ions with Organic Compounds. IV. The Uranyl Fluorescence Quenching by Aliphatic Alcohols
Authors: Sakuraba Shukichi , Matsushima Ryoka 
Published: July 2006

Abstract
The relative rates for uranyl fluorescence quenching by aliphatic alcohols (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and s-butyl alcohols) were measured under various conditions. The rates were increased in proportion to the perchloric acid concentration at pH &lt;1, whereas the rates were smaller and nearly constant at the pH’s between 1–4; thus showing the involvement of both acid-dependent and acid-independent processes. Though the rates for both processes changed with the change in the alcohol structure (the polar substituent effect), the ratio of the two rate constants was nearly constant. The inhibitory effects of cupric ions (as a scavenger for the one-equivalent redox intermediates) suggested that the acid-dependent quenching process involves a two-equivalent redox or two consecutive one-equivalent redox steps between the same partners. The mechanisms of these quenching processes are discussed.
Desorption of Spread Monolayer of 1-Dodecanol into Aqueous Sodium Dodecyl Sulfate Substrate
Authors: Seimiya Tsutomu , Ohbu Kazuo , Nakamura Akio , Sasaki Tsunetaka 
Published: July 2006

Abstract
The process of desorption of dodecanol monolayer into the aqueous sodium dodecyl sulfate (SDS) solutions of varying concentrations was studied by the surface tension measurement. The rate of desorption in its early stage obeyed the simple diffusion law and the plot of logarithms of surface pressure against the square root of time showed a linear relationship. The rate constant of desorption decreased slightly and linearly with an increasing concentration of SDS up to CMC. Beyond CMC it increased rapidly and linearly owing to the increase of dodecanol solubility due to the solubilization. Further, from these rate constants and the surface tension vs. concentration curve, the diffusion coefficient of dodecanol in water and in aqueous SDS solutions, its solubilization in aqueous SDS solution and the partition coefficient of dodecanol between water and SDS micelles were calculated. Critical micelle concentration of sodium dodecyl sulfate was also determined as a break point of desorption constant vs. concentration curve.
Evidence of a Preresonance Raman Effect of the Base Residue in a Nucleic Acid
Authors: Tsuboi Masamichi , Takahashi Seizo , Muraishi Shuichi , Kajiura Teruo 
Published: July 2006

Abstract
The Ramam spectra of β-uridine-5′-phosphoric acid (UMP), its deuterated product, β-uridine-3′-β-uridine-5′-phosphoric acid (UpU), and polyribouridylic acid (poly U) have been observed in their aqueous solutions; and the Raman lines assignable to the phosphate group and to the base residue have been indicated. For UMP, the intensity ratio of a Raman line of the base residue versus that of the phosphate group was found to become greater on changing the exciting line from the 6328 Å line of a helium-neon laser to the 4880 Å line of an argon ion laser. This fact has been taken as indicating that a preresonance Raman effect takes place of the base residue with the effective absorption at 2600 Å.
Solvent Effects on the Spin-Lattice Relaxation Times and Chemical Shifts of N-Methylacetamide and N,N-Dimethylacetamide in Hydrogen Bonding Solvents
Authors: Sato Kazuo , Nishioka Atsuo 
Published: July 2006

Abstract
The proton spin-lattice relaxation and the chemical shift were studied in N-methylacetamide (NMA) and N,N-dimethylacetamide (DMA) in p-dioxane and chloroform. In the p-dioxane solution, it has been found that the self-association of NMA does affect its spin-lattice relaxation, whereas the amide-solvent association does not affect it entirely. This was interpreted in terms of the lifetime of the inter-amide (\simeq10−11–10−12 sec) and the amide-solvent association (much shorter than 10−11–10−12 sec). On the other hand, the effect of the amidesolvent association on the spin-lattice relaxation is pronounced in chloroform, as is the effect of the self-association of NMA. The inter-amide interaction which leads the double-bond character of DMA to be more stable was not reflected distinctly in the concentration dependence of the spin-lattice relaxation times of DMA.
An MO-theoretical Interpretation of the Nature of Chemical Reactions III. Bond Interchange
Authors: Fujimoto Hiroshi , Yamabe Shinichi , Fukui Kenichi 
Published: July 2006

Abstract
The wave functions of a system composed of two mutually-interacting molecules have been expressed in terms of configuration interaction wave functions. The electron configurations have been taken into account with respect to the states of adiabatic interaction, delocalization interaction, and polarization interaction. The electron populations in all of these states have been obtained separately. It has been demonstrated that the adiabatic interaction between two closed-shell molecules can not be the origin of the bond interchange in chemical reactions. The inclusion of charge-transferred states has been shown to be of great importance in explaining the formation of new bonds and the weakening of old bonds in the case of chemical interaction between two molecules. On the basis of the results of numerical calculations on some typical reaction models, the important role of the orbital overlapping interaction of the highest occupied molecular orbital and the lowest unoccupied molecular orbital has been pointed out.
Anodic Oxidation of Aniline in Aqueous Alkaline Solution
Authors: Matsuda Yoshiharu , Shono Akira , Iwakura Chiaki , Ohshiro Yoshiki , Agawa Toshio , Tamura Hideo 
Published: July 2006

Abstract
The anodic oxidation of aniline in an aqueous alkaline solution was studied. The anode materials were Ni, C, Pt, and Pb. An organic deposit (film) was formed on the anodes. The reaction mechanism was estimated through electrochemical measurements, chemical analysis, thin-layer chromatography, and UV, NMR, and IR spectrometries. The de-electronation of lone-pair electrons of the N atom in an aniline molecule caused the radical cation to be produced, (Remark: Graphics omitted.), and this process was the rate-determining step. Some of the radical cations were found to couple together to produce azo-benzene via hydrazobenzene. The other radical cations led to p-amino diphenylamine by head-to-tail coupling; this product was de-electronated again to give the polymer with a quinoid structure.
Mercury Photosensitized Reaction of Deuterio-Propylene Studied by Microwave Spectroscopy
Authors: Sakurai Yuzo , Onishi Takaharu , Tamaru Kenzi 
Published: July 2006

Abstract
The mercury photosensitized reaction of propylene-cis-1-d1 and 1-butene-cis-1-d1 was studied by means of microwave spectroscopy combined with gas chromatography and mass spectrometry. At pressures above 100 mmHg cis-trans isomerization was the main reaction for both the propylene and 1-butene. The number of the absorbed quanta of photons and the number of molecules reacted was almost equal. However, at lower pressures, this condition was not satisfied. At pressures less than 30 mmHg, substantial amounts of the 2-d1 and 3-d1 propylene species were detected in the reaction mixtures. Decomposition of propylene into an allylic radical and a hydrogen atom with subsequent “recombination,” was proposed to account for this observation. Similar results were obtained with 1-butene-cis-1-d1.
Re-examination of the Cycloaddition of Cycloheptatriene with Maleic Anhydride
Authors: Ishitobi Hiroyuki , Tanida Hiroshi , Tori Kazuo , Tsuji Teruji 
Published: July 2006

Abstract
Cycloaddition of cycloheptatriene to maleic anhydride was re-examined and found to produce, in addition to the reported main product anti-tricyclo[3.2.2.02,4]non-6-endo-8,endo-9-dicarboxylic anhydride (1), the exo, exo isomer of this compound (4) and bicyclo[3.2.2]nona-2,6-diene-endo-8,endo-9-dicarboxylic anhydride (5). Evidence for these structures involving the orientation of the cyclopropane ring in 1 and 4 and the configuration of the carboxylic anhydride was provided by PMR spectroscopy using the intramolecular nuclear Overhauser effect and paramagnetic induced shift due to tris(dipivalomethanato)europium(III). The structure assignment by Alder and Jacobs for 1 was found to be correct, but not the one by Schenk et al The difference in free energies of activation leading to 1 and 4 was determined.
Far-infrared Reflection Spectra, Optical and Dielectric Constants, and Lattice Vibrations of Some Fluoride Crystals
Authors: Nakagawa Ichiro 
Published: July 2006

Abstract
The reflection spectra of the crystals of the NaCl structure (LiF, NaF, and NiO), the fluorite structure (CaF2, BaF2, and CdF2), and the rutile structure (MgF2 and MnF2) were measured. The optical and dielectric constants were derived from the measured reflectivities using the Kramers-Kronig transformation. The absorption indices (k) for these crystals are rather large and the peak values of the imaginary dielectric constants amount to 30.0 or more. However, unlike the ferroelectric substances such as oxide perovskites and rutile, these fluoride crystals do not show any anomalous dielectric behaviour. From the real and imaginary dielectric constants ε′(ν) and ε″(ν), the transverse and longitudinal frequencies for the lattice modes are determined. These frequencies are reasonably interpreted on the basis of the crystal structures and satisfy the Lyddane-Sachs-Teller relation. The effective charge on the positive and negative ions and the force constant associated with the short-range elastic force against the ion displacement are obtained for the cubic crystals.
A Comparison of 4-Hydroxynaphthalene-2,7-disulfonic Acid with Chromotropic Acid as a Coupling Component of Azo type Metallochromic Indicators
Authors: Katayama Takeshi , Miyata Haruo , Tôei Kyoji 
Published: July 2006

Abstract
In order to clarify the effect of the hydroxyl group at the 5-position of chromotropic acid on the chelate stabilization, the following six reagents were synthesized by the coupling with 4-hydroxynaphthalene-2,7-disulfonic acid or 4,5-dihydroxynaphthalene-2,7-disulfonic acid(chromotropic acid): 2-(m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(I), 2-(o-methoxy-m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(II), 2-(o-hydroxy-m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(III), 2-(m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(IV), 2-(o-methoxy-m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(V), and 2-(o-hydroxy-m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(VI). The acid dissociation constants of these reagents and the stability constants of their metal chelates with magnesium and calcium were measured by the pH titration method at an ionic strength of 0.10 and at 25°C. From the results obtained, it has become apparent that the hydroxyl group at the 5-position exerts a remarkable influence on the chelation of metal ions with the bidentate ligand, such as 2-(m-sulfophenylazo)-chromotropic acid, but that it has very little effect on those ions with the terdentate ligand, such as 2-(o-hydroxy-m-sulfophenylazo)-chromotropic acid. Such an effect appears even in the bidentate ligand with the methoxy group at the ortho-position of the benzene ring. That is to say, it may be concluded that the effect of the number of the chelate ring formed with a metal ion is preferred to stabilize the metal chelate over the effect of the hydroxyl group at the 5-position in the terdentate ligand.
The Separation of Copper Isotopes by Ion-exchange Chromatography
Authors: Kanzaki Tadao , Kakihana Hidetake 
Published: July 2006

Abstract
A break-through experiment on the separation of copper isotopes was carried out through the use of a cation-exchange resin column. By analysing the experimental results, the approximate values of the single-stage (elementary) separation factors, S6563, were determined. The copper sulphate and copper chloride systems gave significant separation factors (S6563=1.00003–1.00042), but the copper nitrate system gave no isotope separation. These data were analysed in terms of the theory of the two-phase distribution of isotopes previously proposed by one of the present authors (Kakihana). The equilibrium coefficient for isotopic-exchange reaction by complex formation in an external solution (K1=1.00015 for the copper sulphate system, and K1=1.0005 for the copper chloride systems) was estimated.
Metal Complexes Containing Six-Membered Chelate Rings. I. Preparation and Structure of 2,4-Pentanediaminetetraacetato Complexes of Cobalt(III)
Authors: Mizukami Fujio , Ito Haruko , Fujita Junnosuke , Saito Kazuo 
Published: July 2006

Abstract
New cobalt(III) complexes with 2,4-pentanediaminetetraacetate (2,4-ptnta4−) have been prepared. The optically active 2,4-ptnta4− (RR or SS) forms a sexadentate complex and determines the absolute configuration around the metal ion. The meso-2,4-ptnta4− (RS) coordinates to the metal ion as a quinquedentate with a free acetate branch. Such stereospecific formations of sexa- and quinquedentate complexes from the optically active and the meso 2,4-ptnta4− have been attributed to the steric regulation coming from the methyl groups on the α-carbon atoms.
Kinetic Studies of the Electron Transfer Reaction in Iron(II) and Iron(III) Systems. IV, The Reaction in Mixed Solvents of Dimethyl Sulfoxide and Water
Authors: Wada Goro , Aoki Michiko 
Published: July 2006

Abstract
The rate constants, kapp, of the electron transfer reaction between iron(II) and iron(III) in mixed solvents of DMSO and water were measured at various acid and DMSO concentrations at μ=0.50m and 25°C. The kapp decreased linearly with the increase in [DMSO] at a constant [H+] and increased linearly with the increase in 1/[H+] at a constant [DMSO]. The reaction is considered to proceed through two paths: Fe2++*Fe3+→Fe3+*Fe2+ and Fe2++*FeOH2+→FeOH2++*Fe2+, with the rate constants of kO and kH respectively. Both kO and kH were suppressed by the addition of DMSO to water because of the occurrence of molecular association between DMSO and water. The hydration number of DMSO in a very dilute aqueous solution was approximately six, as revealed by the cryoscopic measurements. The suppression of kO and kH was proportional to [DMSO], with a common proportional constant. Consequently, DMSO was deduced to destroy the chains of water molecules connected by hydrogen bondings and to interfere with the ease of hydrogen atom transfer between the reducing and oxidizing iron species. DMSO itself did not serve as a ligand to catalyze the reaction as N-methylacetamide, N,N-dimethylacetamide, and various other anions do.
Mass Spectrometry of Dyes. IV. Electron Impact Reaction of Nitrophenyl Phenyl Ethers and Their Charge Migration
Authors: Yamada Kazutoshi , Konakahara Takeo , Iida Hirotada 
Published: July 2006

Abstract
By the electron impact reaction of substituted 4-nitrodiphenyl ethers (1), the substituents on ring B of (1) cause a reasonable change in the intensity of fragment ions which result from the nitro→ nitrite ester rearrangement. There is a linear correlation of the M+–NO fragment ion intensity of (1) with the ionization potential of the molecules, and with Hammett σ constants. These evidences suggest that the charge of ring B will be free to migrate to ring A in the ion state, even if they are separated by O-atom.
The Reactions of Pyridinium Bromides with Sulfenamides
Authors: Mukaiyama Teruaki , Saigo Kazuhiko 
Published: July 2006

Abstract
It was found that three different types of products, phenylthiomethylpyridinium bromide, ethoxy-bis(phenylthio)-methane and ethyl ethoxy-bis(phenylthio)acetate were obtained by the reactions of pyridinium bromides, such as phenacylpyridinium bromide, acetonylpyridinium bromide and ethoxycarbonylmethylpyridinium bromide, with sulfenamides in ethanol, depending on the nature of the carbonyl carbon of the starting pyridinium bromides.
Group Interactions in Polyelectrolytes. IV. Kinetics of the Alkaline Hydrolysis of Polymethyl Acrylate (Part II)
Authors: Kawabe Hiroshi , Yanagita Masaya 
Published: July 2006

Abstract
Rate equations which express the over-all kinetics of the alkaline hydrolysis of polymethyl acrylate in the presence of a large excess of alkali were derived. The over-all course of this reaction was calculated by using the rate constants given in the previous paper, which were derived from the kinetic data obtained by the reaction in a 29% (v/v) aqueous acetone solution with a slight excess of sodium hydroxide at 55°C. The partially-hydrolyzed polymethyl acrylate (30.6% hydrolyzed) was hydrolyzed by the addition of about sixteen times as much sodium hydroxide as the amount of the ester group; the kinetic data thus obtained were found to be in good agreement with the calculated values.
The Photoreactions of Phenazines via a Semiquinone Radical. The Photoreductive Deacylation of 1- or 2-Acyloxyphenazine
Authors: Inoue Hiroo , Ochiai Tadao , Sugimoto Akira , Imoto Eiji 
Published: July 2006

Abstract
The Photo-irradiation of a solution of 1- or 2-benzoyloxyphenazine in 2-propanol, followed by aeration, affords 1- or 2-hydroxyphenazine, benzaldehyde, isopropyl benzoate, and/or benzoic acid as the reaction products. The spectral change of the solution in the reaction process gives evidence of the fission of the acyl-to-oxygen bond. The addition of ferric chloride or dimethyl sulfate to the reaction system containing 1-benzoyloxyphena-zine in 2-propanol leads to the formation of isopropyl benzoate. When methanol instead of 2-propanol is used as the solvent, methyl benzoate is produced mainly. In cyclohexene as a hydrogen-donating solvent, benzaldehyde and an oxetane are obtained. The irradiation of a solution of 1-benzoyloxyphenazine in t-butyl alcohol or benzene gives no product, and the starting material is recovered in a 90–100% yield. 1-Benzoyloxyphenazhydrin, a photo-reduction intermediate, does not contribute to the formation of benzaldehyde. The intermediary formation of a semiquinoid form during irradiation brings about the fission of the acyl-to-oxygen bond, thus affording the corresponding aldehyde.
Studies on the Baudisch Reaction. IV. The Reaction Mechanism
Authors: Maruyama Kazuhiro , Tanimoto Iwao 
Published: July 2006

Abstract
Mechanism of the Baudisch reaction was investigated using semicarbazide hydrochloride in lieu of hydroxylamine hydrochloride which is one of the reacting components. It was suggested that pyrocatechol-copper-hydroxylamine complex formed as a reaction intermediate is oxidized to o-benzoquinone-copper complex by hydrogen peroxide and one of the carbonyl groups of o-benzoquinone reacts with hydroxylamine hydrochloride to give o-benzoquinone monooxime, i.e. 2-nitrosophenol.
Retardation Effect Induced by Pyridine in the Radical Copolymerization of Styrene and Liquid Sulfur Dioxide
Authors: Enomoto Tsutomu , Iino Masashi , Matsuda Minoru , Tokura Niichiro 
Published: July 2006

Abstract
We have found that the radical copolymerization of styrene and liquid sulfur dioxide (liq. SO2) is retarded when a basic solvent such as pyridine is used; we also investigated the mechanism of the retardation induced by pyridine. The polymerization in pyridine was most strongly retarded when the styrene mole fraction in the feed, [St]0/ ([St]0+[SO2]0), was small (below about 0.2) and when the pyridine mole fraction in pyridine-liq.SO2, [Py]0/ ([Py]0+[SO2]0, was 0.4–0.5. Moreover, from the results in the reaction of the phenylsulfonyl radical (the model radical for the propagating sulfonyl radical) in pyridine or in a pyridine - liq. SO2 mixture, it may be concluded that the end unit of the polymer has the pyridinium sulfonate structure (–SO3−HPy+) and that the retardation may occur by means of the reaction of the propagating sulfonyl radical with the pyridine-SO2 complex.
Conformations of the Esters. IV. The Conformations of Carbamates
Authors: Oki Michinori , Nakanishi Hiroshi 
Published: July 2006

Abstract
It has been confirmed from an infrared spectral study of the C=O, N–H, and N–D stretching regions that primary, secondary, and tertiary carbamates take the s-cis and s-trans conformations with respect to the ester group. The nuclear magnetic resonance spectra and the results of dipole-moment studies support this conclusion.
Syntheses and Reactions of 2-Ethylthio- or 2-Phenylthio-2-cycloalkenones
Authors: Mukaiyama Teruaki , Adachi Takeshi , Kumamoto Takanobu 
Published: July 2006

Abstract
2-Ethylthio- or 2-phenylthio-2-cycloalkenones (five-, six-, or seven-membered ring) were obtained in high yields by the reactions of alicyclic β-ketosulfonium salts with sulfenamides. It was found that dihydrofuran derivatives were obtained in good yields from the sulfonium salts of the cycloalkenones and active methylene compounds.
A Dianthr[14]annulene
Authors: Akiyama Shuzo , Nakagawa Masazumi 
Published: July 2006

Abstract
1,2,3,4,5:8,9,10,11,12-Di(1′,8′-anthr)[14]annulene (III) has been synthesized by the Wittig reaction of 1,8-diformylanthracene (IV) and the bis-ylide (VIII) derived from 1,8-bis(bromomethyl)anthracene (VI).