bluuebunny/crossref_metadata_2025 huggingface dataset:
The Rearrangement of 2α-Hydroxy-10β-pinan-3-one with Acetic Anhydride
Authors: Hirata Toshifumi
Published: July 2006

The reaction of (+)-2α-hydroxy-10β-pinan-3-one (1) with acetic anhydride afforded (+)-2α-acetoxy-10β-pinan-3-one (2), (−)-carvone (3), (−)-4α-acetoxy-10α-pinan-3-one (4), (+)-4β-acetoxy-10β-pinan-3-one (5), and (−)-4β-acetoxy-10α-pinan-3-one (6). The three products, 4, 5, and 6, were newly identified on the basis of a combination of chemical and physico-chemical methods. By examination using the 14C-labelled acetate (2), the formation of 4, 5, and 6 was shown to arise from the intramolecular rearrangement of 2. The mechanistic implications of the reaction are given.
Electron Spin Resonance Studies of Bis(acetylacetonato)copper(II) Adsorbed on X-Type Zeolite. I. Interaction with Ammonia and Aniline
Authors: Yamada Yoshio
Published: July 2006

The interaction of bis(acetylacetonato)copper(II) (Cu(acac)2) adsorbed on X-type zeolite of the sodium form and on silica gel with ammonia and aniline was investigated by ESR. The magnetic and bonding parameters for Cu(acac)2 on the surfaces indicate that the axial-ligand field about the copper on the surfaces is similar to that in a toluene solution. This finding implies that the copper in Cu(acac)2 does not interact strongly with these surfaces. However, it was deduced from the change in the spectrum at higher temperatures that the quasi-π-electrons in Cu(acac)2 interact with the electrostatic field arising from the cations on the zeolite. When ammonia or aniline was introduced, the bonding characters of the complex altered significantly. It was found, from the variation in the parameters, that the axial-ligand field about the complex strengthens and that an adduct is formed. Furthermore, a spectral line at g=2.004, which was observed only for Cu(acac)2 on the zeolite in the presence of aniline, was considered to be due to a cation radical formed by an electron transfer from the aniline to the complex.
Metal Catalysts Supported on Zeolite. II. Dehydrogenation of Cyclohexane and Hydrodemethylation of Toluene over Zeolite-Supported Platinum Catalysts
Authors: Kubo Toshihiko , Arai Hiromichi , Tominaga Hiroo , Kunugi Taiseki
Published: July 2006

Correlations between the amount of hydrogen adsorption and the catalytic activities of the zeolite-supported platinum catalysts were interpreted in terms of the dispersion state of platinum particles. The activities for dehydrogenation of cyclohexane and hydrodemethylation of toluene were directly proprotional to the amount of hydrogen adsorption. The tiny platinum particles with diameters of less than 20 Å, which had little ability to chemisorb hydrogen, showed a poor activity in both reactions.
The Heat of Adsorption from Solution. I. The Heat of Adsorption of Benzene on Silica Gel from the Benzene-Cyclohexane Solution
Authors: Morimoto Tetsuo , Naono Hiromitu
Published: July 2006

The sensitivity and reliability of the improved-flow micro-calorimeter have been examined by supplying given amounts of electric energy to the calibration heater inserted in the calorimeter. The detection limit of the heat amount was found to be 0.01 meal, and its probable error to be ±0.5 and ±0.3% at the heat evolutions of 10 and 40 meal respectively. The heat of the adsorption of benzene on silica gel from a cyclohexane solution has been measured at 30°C by the calorimeter thus constructed. The adsorption calorimetry indicates that benzene is adsorbed reversibly on silica gel, and that the differential heat of the adsorption of benzene is independent of the amount of adsorbed benzene, but that it depends strongly on the pretreatment temperature of the silica gel. The heats of adsorption were found to be 1.2, 1.6, 2.0, and 3.8 kcal/mol on silica gel samples treated at 100, 300, 500, and 800°C respectively. The findings on the heats of adsorption have been elucidated in terms of the interaction between benzene molecules and silanol groups on silica gel.
Isolation of the Intermediate in the Tricyanovinylation of Indole and N-Methylindole
Authors: Shirota Yasuhiko , Ezaki Sadayuki , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

The intermediate has been isolated in the tricyanovinylation of indole and N-methylindole. The neutral adduct structure at the 3-position is assigned on the basis of spectroscopic as well as chemical evidence. The mechanism for tricyanovinylation is discussed.
Excitation Transfer in the Radiolysis of Solid Alkane Mixtures at 77 K
Authors: Miyazaki Tetsuo , Wakayama Terunobu , Fukaya Mitsuharu , Saitake Yoshiyuki , Kuri Zen-ichiro
Published: July 2006

The radiolysis of isobutane-propane (less than 5 mol %) or neopentane-alkane (5 mol%) mixtures has been studied at 77 K by means of ESR spectroscopy. When these alkane mixtures are γ-irradiated, the solute radicals are mainly formed by energy transfer from γ-irradiated isobutane or neopentane to the solutes. It is discussed whether the energy transfer is due to a proton transfer, a positive-charge transfer, or an excitation transfer, and it is concluded, for the following reasons, that the energy tranfser is probably due to the excitation transfer and that the excitation transfer may occur via highly-excited states of isobutane or neopentane; (i) The ionization potentials and the energies of the first singlet-excited states of the some additives are higher than those of isobutane or neopentane. (ii) The decrease in the solvent radical yields and the increase in the solute radical yields upon the addition of the solutes to the isobutane or neopentane amount approximately to 2–2.5 G-units. (iii) The yields of hydrogen increase sharply upon the addition of cyclopentane in the radiolysis of solid neopentane. (iv) It was concluded in previous studies that the formation of the solvent radical in the radiolysis of solid isobutane is due to the fragmentation of excited isobutane produced directly by γ-irradiation.
Line Shapes of the 35Cl Nuclear Quadrupole Resonance in KClO3, AgClO3, Ba(ClO3)2·H2O, and Cu(ClO3)2·6H2O
Authors: Suhara Masahiko , Shimizu Ken-ichi
Published: July 2006

The nuclear quadrupole resonance(NQR) of 35Cl in KClO3, AgClO3, Ba(ClO3)2·H2O, and Cu(ClO3)2·6H2O at room temperature has been measured by using a spectrometer system capable of reproducing with fidelity the line shape. The line-shape parameters were determined from the observed spectrum. All the line shapes of the four chlorates are of an intermediate character between Gaussian and Lorentzian. The line-width in K and Ag salts seems to originate from the inhomogeneity of the electric-field gradient, itself a result of the imperfection of the crystal. In Ba salt, it was found that the line-width is determined by the magnetic dipole-dipole interaction between chlorine and protons in the water of crystallization. The Lorentzian is the superior component of the line shape in Gu salt. This is explained in terms of the anharmonicity of the torsional oscillation of the ClO3− group.
A CNDO Study of Biphenyl
Authors: Tajiri Akio , Takagi Shohji , Hatano Masahiro
Published: July 2006

The ground-state electronic structure of biphenyl were studied by the use of the CNDO/2 method. It was found that the lengthening of the central C–C bond in biphenyl gave a reasonable minimum point for the potential energy curve. A modified version of the CNDO/2 method was used in order to calculate the electronic spectra of biphenyl for three possible (planar, angular, and vertical) conformations. The method gave a reasonable interpretation of the spectral features of biphenyl.
Kinetics of Oxygen Exchange between Selenite Ions and Water
Authors: Okumura Akiko , Okazaki Nobukazu
Published: July 2006

The rate of oxygen exchange between selenite ions and solvent water has been measured at 0°C over the pH range of 8.7–12.5. The rate of exchange, R, may be expressed by the rate law;

R=k1[SeO32−]+k2[HSeO3−]+k3[HSeO3−]2+k4[HSeO3−][SeO32−].

The observed rates were analysed in order to obtain the values of the rate constants. The over-all exchange reaction shows a negative salt effect; this has been shown to be an equilibrium salt effect on the dissociation of the hydrogen selenite ion.
Structure of Ethylene Oxide Oligomer Complexes. II. A 1:1 Complex of Tetraethylene Glycol Diethyl Ether with Mercuric Chloride
Authors: Iwamoto Reikichi
Published: July 2006

Structure of a 1:1 complex of tetraethylene glycol diethyl ether CH3CH2O(CH2CH2O)4CH2CH3 (TGE) with mercuric chloride has been investigated by means of X-ray diffraction. The complex has a cubic unit cell with a=−12.54 Å and four molecules of both TGE and HgCl2 are contained in the unit cell. The space group is Pa3-Th6. Four Hg atoms are located at the positions corresponding to the face centered arrangement. The TGE molecule is statistically arranged around the Hg atom located at the position having site symmetry \bar3. The following molecular conformation of TGE was suggested :

CH3CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O2\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetG–CH2–CH3

where T, G, and \barG indicate trans, gauche, and minus gauche forms, respectively. The TGE molecule encloses the HgCl2 molecule around the Hg atom with close interatomic distances between the Hg and O atoms.
Structure of Ethylene Oxide Oligomer Complexes. III. A 1:2 Complex of Hexaethylene Glycol Diethyl Ether with Mercuric Chloride
Authors: Iwamoto Reikichi
Published: July 2006

Molecular and crystal structure of a 1:2 complex of hexaethylene glycol diethyl ether CH3CH2O(CH2CH2O)6-CH2CH3 (HGE) with HgCl2 has been determined by means of X-ray diffraction. The unit cell is monoclinic with a=23.34, b=7.84, c=16.69 Å, and β=115.0°. The space group is C2/c. The unit cell contains four HGE and eight HgCl2 molecules. The HGE molecule in the complex has the conformation

CH3–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetG–O\undersetG–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2–CH3,

where T, G, and \barG denote trans, gauche, and minus gauche, respectively, two HgCl2 molecules being coordinated with one HGE molecule. The asymmetric unit consists of a half of HGE and one HgCl2 molecule. The four oxygen atoms of either half of HGE, which are coplanar, are coordinated with one Hg atom with close interatomic distances (2.66–2.91 Å) between the O and Hg atoms, the central oxygen atom of HGE being coordinated with two Hg atoms. The HgCl2 molecule is distorted from the linear form by 4°.
The Catalytic Effect of the Bismuth Nitrate on the Autoxidation of Olefins
Authors: Tsuchiya Fujio , Ikawa Tsuneo
Published: July 2006

The catalytic effect of the bismuth nitrate on the autoxidation of olefins has been investigated. Nitrogen dioxide, oxygen atoms, and bismuth oxynitrate, which are the thermal decomposition products of the bismuth nitrate, are not involved in the initiation of the reaction. The bismuth nitrate is only effective on olefinic compounds, not on saturated hydrocarbons, and it does not decompose hydroperoxide. The catalysis of the bismuth nitrate is supposed to result from direct interaction with olefin.
Determination of Catalytic Rate Constants in the Reaction of Lysozyme and Oligosaccharide by Computer Simulation Analysis
Authors: Tada Hiroko , Kakitani Toshiaki
Published: July 2006

We have developed Chipman’s kinetic study on a reaction of lysozyme and oligosaccharide. That is, we have analyzed how each catalytic rate constant affects the pattern of time-course graphs of oligomer concentrations in the reaction. By fitting computer simulation curves to three experimental time-course graphs, values of the catalytic rate constants for the bond-cleavage, transglycosylation and hydration are determined step by step. Also some binding constants are evaluated.
Reaction between p-Toluenesulfinic Acid and Diphenyldiazomethane
Authors: Kobayashi Michio , Minato Hiroshi , Fukuda Hideo
Published: July 2006

Reaction between p-toluenesulfinic acid and diphenyldiazomethane was investigated in several solvents. Reaction was faster in non-polar solvents and slower in polar solvents. Experiments with CH3C6H4SO2D showed that protonation of diphenyldiazomethane is the rate-determining step. In non-polar solvents the main product was benzhydryl p-tolyl sulfone, whereas in polar solvents benzhydryl p-toluenesulfinate was the main product. In ethanol, benzhydryl ethyl ether was also produced. The mechanism of the reaction was discussed.
The Oxidation of 2,3-Dihydro-4H-pyran-4-ones
Authors: Sato Kikumasa , Inoue Seiichi , \={O}hashi Masao
Published: July 2006

The synthesis and oxidation of substituted 2,3-dihydro-4H-pyran-4-ones are described. The reaction of crotonoyl chloride with β-ketoester gave dihydro-4H-pyran-4-ones (I). Dihydro-γ-pyrone (Ia) is oxidized, hydrolyzed, and subsequently decarboxylated to give 6-methyl maltol (IV).
Calculation of the Nonradiative Transition Rate for the 1B1u→1B2u Transition in Benzene
Authors: Shimakura Noriyuki , Fujimura Yuichi , Nakajima Takeshi
Published: July 2006

The nonradiative transition rate for the 1B1u→1B2u transition in benzene was calculated taking into account the pseudo-Jahn-Teller distortion in the 1B1u state and using a crude adiabatic approximation. The calculated rate constant is compared with the experimental one reported by Katz et al.
Effects of Pressure on the Chemical Properties of Solid Surface, VIII. The Surface Acidity of the Compressed Magnesium Sulfate
Authors: Kawakami Takeshi , Banba Hiroyoshi , Ogino Yoshisada
Published: July 2006

In order to clarify the mechanism of the acidity change due to compression, magnesium sulfate was compressed under various pressures ranging from 0 to 12000 kg/cm2, the surface acidities, the powder X-ray diffraction patterns, the DTA data, and infrared spectra of the compressed samples were thus obtained. According to the experimental results, the surface acidity of the sample did not vary upon the compression of low pressures (0–6000 kg/cm2), and a further increase in the compacting pressure resulted in an increase in the surface acidity. From the results of the X-ray diffraction studies, infrared, and far infrared absorption studies and the DTA studies, the relations between the acidity change and the structural changes of the samples were discussed. As a result of this work, the observed acidity change was explained in terms of the distortion of the structural unit of magnesium sulfate.
Solubilization Behavior of Mixed Micelles of Anionic and Nonionic Surfactants in Relation to Their Micellar Structures
Authors: Tokiwa Fumikatsu , Tsujii Kaoru
Published: July 2006

The solubilization behavior of mixed micelles of nonionic and anionic surfactants toward a water-insoluble dye, Yellow OB, has been studied. The surfactants examined were a nonionic surfactant, dodecyl polyoxyethylene ether (C12POE), and anionic surfactants with the chemical structure of (Remark: Graphics omitted.), where m+n=8 and where m or n is 0, 4, or 8 (and sodium decyl sulfonate for reference). The solubilization greatly depends on the position of the benzene ring in the hydrocarbon chain of the anionic surfactant mixed; in the mixture of C12POE and (Remark: Graphics omitted.), the synergistic effect in solubilization is remarkable. The results have been discussed in relation to the structure or compactness of the polyoxyethylene shell of the mixed micelle, and in relation to the interaction of anionic and nonionic surfactants in their mixed micelle, which had previously been observed by NMR measurements.
Chemical Approach to the Radiolysis of Polyphosphate Glass. I. Effects of Sb(III, V), Mo(V, VI) and U(IV, VI) Ions
Authors: Kobayashi Yoshimitsu , Matsuura Niro
Published: July 2006

The yields of radiation-induced electrons and holes trapped in the glass matrix are easily determined by introducing metal ions, such as Sb, Mo, and U ions, into water-soluble NaPO3 polymer glass. Doping 1 mol % of these ions of a lower oxidation state wholly prevents the trapping of holes and results in oxidation to their higher oxidation states. A reaction in the reverse direction also occurs for the same ions of a higher oxidation state, which are converted into a lower one by reduction. This radiation-induced redox reaction has a minimum yield at a dopant composition corresponding to Sb2O4 for Sb(III)–Sb(V), Mo6O17 for Mo(V)–Mo(VI), and U3O8 for U(IV)–U(VI) redox couples. The largest effective volume among these ions for capturing the holes is for Sb(III). In a high-dose region (1020 to 1021 eV/g), the yields of the redox products of these ions increase logarithmically with the γ-dose absorbed. This makes it difficult to determine the G-value of the redox products precisely. The approximate values are in an order of magnitude of 0.1 atom per 100 eV absorbed.
The Dielectric Relaxation of γ-Alumina
Authors: Kondo Seiichi , Muroya Masa-aki , Fujiwara Hirofumi , Yamaguchi Noboru
Published: July 2006

The dielectric constant of high-purity γ-alumina, synthesized in this laboratory and having the specific surface area of 220 m2/g, was measured in the frequency range from 30 Hz to 3 MHz and 9.72 GHz and at temperatures ranging from 120 to −196 °C. About 180 °C was found reasonable as the desorption temperature of the water adsorbed on γ-alumina. Three dielectric relaxations, I, II, and III, were found, and some inferences were given as to their mechanism in relation to loosely-adsorbed water, a surface hydroxyl group which can be easily dehydrated, and some other kind of hydroxyl group with a weak interaction with its neighbors, respectively.
ESR Studies on Radiation-Induced Polymerization of 1,3-Butadiene in Urea Canal Complexes
Authors: Ohmori Toshio , Ichikawa Takahisa , Iwasaki Machio
Published: July 2006

The ESR spectrum of γ-irradiated 1,3-butadiene in urea canal complexes at 77 K consists of 7 lines with a hyperfine splitting of 15 G and is assigned to the monomer radical CH3–CH=CH–\dotCH2 which may be produced by hydrogen addition to the 1,3-butadiene. Upon warming to room temperature the spectrum changes into a 6×2-line spectrum (a1=14 G and a2=4 G), which is attributed to the propagating radical R–CβH2–CαH=CH–\dotCH2 occluded in the urea canals. On cooling back to 77 K, the 6×2-line spectrum is transformed into a 5-line spectrum (a=14 G); this spectral change is reversible with temperature and is interpreted in terms of oscillation of the propagating radical around the Cβ–Cα bond. On further warming to 400 K, the propagating radical is converted to the “chain” allyl type radical R–CH2–CH=CH–\dotCH–CH2–R′, of which room-temperature spectrum consists of 7×2 lines (a1=14 G and a2=4 G). This radical conversion is explained by hydrogen atom transfer reaction within the propagating radical through the radical chain and/or between the propagating radical and a neighbouring polymer chain. Irradiated 1,3-butadiene-1,1,4,4-d4 in urea canals is also examined and the results obtained confirm the above-mentioned identifications.
A Study on Restricted Rotation in 1-Acylpyrroles
Authors: Matsuo Taku , Shosenji Hideto , Miyamoto Reiji
Published: July 2006

Restricted rotation of the N-acyl group in 1-acylpyrroles was studied by means of NMR spectroscopy. The free energy of activation (ΔFc\eweq) for 1-formylpyrrole is 14.1 kcal/mol, which is less than that for DMF by 6.8 kcal/ mol. The value of ΔFc\eweq decreases in the order 1-formyl-, 1-acetyl-, and 1-benzoyl-pyrrole in exactly the same manner as is found in the series of N,N-dimethylamides with the corresponding acyl group: the difference in ΔFc\eweq between a pair of compounds with the same acyl group in the two series remains constant (ca. 6 kcal/mol). The ΔFc\eweq-value for 3,4-dimethyl-1-acetylpyrrole is larger than that for 1-acetylpyrrole by 1 kcal/mol. In this particular case, the entropy of activation was found to be responsible for the difference in barrier height.
The Crystal and Molecular Structure of 4,10b-Methano-8H-benzo[ab]cyclodecen-8-one
Authors: Yahashi Ryosuke , Shimanouchi Hirotaka , Sasada Yoshio
Published: July 2006

4,10b-Methano-8H-benzo[ab]cyclodecen-8-one (C14H10O), a stable derivative of so-called 1,6-methano[10]annulene, forms reddish orange crystals of the space group Pbca, with eight molecules in a unit cell with dimensions of a=16.567, b=14.090, and c=8.418 Å. The structure was solved by the symbolic addition method and refined by the block-diagonal least-squares method. The final R factor was 0.080 for the 1386 independent observed reflections. The lengths of the peripheral bonds of the [10]annulene nucleus do not exhibit any apparent alternation. The peripheral eight atoms are approximately coplanar. The C–O distance (1.236 Å) is longer than those in quinones and tropones, and it is consistent with the large dipole moment and high basicity of the present molecule.
Identification of Normal Paraffins and Olefins from Thermal Decomposition Products of Polyethylene
Authors: Iida Takeaki A , Honda Kenichi , Nozaki Hiroshi
Published: July 2006

Straight-chain components of the high boiling fractions of thermal decomposition products of low-density polyethylene were obtained through urea adduct formation, and analyzed by chromatographic separation methods. They were found to be a mixture of approximately 60 wt% of paraffins (C10 to C30), 35 wt% of terminal olefins (C10 to C26), and 5 wt% of nonterminal olefins (C10 to C26) with predominantly 2-alkenes. A silica gel–silver nitrate mixture was found to be useful for chromatographic separation of hydrocarbon components.
Arylation of Olefin with Iodobenzene Catalyzed by Palladium
Authors: Mori Kunio , Mizoroki Tsutomu , Ozaki Atsumu
Published: July 2006

Arylation of propylene, ethylene, styrene, and methyl acrylate with iodobenzene was found to be catalyzed by metallic palladium in methanol to give methylstyrene, styrene, t-stilbene, and methyl cinnamate, respectively. Their yields and selectivities increased significantly by the addition of excess potassium acetate as an acceptor of hydriodic acid formed. The course of catalytic reaction is discussed in terms of the oxidative addition of iodobenzene to a palladium complex of low oxidation state.
Charge-transfer and Proton-transfer in the Formation of Molecular Complexes. VI. 3,3′,5,5′-Tetranitrobiphenyl-4,4′-diol Complexes with Aromatic Amines
Authors: Saito Gunzi , Matsunaga Yoshio
Published: July 2006

The 3,3′,5,5′-tetranitrobiphenyl-4,4′-diol complexes with twenty-eight aromatic monoamines were prepared and characterized on the basis of their compositions and vibrational and electronic spectra. Many amines were found to form yellow-colored complexes with a 1 : 1 composition and orange- or red-colored complexes with a mole ratio of 2 : 1 or higher. The former complexes appeared to be salts formed by means of the proton-transfer from the diol to the amine molecule, while the latter appeared to be complexes of a new type where charge-transfer and proton-transfer interactions simultaneously operate. The deep coloration of the latter complexes was interpreted in terms of a charge-transfer interaction between the anion derived from the diol and the second monoamine molecule. Furthermore, the complexes with ten aromatic diamines were examined. The 1 : 1 o-dianisidine complex was of particular interest in that it is either of the charge-transfer type or of the proton-transfer type, depending upon the preparative conditions.
The 2288 Å Photolysis of Hydrogen Iodide in the Presence of Ethylene and Propylene
Authors: Sano Yasuhisa , Sato Shin
Published: July 2006

The photolysis of hydrogen iodide at 2288 Å has been investigated in the presence of ethylene or propylene. The combinations studied were DI-C2H4, HI-C2D4, and DI-C3H6. In all combinations, the formation of a large amount of HD was observed; this may be attributed to the reaction of hot hydrogen atoms. The pressure dependence of the relative yields of HD and total hydrogen suggested that, of the two possible hot hydrogen atom reactions with ethylene, the abstraction reaction,

D*+C2H4→C2H3+HD (2)

does not occur, while the substitution reaction,

D*+C2H4→C2H3D+H (3)

is the important process. In the case of propylene, however, the abstraction of H by D* is important for the formation of HD. The measured ratios of C2H3D/HD in the DI–C2H4 system and of C2D3H/HD in the HI–C2D4 system were consistent with the above conclusion. Reaction (3) is probably not a real substitution reaction, but a combination of the addition reaction of a hydrogen atom to ethylene and the rapid decomposition of the excited ethyl radical produced.
Ultrasonic Absorption in Aqueous Solutions of Octylamine. Kinetic Investigation of Proton Transfer Reaction
Authors: Nishikawa Sadakatsu , Yasunaga Tatsuya , Tatsumoto Nobuhide
Published: July 2006

The ultrasonic absorption in the mesomorphic state of octylamine water system was characterized by double relaxations. One in the lower frequency range has been explained by the structural relaxation theory of the two state model. In order to clarify the mechanism of the relaxation in the higher frequency range, the ultrasonic absorption in a relatively dilute aqueous solution was measured. The mechanism of the absorption was attributed to hydrolysis from the concentration dependence of the relaxation time. The rate constant kf for the proton transfer reaction, the equilibrium constant K=kb⁄kf, and the standard volume change ΔV resulting from the reaction were determined to be 1.0×1010 M−1 sec−1, 7.6×10−3M, and 32 cc mol−1 respectively.
Stability Constants of Lanthanoid(III) Complexes with 7-Bromo-8-hydroxy-5-quinolinesulfonic Acid
Authors: Manku Gurcharan Singh
Published: July 2006

Stability constants of the tervalent yttrium and lanthanoid complexes with 7-bromo-8-hydroxy-5-quinolinesulfonic acid have been determined in aqueous medium containing 0.100 M sodium perchlorate at 25±1°C by means of pH-titration. The trends in the order of the stability constants of these complexes are also discussed.
Cobalt(II) Complexes of Diethylenetriamine-N,N′,N″-triacetic Acid
Authors: Kawato Toshio , Kanatomi Hajime , Murase Ichiro
Published: July 2006

Cobalt(II) complexes of diethylenetriamine-N,N′,N″-triacetic acid (DTTA) were prepared. From spectrophotometric and magnetic data, diaquo-DTTA-Co(II) was found to have an octahedral arrangement in which the N,N′-diacetate moiety and two water molecules are in the coordination sphere, and the terminal amino acid residue dangles outside. On heating the diaquo-complex, thermal rearrangement occurred with loss of water and the complex took a tetrahedral configuration. This was confirmed by its electronic spectrum and magnetic moment. The tetrahedral complex turned to another octahedral complex with absorption of water, the configuration of which seemed to differ from the original as judged by spectral difference. Cobalt(II) complexes of ethylenediamine-N,N′-diacetic acid (EDDA) were also prepared and investigated for the sake of comparison.
Studies on Nitro Carboxylic Acids. III. The Reaction of α-Nitroolefins with Triethyl or Diethyl Phosphite
Authors: Shin Chung-gi , Yonezawa Yasuchika , Katayama Katsuhiro , Yoshimura Juji
Published: July 2006

The reaction of α-nitroolefins with triethyl or diethyl phosphite was studied and structural assignment of the products was made by spectroscopic analyses. Ethyl α,β-unsaturated α-nitrocarboxylates (IV) and 1-nitroalkenes (V) reacted with triethyl phosphite to afford ethyl β-diethoxyphosphinyl-α,β-unsaturated-carboxylates (IX) and 2-diethoxyphosphinyl-1-alkenes (X), respectively. Compound (IV) reacted with diethyl phosphite to give ethyl β-diethoxyphosphinyl-α-nitrocarboxylates (VI). The geometrical isomerism in IX and the reaction mechanism were discussed.
Preparation, Polymerization, and Copolymerization of N-Vinyl Phthalimidine
Authors: Murata Kenichi
Published: July 2006

The preparation, polymerization, and copolymerization of N-vinyl phthalimidine were investigated. The monomer was prepared by the dehydrochlorination of N-(β-chloroethyl) phthalimidine. Polymerization was carried out in the presence of radical or cationic initiators in bulk and in solution. It was found that polymerizability with cationic initiators was larger than that with radical ones. The resulting polymers had a softening point in the range of 160–180°C, the reduced viscosities being small. Copolymerization with acrylonitrile and styrene was carried out in dimethylformamide and benzene by radical initiators. The monomer reactivity ratios and Alfrey-Price Q, and e values calculated from the copolymerization data of the monomer (M1) and styrene (M2) were r1=0.05, r2=7.4, Q1=0.30, and e1=−1.80. Values for N-vinyl pyrrolidone (M1) were likewise determined for the sake of comparison, and found to be r1=0.02, r2=12.0, Q1=0.22, and e1=−1.99.
The Synthesis of 4-Chloro-3-benzoyl-2-azetinone Derivatives and Their Conversion into N-Benzoyl-2,4-azetidinedione Derivatives
Authors: Matsui Kiyotada , Motoi Masatoshi
Published: July 2006

The treatment of ethyl α-cyanophenylacetate with benzoyl chloride in the presence of 2 equivalents of aluminum chloride in nitrobenzene afforded 4-chloro-3-benzoyl-3-phenyl- (6% yield) and 4-chloro-3-benzoyl-3-(p-benzoylphenyl)-2-azetinone (28%) at 50°C. The same treatment of ethyl α-cyanopropionate afforded 4-chloro-3-benzoyl-3-methyl-2-azetinone (37%). The hydrolytic splitting of the chlorine atoms from the first two azetinones resulted in the formation of N-benzoyl-2,4-azetidinedione derivatives (36 and 20% respectively), whereas from the last we obtained N-benzoyl-α-carboxypropionamide (18%). These azetinone derivatives, when warmed with sodium methoxide in methanol, were converted into α-benzoyl α-cyano esters. The treatment of α-benzoyl α-cyano esters with aluminum chloride also afforded the azetinone derivatives in low yields.
Sterically Controlled Syntheses of Optically Active Organic Compounds. XVII. Asymmetric Syntheses of Amino Acids by Addition of Benzoyl Cyanide to the Azomethine Compounds
Authors: Harada Kaoru , Okawara Tadashi
Published: July 2006

The addition reactions of benzoyl cyanide to the Schiff’s bases prepared from several aliphatic aldehydes with optically active benzylic amines were studied. The adioditn products were hydrolyzed and hydrogenolyzed to form optically active amino acids. The synthetic yields of optically active amino acids were in a range 15 to 57% and the optical purities were in a range 15–37%. When S-α-alkylbenzylamines were used, S-amino acids were obtained.
Synthesis and Biological Activity of Peptides Related to Eledoisin. I. Hexapeptide Amides Containing α-Hydroxy Acids
Authors: Sugano Hiroshi , Higaki Ko , Miyoshi Muneji
Published: July 2006

A new series of eledoisin-like depsipeptides was synthesized in order to obtain some information about the relationship between the structure of the peptide backbone of eledoisin and the biological activity. Specific amino acids in the biologically-active hexapeptide analog of eledoisin, H–Lys–Phe–Ile–Gly–Leu–Met–NH2 (1), were replaced by the corresponding α-hydroxy acids. The biological activities of these analogs were then compared with that of the standard one (1). On the blood pressure in rabbits, H–Lys–Phe–Ile–Glyc–Leu–Met–NH2 (4) and H–Lys–Phlac–Ile–Gly–Hylc–Met–NH2 (6) possessed a substantial activity, though lower than 1, and H–Lys–Phlac–Ile–Gly–Leu–Met–NH2 (2) and H–Lys–Phe–Ile–Gly–Hylc–Met–NH2 (5) were almost as active as 1. On the other hand, H–Lys–Phe–HyMeV–Gly–Leu–Met–NH2 (3) exhibited much less activity. The results indicate that the amide bond between the phenylalanine residue and the isoleucine residue is essential for the hypotensive activity.
Distribution of Uranyl Nitrate between 1- or 2-Butanol and Aqueous Phases
Authors: Yui Norio , Kurokawa Y\={o}ichi , Fujita Taketoshi
Published: July 2006

The distribution of uranyl nitrate between 1- or 2-butanol and aqueous phases and the effect of nitric acid or sodium nitrate on the distribution at 25°C have been studied. Conductance measurements have been carried out for the butanol solutions of uranyl nitrate. It was found that high water content in the butanol phase gives rise to the dissociation of the salt. Semi-empirical relations hold for the distribution considering the dissociation of salt in the butanol phase. Observed and calculated slopes agree in the plots of distribution ratio vs. nitrate concentration. The results were discussed in comparison with distribution data in literature.
Syntheses of Decadiendiyndials and Tetradecatetraendiyndials and Intramolecular Cyclization of Former Dialdehydes
Authors: Muneyuki Ryonosuke , Morimoto Mamoru , Tanaka Motomu , Katakami Tsutomu , Kashitani Takayoshi , Iyoda Masahiko , Nakagawa Masazumi
Published: July 2006

Substituted 2,8-decadien-4,6-diyndials (I, II and III) were synthesized by the oxidative coupling of corresponding substituted pentenynals (VII and XIII) or acetal (XI). It was found that decadiendiyndials (I, II and III) give readily dihydrofuranylidene derivatives (X, XIV and XXV) by the addition of methanol followed by intramolecular cyclization. Thermal reaction of dialdehyde (I, II, and III) afforded difuranylacetylene derivatives (IX, XXI and XXII). 5-Phenyl-2,4-heptadien-6-ynal (XXXII) was prepared from 3-phenyl-2-penten-4-ynal (VIII) or its acetal (XI) by a modified Wittig reaction or by the condensation of ethyl vinyl ether. Oxidative Coupling of XXXII or 5-t-butyl-2,4-heptadien-6-ynal afforded 5,10-diphenyl-(XXIX) or 5,10-di-t-butyl-2,4,10,12-tetradecatetraen-6,8-diyndial (XXX) which showed no tendency for intramolecular cyclization.
An X-Ray Study of Coal Tar Pitch
Authors: Shiraishi Minoru , Kobayashi Kazuo
Published: July 2006

The diffuse X-ray scattering from coal tar pitch has been investigated by using Fourier transformation for the 002 band and Diamond’s least-squares method for the 11 band. From the results of this investigation, the layers were found to be stacked parallel to each other, partly in groups of 8–9 layers, the average number of the layers being 2.46. The distribution of the layer size showed a peak at the diameter of 8.4–10 Å, the average layer size was 8.9 Å, which corresponded to 25 atoms per layer.
The Primary Process of the Photochemical Dimerization of Carbostyril (2-Quinolone) in an Aqueous Solution
Authors: Yamamuro Tetsu , Hata Norisuke , Tanaka Ikuzo
Published: July 2006

Carbostyril dimerizes photochemically in an aqueous solution, in order to investigate the effect of a hydroxide ion on the primary process of the photochemical dimerization in an aqueous solution, both measurements of the quantum yields and flash spectroscopic experiments were carried out under various conditions. The experiments revealed that the photodimerization reaction proceeded through a bimolecular interaction between the triplet and the unexcited carbostyril molecules, although the triplet carbostyrilate ion was in equilibrium with the triplet carbostyril. The triplet carbostyrilate ion was proved not to be involved in the dimerization process.
The Crystal Structure of an N-Methylphenothiazine–7,7,8,8-Tetracyanoquinodimethane Complex, N-MePZT–TCNQ
Authors: Kobayashi Hayao
Published: July 2006

Crystals of the 1 : 1 charge-transfer complex of N-MePZT–TCNQ, are monoclinic with those lattice constants: a=10.904, b=13.321, c=7.086 Å, and β=91.06°, and with the space group C2/m. X-ray structure analysis showed that the mixed-stacks of N-MePZT and TCNQ, exist along the c axis. N-MePZT is disordered, and its apparent molecular symmetry is C2h, taking four possible conformations. The molecular geometry of TCNQ, indicates that the amount of the charge transferred from N-MePZT is very small (<0.2e).
Studies on Nitrile Salts. III. Dimerization of Nitriles Having No α-Hydrogen with Hydrogen Chloride
Authors: Yanagida Shozo , Fujita Tetsuo , Ohoka Masataka , Katagiri Ichiro , Miyake Mikio , Komori Saburo
Published: July 2006

The reaction of nitriles having no α-hydrogen, such as aromatic nitriles and thiocyanates, with hydrogen chloride was investigated. Benzonitrile, p-tolunitrile, m-tolunitrile and some thiocyanates gave analytically pure 2:2 adducts in their reactions with HCl in a sealed glass tube at 30–60°C. The structure of the adducts was elucidated on the basis of NMR analysis and the mechanism of the generalized dimerization of nitriles was discussed.
Studies on Nitrile Salts. IV. Trimerization of Nitriles to 1,3,5-Triazines by the Combined Catalyst PCl5–HCl
Authors: Yanagida Shozo , Yokoe Masaaki , Katagiri Ichiro , Ohoka Masataka , Komori Saburo
Published: July 2006

The combined catalyst PCl5–HCl shows effective catalysis in the trimerization of some aromatic nitriles or trichloroacetonitrile to s-triazines (III). The scope and limitation of the trimerization, in comparison with other Lewis acids, and its mechanism were studied. It was confirmed that PCl5 is effective both in the formation of an intermediate, nitrile–HCl 2:2 adduct, and in the reaction of the 2:2 adduct with another nitrile to s-triazine.
ESR Line Width and Exchange Narrowing in Powder Samples
Authors: Misra B N , Gupta S K
Published: July 2006

Electron Spin Resonance Spectra of 1-1 Diphenyl-2-Picryl Hydrazyl (DPPH) recrystallized from some aliphatic and aromatic solvents have been studied at room temperature in the X-band region. Measurements of lineshape, linewidth and g value were carried out, all the samples being subjected to microchemical analyses with determination of density and melting point. A theoretical study of ESR linewidths has been carried out by means of the Kubo-Tomita theory of ESR linewidth. A quantitative estimation of dipolar width, exchange frequency, exchange integral and asymptotic Curie temperature for each sample was made. A reduction of exchange narrowing has been suggested to be the main cause of broadening.
Thermometric Titration in the Investigation of the Formation of Polyanions of Molybdenum(VI), Tungsten(VI), Vanadium(V), and Chromium(VI). III. Titration of Molybdic Acid with Sodium Hydroxide Solution
Authors: Kiba Nobutoshi , Takeuchi Tsugio
Published: July 2006

To define the properties of molybdenum-containing species which appear in the acidification of neutral molybdate solution with mineral acid, the reverse process, i.e. the titration of molybdic acid of acidified molybdate solution with sodium hydroxide, was examined and the titration curves were obtained thermometrically as well as potentiometrically. In the thermometric titration curves there are inflections not found on the pH-titration curves of the same systems. Titration curves of both methods change with molybdenum concentration, the reaction process being found to be responsible for the change. Polymolybdate anions were identified with the aid of the ultraviolet spectrophotometry of Punger et al. A neutral salt such as sodium perchlorate or lithium perchlorate was found to affect the shape of the thermometric titration curve, since in the presence of such salt octamolybdate ion was readily converted into heptamolybdate ion.
Liquid Crystalline Properties of Substituted Azo- and Azoxy-benzenes. I
Authors: Murase Kei , Watanabe Haruaki
Published: July 2006

In order to obtain low-temperature mesomorphic materials, thirty-two p-alkyl-p′-alkoxy-azo- and -azoxybenzenes have been synthesized. The former have been made by the condensation of p-n-alkylnitrosobenzenes and p-n-alkoxyanilines, and the latter, by the oxidation of the former. Twenty-nine of the compounds show nematic behavior. In the majority of cases, the nematic temperature range of the azoxy compounds, which have been considered to consist of two isomers synthesized simultaneously, is appreciably wide.
The Catalytic Effect of Bases on the O→N Migration of the s-Triazinyl Group in O-(s-Triazinyl)-2-aminophenols
Authors: Shiojima Takeo , Hashida Yoji , Matsui Kohji
Published: July 2006

The catalytic effect of bases on the O→N migration of the s-triazinyl group in O-(s-triazinyl)-2-aminophenols has been studied kinetically. In the rearrangement of N-(acyl)-O-(s-triazinyl)-2-aminophenols (II) in alkaline aqueous methanol, the reactive species was found to be an ion formed by the ionization of the acylamino group. In the case of O-(s-triazinyl)-2-aminophenols (I), the rearrangement was subjected to a general base catalysis, although the extent was small.
Polycondensation of Malononitrile and Methylenedimalononitrile with Bis(chloromethyl)Aromatic Compounds Using Triethylamine as Acid Acceptor
Authors: Kawabata Nariyoshi , Matsubara Kenichi , Yamashita Shinzo
Published: July 2006

Malononitrile was found to undergo condensation reaction with benzyl chloride to give dibenzylmalononitrile in a quantitative yield under mild conditions when an organic base such as triethylamine was used as acid acceptor in dimethyl sulfoxide. The reaction was applied to the polycondensation of malononitrile and methylenedimalononitrile with p-xylylene dichloride and p,p′-bis(chloromethyl)diphenyl ether, polymers with intrinsic viscosity 0.14–0.22 dl/g being obtained in quantitative yields.
Compounds Relating to Dibenzoyladenine Riboside. The Choice between the N6,1-Dibenzoyl and N6,N6-Dibenzoyl Structures
Authors: Anzai Kentaro , Matsui Masanao
Published: July 2006

It was clarified, by NMR analysis and on the grounds of synthetic work, that dibenzoyladenine riboside and its analogues have the N6,N6-dibenzoyl structure rather than the N6,1-dibenzoyl structure, which has customarily been used to describe the benzoyl derivatives of adenosine.
A Note on the Intermolecular Orthogonalized Orbital
Authors: Kato Hiroshi , Ishimaru Shingo
Published: July 2006

The procedure for treating the molecular interaction is simplified by using the intermolecular orthogonalized orbital given by the method of Löwdin, and the accuracy of the approximation is examined, giving examples of the proton spin density of the solvated electron and the delocalization energy between chemically-interacting molecules. The following is then concluded: the intermolecular orthogonalized orbital is a kind of perturbed wavefunction of the molecule interacting with the other system and can most reasonably be applied when the Mulliken-type approximation for the intermolecular integrals can well be used. Its utility with regard to the three-system problem is also briefly discussed.
Mixed Ligand Complex Formation between Monodentate Ligands and Various Tridentate Ligand-Copper(II) Complexes
Authors: Yamauchi Osamu , Benno Hiroshi , Nakahara Akitsugu
Published: July 2006

Formation of mixed ligand complexes between monodentate ligands (L) and copper(II) complexes of tridentate ligands (A) has been investigated by potentiometric titration and thermal analysis. Thus, the constants, logKm, for the formation of the complexes of type CuA·L from CuA and L have been calculated from the titration curves by the method of non-linear least-squares. A refers to diethylenetriamine, dipicolylamine, 2,2′,2″-terpyridine, ethylenediamine-N-monoacetic acid, iminodiacetic acid, or pyridine-2,6-dicarboxylic acid and L to pyridine, p-phenolsulfonic acid, n-butylamine, or hydroxy group. The stability series in each system with L fixed has been interpreted in terms of the strength of A as a Lewis base, expressed by the sum of pKa (ΣpKa), as well as back-donation. In the absence of significant steric hindrance, favorable combination of donor atoms around copper(II) has been found to be between aromatic nitrogens and negative oxygens. Thermal stability of the isolated complexes of type CuA·PY, where PY is pyridine, was also in line with the stability sequence in solution.
Carboxylation of Phenol Derivatives. XXI. The Formation Reaction of the Complex from Alkali Phenoxide and Carbon Dioxide
Authors: Hirao Ichiro , Kito Taketoshi
Published: July 2006

The yield of the complex was examined using eleven potassium phenoxide or substituted phenoxides. The phenoxide with an electron-donating group gave a complex in a better yield than did that with an electron-attracting group. The infrared spectra of the four complexes were measured. From these results, it was concluded that, in the complex, the carbon atom of carbon dioxide binds to the oxygen atom or the π-electron of alkali phenoxide. The thermal analyses of the complex were also conducted by DTA and TGA in an atmosphere of carbon dioxide; a strong endothermic peak and a rapid weight loss were observed at the temperatures from 120 to 140 °C.
The Activation of Bivalent Sulfur Compounds with Cupric Chloride and Zinc Chloride. The Benzylation and Acylation of Aromatic Compounds with Sulfides and Thiol Esters
Authors: Maekawa Kazuo , Narasaka Koichi , Mukaiyama Teruaki
Published: July 2006

Benzylation of aromatic compounds, such as anisole, m-xylene, toluene, and benzene, with various benzyl sulfides in the presence of equimolar amounts of cupric chloride and zinc chloride was investigated. For example, in the case of benzylation of anisole with 4-benzylthiopyridine, o- and p-benzylanisoles were obtained in 79% yield in the presence of cupric chloride and zinc chloride. On the other hand, when the reaction was carried out in the presence of cupric chloride alone, the yield of benzylanisoles was low. The similar activation with cupric chloride and zinc chloride was successfully applied to the reaction of aromatic compounds with benzaldehyde diethylthioacetal and to the acylation of aromatic compounds with 1,2-bis(acylthio)ethanes.
Kinetic Study of the Pyrolysis of 1- and 2-Phenylethyl Phenyl N-Tosylsulfilimines
Authors: Oae Shigeru , Harada Katsumasa , Tsujihara Kenji , Furukawa Naomichi
Published: July 2006

The pyrolysis of 1-phenylethyl phenyl N-tosylsulfilimine was found to proceed more than 103 times faster than that of ethyl phenyl derivative. The large rate enhancement suggests that the mechanism changes from an ideal cis-elimination to nearly El type. However, substituent effect, kinetic isotope effect with 1-phenylethyl-2,2,2-d3 phenyl N-tosylsulfilimine and solvent effect clearly reveal that the reaction proceeds via an intramolecular concerted process.
Optical Resolution and Stereochemistry of γ-Hydroxyglutamic Acid
Authors: Lee Yong Kyun , Kaneko Takeo
Published: July 2006

Four optical isomers of γ-hydroxyglutamic acid were prepared in pure states by optical resolution of two racemic diastereoisomers through brucine salt of N-benzyloxycarbonyl amino acid or strychnine salt of N-benzoyl derivative. Configurations of α- and γ-asymmetric carbon atoms of these isomers were estimated from contribution to molecular rotation and character of taste exhibition. These determinations were confirmed by chemical degradations to aspartic acid and malic diamide of the definite configurations. Cyclization of each racemic diastereomer to either lactone or lactam was also investigated.
Stereochemistry of the C and D Rings of C-Nor-D-homosteroids. I. The Birch Reduction of “Jervine-11β-ol” and Related Compounds
Authors: Murai Akio , Arita Keiko , Masamune Tadashi
Published: July 2006

The Birch reduction of “jervine-11β-ol” (4) was reinvestigated in detail. Two unknown (6 and 7) and two known compounds (8 and 9) with established configurations were newly isolated besides the previously obtained products (2 and 5). The main product (2), the C17 configuration of which has been left undefined, was degraded into a methyl ketone (18) via a known saturated compound (14) (Chart 2) or correlated with an α,β-unsaturated ketone (23) (Chart 3). These transformations confirmed the configuration of 2 (C17–H) to be β, since the steric structures of compounds 18 and 23 have been determined in an unambiguous manner. On the other hand, the structures and configurations of 6 and 7 were elucidated as shown by the formulas on the respective spectral data as well as by hydrogenation of 6 to 14 (Chart 4) and by hydrolysis of an 11β-alcohol (24=7a), obtained by reduction of the ketone 23, to 7 (Chart 4). These results together with those of the Birch reductions of 11-deoxojervine (1) and product 7 are summarized as follows: Products 2, 6, 7, and 9 with the saturated 17-carbon all take the β-hydrogen configuration at C17, products 3 and 5 with the C13–C17 double bond the α-hydrogen configuration at C12, and products 8 and 9 with the saturated carbons at C13 and C17 the β-hydrogen configuration at C12.