bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Crystal Structure of 2,2′-Bipyridinium Tetrabromocobaltate(II)
Authors: Koda Shigetaka , Ooi Shun’ichiro , Kuroya Hisao 
Published: July 2006

Abstract
The crystal structure of 2,2′-bipyridinium tetrabromocobaltate(II) has been established by successive Fourier analyses. The atomic parameters were refined by least-squares techniques, using the three-dimensional X-ray data, to an R factor of 0.127 for 1461 non-zero reflections. The complex crystallizes in the space group P21/c with four formula units in the unit cell with dimensions of a=8.42, b=14.00, c=12.88 Å, and β=98.7°. The crystal consists of slightly distorted tetrahedral [CoBr4]2− anions and 2,2′-bipyridinium cations, in which two pyridinium ring planes are inclined toward one another at an angle of 39°. The two N+–H groups in the cation participate in N+–H···Br− type hydrogen bonds (N···Br=3.23 Å and 3.31 Å). The mean value of the four Co–Br bond lengths is 2.42 Å.
Sound Velocity in Aqueous Solutions of Lead Nitrate and Ammonium Iodide
Authors: Nomoto Otohiko , Endo Harumi 
Published: July 2006

Abstract
The sound velocity in aqueous solutions of NH4I and Pb(NO3)2 is investigated in relation to the temperature and the concentration. In both solutions the V(T) curves show maxima Vp at the peak temperature Tp the Tp shifting to a lower temperature with an increase in the concentration. While the shift of Tp is sensibly linear with the concentration for Pb(NO3)2, the curve for NH4I is almost constant up to 25 wt%, though it decreases linearly above this concentration. This corresponds to the rather abrupt change in the degree of dissociation obtained from the conductivity data. The constancy of Tp below 25wt% is tentatively explained on the basis of Danford and Levy’s X-ray diffraction study which concluded that NH3 is included in cavities of the water framework and that the framework molecules are partially replaced by NH3.
Studies of the Pyrolysis of Triglycerides
Authors: Kitamura Kazuo 
Published: July 2006

Abstract
The pyrolysis of triglycerides (trilaurin and tripalmitin) in an atmosphere of nitrogen at 300–700°C has been attempted. Fatty acids, acrolein, ketones, and olefins have been identified as pyrolysis products. As intermediates of the pyrolysis, unsaturated glycol difatty acid esters and acid anhydrides were also detected. These results suggest a reaction mechanism of the pyrolysis involving the above compounds.
A Novel Synthesis of 4H-1,3-Thiazin-4-one Derivatives
Authors: Yokoyama Masataka 
Published: July 2006

Abstract
4H-2,5,6-Substituted-2,3-dihydro-1,3-thiazin-4-ones were synthesized by the condensation reaction of β-alkylthio-β-mercapto-α-cyanoacrylamide with a variety of ketones and aldehydes in an acidic medium.
The Radical Polymerization and Copolymerization of Triallylidene Sorbitol with Styrene or Acrylonitrile
Authors: Oughi Tatsuro , Yagughi Yoshikazu , Oiwa Masayoshi 
Published: July 2006

Abstract
The polymerization of triallylidene sorbitol (TAS) and the copolymerization of TAS with styrene (St) or acrylonitrile (AN) have been carried out, using benzoyl peroxide as an initiator at 80°C. They were kinetically investigated in relation to the degradative or effective chain transfer by the allylidene group, and by the cyclization by three double bonds. The results can be summarized as follows: 1) the relation among the rate of polymerization, Rp, the initiator concentration, (I), and the monomer concentration, (M), can be expressed by the following equation: ((I)/Rp–a)−1=A(M)+B, where a, A, and B are constant; 2) the ratio of the rate of unimolecular cyclization to the total rate of bimolecular propagation and the chain transfer of uncyclized radical was estimated to be 0.291; 3) the degree of polymerization depends on the monomer concentration, but not on the initiator concentration; 4) the rates of copolymerization decrease markedly with an increase in the TAS or tricrotylidene sorbitol (TCS) mole fraction in monomer mixtures; and 5) the following monomer reactivity ratios were ascertained: St(M1)-TAS(M2)r1=4.60, r2=0.13, AN(M1)-TAS(M2) r1=0.70, r2=0.26, St(M1)-TCS(M2) r=2.31, r2=0.39, AN(M1)-TCS(M2) r1=0.30, r2=0.36. The Q and e values for the functional group were calculated from the above values as 0.05 and −0.08 (TAS), and 0.10 and −0.25 (TCS) respectively.
The Hofmann Rearrangement. I. Kinetic Substituent Effects of ortho-, meta-, and para-Substituted N-Bromobenzamides
Authors: Imamoto Tsuneo , Tsuno Yuho , Yukawa Yasuhide 
Published: July 2006

Abstract
The kinetic substituent effects on the Hofmann rearrangements of ortho-, meta-, and para-substituted N-bromobenzamides were studied in an aqueous sodium hydroxide solution. The rate constants of the meta- and para-derivatives were correlated by means of our equation:
logk⁄k0=−2.39(σ0+0.41Δ\barσR+)+0.002
The reaction rates of ortho-derivatives were found to be 2–20 times faster than those of the corresponding para-derivatives. The reaction mechanism of this rearrangement was discussed in terms of LFER, the ortho/para rate ratios, and the activation parameters; as a result, the concerted mechanism (the participation of the phenyl group in electron-deficient nitrogen at the transition state) was favored rather than the two-step mechanism. The similarity of the reaction mechanism of the Hofmann to the Lossen rearrangement was also shown on the basis of LFER.
Photochemical Reaction of 3,4-DiphenyIsydnone
Authors: Huseya Yoshiharu , Chinone Akiko , Ohta Masaki 
Published: July 2006

Abstract
In a recent communication, we proposed 1H-1,3-diphenyldiazirine for the photolysis product of 3,4-diphenylsydnone. However, it was found later that the product was identical with the already known 2,4,5-triphenyl-1,2,3-triazole. In this paper, details of the photolysis of 3,4-diphenylsydnone and identification of the product are described. The formation of triazole derivative by the photolysis of 3,4-diphenylsydnone seems to be interesting. The reaction mechanisms are discussed.
Aroyloxy-Radikal. Die Aktivierungsenergien bei der Kohlendioxyd-Abspaltung und bei der Anlagerung an Benzol-Doppelbindung
Authors: Suehiro Tadashi , Ishida Mototoshi 
Published: July 2006

Abstract
Bei der Einwirkung von Trityl-Radikal auf Benzoylperoxyd-carbonyl-14C,p-Chlorbenzoylperoxyd-carbonyl-14C bzw. auf p-Methoxybenzoylperoxyd-carbonyl-14C in Benzol bei 25°C und 45°C wurde die Ausbeute an Kohlendioxyd, Tetraphenylmethan und an Benzoesäure-trityl-ester nach der Isotopen-Verdünnungsmethode bestimmt. Aus der Abhängigkeit der Ausbeute von Temperatur wurden die relativen Aktivierungsenergien der Aroyloxy-Radikale bei der Kohlendioxyd-Abspaltung (E1,r) und bei der Anlagerung an die Benzol-Doppelbindung (E4,r) im Vergleich zu der bei der Kombination mit Trityl-Radikal (E5) errechnet. Die relativen Aktivierungsenergien waren wie folgt: Bei Benzoyloxy-Radikal E1,r=12.9 Kcal/Mol und E4,r=6.3 Kcal/Mol; bei p-Chlorbenzoyloxy-Radikal E1,r=13.5 Kcal/Mol und E4,r=6.2 Kcal/Mol; bei p-Methoxybenzoyloxy-Radikal E1,r=14.7 Kcal/ Mol und E4,r=6.1 Kcal/Mol.
Configuration Interaction Studies on Contact Shift and Contact Nuclear Spin-Spin Coupling in Paramagnetic Transition Metal Complexes
Authors: Katô Hajime , Kato Hiroshi 
Published: July 2006

Abstract
The magnitude of the contact shift for hydrogen nuclei is directly related to the unpaired electron density, ρH, on the proton. The mechanism by which the unpaired electrons transfer from the transition metal d-orbitals to the ligand orbitals is studied on the basis of the method of intergroup (ligand and metal) configuration interaction. The ρH is given as a sum of two terms, ρHP and ρHD, due to the spin-polarization mechanism and the spin-delocalization mechanism respectively. When the interaction between metal and ligand is restricted to a localized bond N–M, such as nickel(II)-benzylamine, ρHP\simeq−(CMm)2|χH(0)|2πHN&lt;NM|NM&gt;⁄3\simeq0.001–0.0001 (Here πHN is the mutual atom(H)-atom(N) polarizability.). When the interaction between metal and ligand is not restricted to a special localized bond, as in metalocene, ρHP\simeq−(CMm)2|χH(0)|2πHH&lt;HM|HM&gt;⁄3\simeq0.01–0.001. The spin delocalization term has the order of magnitude of: ρHP\simeq−(CMm)2(βMN)2|χH(0)|2(PHN)2⁄2(δE)2 (Here PHN is the bond order between the H and N atomic orbitals.). If the proton H is not directly bonded to the atom N, ρHD\simeq0.0001. If the proton H is directly bonded to the atom N, ρHD\simeq0.001. By disregarding the contributions smaller than the order of magnitude O(S2), the formulation of the contact nuclear spin-spin coupling constant is derived. The most dominant term is identical with the formula which was derived by Pople and Santry for singlet free-ligand molecules.
Studies of the Surface of Titanium Dioxide. I. The Effect of Reduction by Hydrogen on the Heat of Immersion in Water
Authors: Iwaki Toru , Miura Masaji 
Published: July 2006

Abstract
The reduced state of the surface of titanium dioxide was studied by the measurement of the heat of immersion in water. When the titanium dioxide was reduced by hydrogen at 500°C, the heat value decreased appreciably with an increase in the pressure of hydrogen, in contrast to the increase in the heat value due to the reduction by an organic contaminant. The heat value was not restored to the original state even after oxygen had been introduced at 500°C to the reduced sample, while the color of the sample returned to white from bluish gray. These phenomena were interpreted by examining the adsorption of water, the reduced amount, and the reflectance spectrum.
Positron-lifetime Measurements in Polymerizing Organic Solids
Authors: Ito Yasuo , Okuda Kouji , Tabata Yoneho 
Published: July 2006

Abstract
The measurement of the e+ lifetime in solid monomers during polymerization has been carried out. The mechanism of solid-state polymerization can be analyzed by the measurement of the lifetime of positrons and the amounts of positronium formed. This method was applied to the solid-state polylmerization of acrylamide. It was found from the experiments that the lifetime spectrum changes remarkably in the induction period of polymerization. The decrease in the annihilation rate λ2 was interpreted in terms of the formation of a larger free volume during polymerization. The intensity of the slow component was also observed to decrease in the induction period of polymerization. The accumulation of active species which capture positrons and the decrease in the number of free volumes were suggested as explanations of the phenomena.
Radiotracer Studies on Adsorption of Surface Active Substance at Aqueous Surface. III. The Effects of Salt on the Adsorption of Sodium Dodecylsulfate
Authors: Tajima Kazuo 
Published: July 2006

Abstract
The adsorbed amounts were measured on the surface of aqueous solutions containing tritiated sodium dodecylsulfate (TSDS) and varying amounts of NaCl by the direct radiotracer method. The surface tensions were also measured for the same solutions by the drop-volume method. The Gibbs adsorption isotherm, derived without assuming the adsorption of the chloride ion, was applied, and the amounts of adsorption were calculated for both dodecylsulfate and chloride ions. The observed amounts of dodecylsulfate adsorption were confirmed to be in good agreement with those calculated, and the calculated amounts of chloride adsorption turned out to be nearly zero or slightly negative, which is usually theoretically assumed because of the ionic repulsion due to the adsorbed dodecylsulfate. Further, the adsorption of the dodecylsulfate ion attained a constant and saturate value beyond a certain concentration (SAC) below the critical micelle concentration (CMC). The logarithms of SAC were found to vary linearly with the logarithms of CMC for the range of salt concentration studied. The value of SAC being in a close relation with the surface phenomena is considered to be another measure of the surface activity of surfactants.
Effects of Pressure on the Chemical Properties of Solid Surfaces. V. The Surface Acidity of the Compressed Aluminum Sulfate
Authors: Kawakami Takeshi , Konno Akihiro , Ogino Yoshisada 
Published: July 2006

Abstract
In order to clarify the mechanism of the acidity change due to compression, aluminum sulfate was compressed under various pressures ranging from 0 to 4200 kg/cm2 and at a temperature of 20, 65, or 80°C, and the surface acidity and the structure of these samples were measured. It was found that the acidity change due to compression was proportionate to the protonic acid. Lewis acid was made to appear only by heating the sample at temperatures higher than 90°C. Further, for the purpose of increasing the surface acidity, the compression of the sample at lower temperatures was found to be more effective than the compression at higher temperatures. In addition to the spectroscopic data, the results of DTA and TGA experiments supported the idea that the observed acidity change resulted from the distortion of the structural unit of aluminum sulfate.
Ionization of Some Quinones by the Interaction with Aliphatic Amines
Authors: Yamaoka Tsuguo , Nagakura Saburo 
Published: July 2006

Abstract
The interactions of alkylamines with p-benzoquinone and its chloro-derivatives in ethanol and ethyl ether were studied by the rapid scan spectrophotometric method. The formation of anion radicals was found spectroscopically for the n-butylamine-p-benzoquinone, n-butylamine-chloranil, dimethylamine-p-benzoquinone, and tri-n-butylamine-chloranil systems. The rates of ionization reactions were determined to be 0.30 sec−1 mol−1 (at 253.7°K), 0.89 sec−1mol−1 (at 222.7°K), and 1.39 sec−1mol−1 (223.2°K) for the tri-n-butylamine-chloranil, n-butylamine-chloranil, and n-butylamine-p-benzoquinone systems, respectively. The activation energy for ionization of the tri-n-butylamine-chloranil system in ethanol was estimated to be 0.57 kcal/mol.
Structures of Bicyclo[2.2.2]octene and Bicyclo[2.2.2]octadiene as Studied by Gas Electron Diffraction
Authors: Yokozeki Akimichi , Kuchitsu Kozo 
Published: July 2006

Abstract
Bicyclo[2.2.2]oct-2-ene and bicyclo[2.2.2]octa-2,5-diene have been investigated by gas electron diffraction. They are found to have C2v symmetry in respect of the thermal-average nuclear positions. The structural parameters with estimated limits of error (the γg bond lengths and the angles difined in the γα structure) determined by a leastsquares analysis on the molecular intensities are as follows for octene and octadiene, respectively: C(sp3)–C(sp3) (weighted average of the C1–C7, and C7–C8 bonds)=1.549±0.008 and 1.553±0.017 Å, C(sp2)–C(sp3)=1.509±0.015 and 1.521±0.008 Å, C(sp2)–C(sp2)=1.341±0.008 and 1.339±0.005 Å, C(sp3)–H (average)=1.112±0.008 and 1.105±0.012 Å, ∠C–C=C=114.2±0.6° and 113.5±0.5°, The dihedral angle θ between the C1–C2–C3 C4 and C1–C6–C5–C4 planes=121.2±2.1° and 123.4±2.2°, ∠C=C–H=122.4±6.0° and 125.5±4.0°, ∠H–C–H=109.2±4.0° and 111.3±7.0°. A conformational analysis based on an empirical prescription of strain energies, similar to that of Jacob et al., and a molecular-orbital analysis (CNDO/2) have accounted for the observed bond angles given above to within 1.5°.
Some New Oxygenated Cobalt Complexes
Authors: Munakata Megumu 
Published: July 2006

Abstract
Cobalt(II) complexes with ornithine, 2,4-diaminobutyric acid and 2,3-diaminopropionic acid were studied as new oxygen complexes. The former complex was reversibly, while the latter two complexes were irreversibly oxygenated at room temperature. These oxygenated complexes were diamagnetic and showed electronic absorption spectra similar to that of oxygenated cobalt histidine complex, and they were assumed to be O2-bridged binuclear complexes, L2Co–O2–CoL2 (L: ligand). Cobalt and O2 of the binuclear complexes existed in the state of Co(III) and O22−, respectively. Thermodynamic measurements showed that oxygenation was an exothermal process, and deoxygenation an endothermal one. The reversibility correlated with the reduction potential of the central cobalt(III) ion and the enthalpy change of the oxygenation. Easier deoxygenation corresponded to more positive reduction potential and to smaller enthalpy change.
The Photonuclear Reactions Leading to 24Na and 28Mg
Authors: Saito Tatsuya 
Published: July 2006

Abstract
The photonuclear reaction yields of 24Na and 28Mg in magnesium, aluminum, silicon, phosphorus, and sulfur were obtained at energies between 20 MeV and 250 MeV by the induced radioactivity method. The 12C(γ,n)11C yield was used as a standard for the beam monitor. The excitation curves of the 27Al→24Na, 28Si→24Na, Si30→28Mg, 31P→24Na, 31P→28Mg, 32S→24Na, and 32S→28Mg reactions were obtained from the yields by the photon-difference method. Each of these excitation functions indicates a peak in the 50–70 MeV energy range, except in the case of the sulfur target, in which the peak is due to the contribution from the compound-nucleus process. The interaction of photons with nuclei at photon energies exceeding the peak energy region probably does not lead to the formation of the compound nucleus. In the energy range from 70 MeV up to 150 MeV, the cross sections are due to the contribution from the quasi-deuteron process. At energies above 150 MeV and up to 250 MeV, the quasi-deuteron and pion production processes compete. In the high-energy photonuclear reaction mechanisms, the quasi-deuteron and pion production processes must be considered at the initial cascade process, but the evaporation process may be considered after the cascade process.
Conductometric Determination of Ion-pair Formation Constants of Tris(ethylenediamine)cobalt(III) Ion with Maleate and Fumarate Ions in Aqueous Solutions
Authors: Katayama Shunzo , Tamamushi Reita 
Published: July 2006

Abstract
The conductance behavior of mixtures was investigated for the systems tris(ethylenediamine)cobalt(III)chloride-sodium maleate and tris(ethylenediamine)cobalt(III)chloride-sodium fumarate in aqueous solutions of various ionic strengths at 25°C. Appreciable deviation of the measured conductivity from additivity was attributed to the ion-pair formation of tris(ethylenediamine)cobalt(III) ion with maleate Ma2− and fumarate Fu2− ions. The concentration formation constants Kc at various ionic strengths were determined by means of computer analysis of the deviation. The thermodynamic ion-pair formation constants K at 25°C were as follows: logK=3.60 for [Co(en)3]3+·Ma2− and logK=2.95 for [Co(en)3]3+·Fu−2.
Hydrolysis of Nickel(II) Ion in Aqueous 3m Sodium Chloride Medium
Authors: Ohtaki Hitoshi , Biedermann Georg 
Published: July 2006

Abstract
The hydrolytic reaction of nickel ion was studied at 25°C in an aqueous 3m sodium chloride medium. In the range of the total nickel concentration of 0.0145–1.000m, the emf data obtained could be explained in terms of the formation of the complex Ni4(OH)4 (the charge is omitted), the formation constant of the species being found to be log*β4,4=−28.55±0.10, together with some minor species NiOH (log*β1,1≤−10.5) and Ni2OH(log*β1,2≤−10.5).
Studies of the Solvent Extraction of Potassium by Nitrobenzene in the Presence of Organic or Inorganic Acids
Authors: Iwachido Tadashi 
Published: July 2006

Abstract
Aromatic compounds with an acidic group, such as –OH, –SH, –COOH, –SO3H, &gt;NH, (Remark: Graphics omitted.)CH, and (Remark: Graphics omitted.)B− (tetraphenylborate) were tested as extracting agents for potassium. The first four acids showed an extractability lower by far than that of the last three. Most inorganic acids exhibited no signs of extraction. Bulky and electronattracting substituents, such as nitro or halogen group, were proved to be effective in enhancing the extractability. The addition of iodine was also effective. A few kinds of surfactants showed considerably high extractability. Some factors influencing the extraction were speculated upon.
The Fluorine, Chlorine, Bromine, and Iodine Contents of Volcanic Rocks in Japan
Authors: Yoshida Minoru , Takahashi Kazuyoshi , Yonehara Norinobu , Ozawa Takejiro , Iwasaki Iwaji 
Published: July 2006

Abstract
The halogen contents of 49 Japanese volcanic rocks are; F: 50–1700 (average 410), Cl: 17–1220 (av. 270), Br: 0.09–8.10 (av. 0.85), I: 0.011–0.32 (av. 0.088) μg/g. The fluorine and chlorine were determined by usual photometric methods, and the bromine and iodine, by photometric methods based on their catalytic action, after decomposition and separation procedures suitable for each case. The bromine and iodine contents are appreciably lower than the values generally accepted for igneous rocks. The bromine content agrees with Sugiura’s value. The frequency distribution of each halogen content shows an approximate lognormality. The chlorine and bromine contents are strongly correlated, and the Br/Cl atomic ratio is in a narrow range (0.66–3.7)×10−3 (av. 1.5×10−3). No other correlation is observed among the halogen contents at all. Each halogen content has no marked relation to the type of rock. A regional difference is seen in the F/Cl and I/Br ratios. Three ultrabasic rocks have very low fluorine (≤20) and chlorine contents (≤50 μg/g). On the other hand, they have a slightly lower bromine content (0.15–0.34 μg/g) than, and almost the same iodine content (0.07–0.13 μg/g) as, the volcanic rocks.
The Synthesis of Phosphonophenylazochromotropic Acids and the Stability Constants of Its Alkaline Earth Metal Chelates
Authors: Kina Kenyu , Miyata Haruo , Tôei Kyoji 
Published: July 2006

Abstract
The acid dissociation constants of the three isomeric phosphonophenylazochromotropic acids and their chelate stability constants with alkaline earth metals have been measured by the pH titration method at an ionic strength of 0.10 and at 25.0±0.1°C. The stability order with respect to the ligands is as follows: ortho-&gt;meta-&gt;para-, and the stability constant of each ligand decreases in the order: Mg&gt;Ca&gt;Sr&gt;Ba; this order is parallel to the reciprocal of the ionic radii of the metal ions. From a comparison between the chelate stability of o-phosphonophenylazochromotropic acid and that of Neo-Thorin, it has been concluded that the magnesium ion forms a more stable chelate bond with the phosphonic group than with the arsonic group.
Intramolecular Hydrogen Bonds. XVII. Intramolecular Hydrogen Bonding Involving the Mercapto Group as a Hydrogen Donor
Authors: Mori Nobuo , Kaido Shinichi , Suzuki Koichi , Nakamura Mikio , Tsuzuki Yojiro 
Published: July 2006

Abstract
The SH stretching absorption spectra of some mercapto compounds in dilute carbon tetrachloride solutions and also in acetonitrile solutions have been measured at 20°C. Alkyl mercaptans show absorption bands which are suggestive of the rotational isomerism around the C–S bond. The spectral data indicate that benzyl mercaptan, ω-ethoxyalkyl mercaptans, and ethyl α- and β-mercaptoalkanoates form practically no intramolecular hydrogen bond between the SH group and the hydrogen-acceptor group. In thiosalicylic acid and its ethyl ester, the hydrogen-bonding to the carbonyl group is partially possible even in acetonitrile. On the other hand, the corresponding free carboxylic acids are not hydrogen-bonded between the S atom and the carboxyl group.
The Preparation and Properties of Mesoionic 5-Iminothiazole Derivatives
Authors: Shiba Toshie , Kato Hiroshi 
Published: July 2006

Abstract
Mesoionic 5-iminothiazoles were prepared by the cyclization of N-thiobenzoyl-methylaminoacetonitriles with hydrogen chloride or acyl chlorides. The reaction between a 5-aminothiazolium chloride and acyl chlorides, isocyanate, sulfonyl chloride, and nitrous acid gave the corresponding N-substituted mesoionic 5-iminothiazole derivatives. The spectral data of these compounds as well as the ready bromination of the ring support the view that this ring system is aromatic.