Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 48 , Issue 6
Showing 1-50 articles out of 64 articles from the selected issue
  • Isao Suzuki
    1975 Volume 48 Issue 6 Pages 1685-1690
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Twelve force constants in the general quartic force field of carbon disulfide have been determined by a least-squares method from the available spectroscopic data on four isotopic species of carbon disulfide: 12C32S2, 13C32S2, 12C32S34S, and 13C32S34S. A reasonable set of force constants is obtained together with a set of the third-order parameters λ1, λ2, λ3, and δ which appear in Fermi coupling off-diagonal matrix elements. From the converged set of force constants, l-type doubling constants for a few π-vibrational states are calculated through a direct numerical diagonalization method of vibrational Hamiltonian matrix. They agree well with the observed l-type doubling constants.
  • Ken-ichi Karakida, Kozo Kuchitsu
    1975 Volume 48 Issue 6 Pages 1691-1695
    Published: 1975
    Released: March 27, 2006
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    The molecular structure of trimethylene sulfide (thietane) has been determined by an analysis of electron diffraction intensities combined with the rotational constants determined by microwave spectroscopy by Harris et al.: rg(C–S)=1.847±0.002 Å, rg(C–C)=1.549±0.003 Å, rg(Cα–H)=1.09±0.02 Å, rg(Cβ–H)=1.12±0.04 Å, ∠C–S–C(rav)=76.8±0.3°, ∠H–Cα–H(rav)=112±4°, ∠H–Cβ–H(rav)=114±5° and the dihedral angle, ∠C2SC4–C2C3C4(rav)=26±2°. The uncertainties represent estimated limits of error. The definitions of the geometrical parameters have the usual physical significance except that the normal coordinate representing the large-amplitude ring-puckering motion is extrapolated to its equilibrium position. The conventional formula used in the joint analysis has been modified to account for the large-amplitude vibration.
  • Ken-ichi Onuma, Yasushi Kai, Noritake Yasuoka, Nobutami Kasai
    1975 Volume 48 Issue 6 Pages 1696-1700
    Published: 1975
    Released: March 27, 2006
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    The molecular structure of the title complex has been determined from three-dimensional X-ray diffraction data. The crystal belongs to the monoclinic system, space group P21/c, a=14.934(2), b=8.997(1), c=20.221(3)Å, β=97.44(2)°, Z=4. The molecular structure showed that the tetracyanoquinodimethane (TCNQ) molecule has reacted with one of the propynyl groups of trans-{(PMe3)2Pt(C≡CMe)2} : part of the TCNQ is bonded to the α-carbon atom and the other part to the β-carbon of the propynyl ligand. The platinum atom has a squareplanar geometry; Pt–P=2.302(5) and 2.290(5), Pt–C(C≡CMe3)=2.009(15) and Pt–C(reacted)=2.057(15) Å.
  • Keizo Suzuki, Masao Tsuchiya
    1975 Volume 48 Issue 6 Pages 1701-1704
    Published: 1975
    Released: March 27, 2006
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    The near-UV absorption spectra of phenol-dioxane in n-hexane were observed under hydrostatic pressures up to 1480 atm and at 30 °C. With an increase in the pressure, the spectra shift toward the longer wavelength side and the amount of the hydrogen-bonded phenol increases. The equilibrium constant for (Remark: Graphics omitted.) was obtained, and the volume change accompanying the hydrogen-bond formation was estimated to be −3.0–−3.4 cm3/mol.
  • Minoru Sakiyama, Toshiro Nakano, Syûzô Seki
    1975 Volume 48 Issue 6 Pages 1705-1708
    Published: 1975
    Released: March 27, 2006
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    A rotating-oxygen-combustion bomb calorimeter equipped with a platinum lined bomb has been constructed and calibrated. The enthalpy of combustion of 8-quinolinol(c) was determined. Thermodynamic quantities obtained are as follows: ΔEc°=−4458.90±1.60, ΔHc°=−4460.76±1.60 and ΔHf°=−81.24±2.00 kJ mol−1 for the crystalline state and ΔHf°=27.6±2.6 kJ mol−1 for the gaseous state.
  • Motoyuki Tsuda
    1975 Volume 48 Issue 6 Pages 1709-1712
    Published: 1975
    Released: March 27, 2006
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    The aggregation process of acridine orange (AO) onto the helical poly-α,L-glutamic acid (PLGA) was studied by means of a stopped-flow and rapid-scan spectrophotometer. After the flow stop, a rapid spectral change was observed in which the α-band and the β-band fell, and the γ-band and the polymer band rose. A mechanism of the process was proposed by which after a rapid nucleative process, AO molecules are cooperatively bound to form a dimer and that then the dimer grows to the oligomer and to the polymer of AO which has the form of a super-helix around the core of the α-helix of PLGA.
  • Noboru Moriyama
    1975 Volume 48 Issue 6 Pages 1713-1719
    Published: 1975
    Released: March 27, 2006
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    The effects of various types of anionic surfactants and inorganic phosphates on the apparent viscosities of ferric oxide–water suspensions of high pigment concentrations are examined. The additions of surfactants or inorganic phosphates to the suspensions cause depressions in their apparent viscosities from values of more than 10000 centipoise (cP) to about 10 cP. The concentration of the surfactants or the inorganic phosphates required to depress the apparent viscosity, which is designated as C0, is highly dependent upon the alkyl-chain length of the 1-1-type surfactants, the degree of the polymerization of the surfactants of the type of the vinyl copolymers and the degree of the condensation of the surfactants of the type of the formalin condensates or inorganic phosphates. With the 1-1-type surfactants, the values of the C0 decrease with the increases in the alkyl-chain length, and the surfactants with much shorter alkyl-chain lengths, such as Na octyl sulfate, linear-chain Na hexylbenzene sulfo-nate, and Na butyl-naphthalene sulfonate, have no marked viscosity depression effects. With the formalin condensates and the inorganic phosphates, the values of C0 decrease with the degree of condensation. With the vinyl copolymers, the C0 show smallest values at the appropriate degree of polymerization, e.g., about 10–40 for the Na salt of polyacrylic acid. Both the absolute value of the zeta potential and the amount of adsorption increase remarkably in the concentration regions showing marked viscosity depressions. The viscosity depressions of the suspensions upon the additions of the surfactants or inorganic phosphates can be qualitatively explained by taking into account the contributions of the zeta potential values and concentrations to the dispersion-coagulation of the pigment particles.
  • Akio Nakamura
    1975 Volume 48 Issue 6 Pages 1720-1724
    Published: 1975
    Released: March 27, 2006
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    The amounts of adsorption of an ampholytic surfactant, N-dodecyl-β-alanine(NDA), and an anionic surfactant, sodium alkylsulfate(SAS), at nitrogen-solution interface from aqueous equimolar mixtures of them were measured directly by the radiotracer method, using tritiated and non-tritiated samples of NDA and 35S-labeled and non-labeled samples of SAS: sodium tetradecylsulfate(STS), sodium dodecylsulfate(SDS), and sodium decylsulfate(SDeS). The adsorption of both components of the mixed systems was observed at concentrations lower than those for the systems containing each component alone. A stronger adsorption of NDA than that of SAS was observed for all mixed systems. The overall area per alkyl chain at the maximum adsorption was about 26 Å2 for each system, showing the adsorbed layer to be in a highly condensed state. Electrophoresis measurements, together with surface tension measurements of NDA-SDS systems and the elemental analysis of the precipitates from concentrated NDA-SDS solutions, suggested the presence of a 1 : 1-complex formed between NDA and SDS. The Gibbs adsorption isotherm for the binary system was derived. The calculated amounts of adsorption agreed with the observed values. A linear relationship was found to hold between the logarithm of the constants of complex formation and the number of carbon atoms of SAS. A free energy of the complex formation of −0.50 kcal per mole of the methylene group was found.
  • Yukako Oohashi, Tadayoshi Sakata
    1975 Volume 48 Issue 6 Pages 1725-1731
    Published: 1975
    Released: March 27, 2006
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    Reflection measurements of the pressed pellets of two 2 : 3 complex salts and six 1 : 2 complex salts of the tetracyanoquinodimethane (TCNQ) anion radical were carried out over the 5000–43000 cm−1 range by the use of Avery’s method. The polarized normal-incidence reflection was measured for the Ph3PCH3(TCNQ)2single crystal. The observed results were examined on the basis of the composite-system method. For 2 : 3 salts, the transition energy and the oscillator strength are interpreted by the use of the N-A-A model (N: TCNQo and A-A: TCNQ anion dimer); it is concluded that the interaction between the two components, N and A-A, is weak. In the solid-state spectra of 1 : 2 salts, the assignments were made by the use of the polarization results of the normal-incidence reflection of the Ph3PCH3(TCNQ)2 crystal. Besides the four transitions corresponding to those of 2 : 3 salts, two new CT bands with weak intensities were observed and assigned. Except for quinolinium(TCNQ)2, a spectral change correlative to the electrical conductivity was found in the 1 : 2 salts and discussed in relation to the extent of the delocalization of the negative charge of (TCNQ)2. The spectrum of quinolinium(TCNQ)2 exhibits a remarkable intensity decrease compared with those of the other 1 : 2 salts.
  • Kohji Watanabe
    1975 Volume 48 Issue 6 Pages 1732-1739
    Published: 1975
    Released: March 27, 2006
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    The electron spin resonance (ESR) and the electron nuclear double resonance (ENDOR) spectra of tetraaryl allyl radicals have been observed. A comparison of the ENDOR spectra of α,α,γ,γ-tetraphenyl allyl, α,α-diphenyl-γ,γ-dianisyl allyl, and α,α,γ,γ-tetraanisyl allyl revealed that the four aryl groups are not equivalent, but are apparently to be classified into two types with different conformations in their molecular frameworks. The molecular orbital calculations on the basis of this model have shown a fairly good agreement with the observed spectra. The temperature dependence of the ENDOR spectra at −60∼−110 °C were analyzed, assuming mutually different twisting angles for the allyl skeleton. The activation energy of the torsional vibration of the allyl skeleton is estimated to be about 2.5 kcal/mol. The ESR spectra of α,α,γ,γ-tetraphenyl allyl and α,α-diphenyl-γ,γ-diphenylene allyl change drastically with the temperature at around +115°C and show a marked line-width alternation effect. It is concluded from the results that the torsional vibration becomes vigorous with an increase in the temperature and that the allyl skeleton begins to rotate internally at high temperatures. The activation energy of the internal rotation of the allyl skeleton has been estimated to be about 15∼20 kcal/mol. The temperature-dependent hyperfine splitting of the methine proton has also been explained by assuming a model of the internal rotation of the allyl skeleton.
  • Kazuyoshi Tanaka, Tokio Yamabe, Hiroshi Kato, Kenichi Fukui
    1975 Volume 48 Issue 6 Pages 1740-1744
    Published: 1975
    Released: March 27, 2006
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    The optimized configurations of several ion-non polar molecule complexes (NH4+–CH4, H3O+–CH4 and NH4+–H2) have been discussed by the use of the CNDO/2 method. The results for NH4+–CH4 and H3O+–CH4 turn out to be quite different from those previously proposed by the calculations based on the classical electrostatic model. It may be demonstrated that these systems are stabilized by a kind of hydrogen bond where the charge transfer effect from a neutral molecule to a cation plays an important role, according to the configuration analysis.
  • Koichi Kobayashi
    1975 Volume 48 Issue 6 Pages 1745-1749
    Published: 1975
    Released: March 27, 2006
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    The ion flotation of Cd2+ ions has been investigated from the surface chemical point of view in comparison with the case of Cu2+ ions reported previously. The effects of the change in the pH, the anionic and cationic surfactants, and bentonite on the flotation rate have also been studied. Sodium α-sulfolaurate proved to be one of the best surfactants among the anionic surfactants used for removing Cd2+ ions, showing as high as a 97% removal. About 97% of the Cd2+ ions could be floated in the region of pH 11.3 when a cationic surfactant was used with bentonite, regardless of the exact surfactant used. The addition of bentonite reduced the foam formation and liquid hold-up, resulting in effective bubble flotation. This behavior was as a whole similar to that of Cu2+ ions. However, in all the flotation systems tested, the flotation rate increased sharply at about pH 8, and the flotation rate vs. pH curve for Cd2+ shifted towards a more alkaline region than that for Cu2+, because of the stronger basic nature of the former. Also, the flotation rate of Cd2+ ions for the Cd2+-anionic surfactant systems attained a steady value after about 7 min, longer than the 2-min gas flow required in the case of Cu2+ ion flotation. The adjustment of the pH using ammonia gave a lower rate of flotation than in the case of flotation using sodium hydroxide.
  • Koichi Kobayashi
    1975 Volume 48 Issue 6 Pages 1750-1754
    Published: 1975
    Released: March 27, 2006
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    The conditions for the removal of Cd2+ ions from an aqueous solution by adsorbing particle flotation using bentonite and a cationic surfactant has been investigated. It has been found that the most suitable method was to conduct notation in the region of the coagulation notation of bentonite. The addition of polyacrylamide (PAA) extended not only the region of coagulation flotation towards lower and higher hexadecyltrimethylammonium chloride (HTAG) concentrations tested, but also increased the flotation efficiency (expressed as the percentage of ions removed from the total solution). The selective flotation from an aqueous solution containing two kinds of metal ions was also investigated. Each metal ion could be floated from the solution with the pH of the metal hydroxide formation. By selecting proper conditions, it was possible to remove each metal ion separately from a mixed solution.
  • Teruko Yamanaka
    1975 Volume 48 Issue 6 Pages 1755-1759
    Published: 1975
    Released: March 27, 2006
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    The additional tension and the rate of growth of black films formed from aqueous solutions of polyoxyethylated nonionic surfactants and sodium dodecylsulfate, which contain inorganic electrolytes in high concentrations, were measured for the large vertical films drawn from these solutions. It was found that the rate of growth of black films was proportional to the additional tension in both systems. The reciprocal of the slope of each line was concluded to be a viscosity parameter, since the additional tension acted as the driving force for the growth of black films, and the viscosity parameter, as the resistance. The effect of added glycerol on the rate of growth of black films was compared with that of electrolytes for the films of nonionic surfactants. The former affected both the viscosity parameter and the additional tension, while the latter showed an effect on only the additional tension.
  • Teruko Yamanaka
    1975 Volume 48 Issue 6 Pages 1760-1763
    Published: 1975
    Released: March 27, 2006
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    The properties of black film, the surface tension of solution and the foam stability in the aqueous solutions of polyoxyethylene-type nonionic surfactants containing various electrolytes were studied. The additional tension \barΔ of black films showed a maximum and a minimum in the concentration range of electrolytes of 1×10−5–1 N. The concentration at this minimum shifted in accordance with the lyotropic series of anions. The surface tension was unaffected by the electrolyte of the concentration less than about 1×10−2 N, whereas \barΔ exhibited a maximum in this range. The overall rate of growth of the black film was found to be proportional to \barΔ over a wide range of electrolyte concentration. The effects of electrolytes on the foam stability were discussed being based upon the properties of the black films.
  • Katsumi Kaneko, Mamoru Serizawa, Tatsuo Ishikawa, Katsuya Inouye
    1975 Volume 48 Issue 6 Pages 1764-1769
    Published: 1975
    Released: March 27, 2006
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    The change in the dielectric constant of α-FeOOH, β-FeOOH, and γ-FeOOH with the amount of adsorbed water was examined at 30.0 °C in the frequency range 200 Hz–100 kHz for the purpose of clarifying the mechanism of water adsorption. The adsorption isotherms belong to the BET II type. The sample with the adsorbed water shows a particular dispersion of the dielectric constant with frequency in the low frequency range. The dispersion was ascribed to the transition between different orientational directions of the dipole moment of the adsorbed water. The change in the dielectric constant with the amount of adsorbed water for each iron(III) oxide hydroxide was interpreted in relation to the surface structure of predominant faces of crystals, in particular the number and position of hydroxyls on crystal surfaces. The following adsorption process was suggested below the monolayer adsorption coverage for each iron(III) oxide hydroxide. For α-FeOOH, water molecules are adsorbed on the (100) planes in three successive steps. For β-FeOOH, water molecules are primarily bound in the tunnels existing in the crystal along a direction parallel to the c-axis and then are adsorbed on the cracked tunnels exposing to the outer surface. For γ-FeOOH, water molecules are adsorbed on the (010) planes in two steps.
  • Haruhiko Yokoyama, Hideo Yamatera
    1975 Volume 48 Issue 6 Pages 1770-1776
    Published: 1975
    Released: March 27, 2006
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    The classical Debye-Hückel theory of strong electrolyte solutions was re-examined in order to explain ion association. Regarding a symmetrical electrolyte in very dilute solutions, a more precise expression was derived for excess chemical potential due to electrostatic ion-ion interactions. This expression has, in addition to the Debye-Hückel term, a supplementary term resulting from a more proper account of the energy of the interactions of ions existing near each other. If the concept of ion association is taken as a complement of the Debye-Hückel theory, the contribution to the chemical potential of the electrolyte from ion association should correspond to the supplementary term. The following equation was thus obtained for the ion-association constant:
    K=(8πNa^3/1000) \overset∞\undersetn=1∑b^2n+2/[(2n+2)! (2n-1)]
    This equation is in agreement with that derived by Ebeling on the basis of the cluster theory and has an asymptotic representation (at b→∞) in common with Bjerrum’s. For practical b values, the present equation has the merit that it gives moderate K values, decreasing monotonously with an increase in the a value, and eliminates the disadvantages of Fuoss’s result, giving a minimum K value at b=3, and of Bjerrum’s, giving K=0 at ≤2.
  • Hiroyuki Shinoda
    1975 Volume 48 Issue 6 Pages 1777-1782
    Published: 1975
    Released: March 27, 2006
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    The values of the transition moment of Raman scattering have been calculated according to the formula derived from the vibronic expansion approach. The calculations have been performed for the symmetry coordinates of several small molecules and for the normal vibrations of methane. The electronic wave functions were calculated by the CNDO/2-CI method. The calculated results are large in comparison with the experimental ones. The calculated Raman intensities for the symmetric stretching vibrations were almost all contributed by the term A in the vibronic expansion theory. From the calculated results for the normal vibrations of methane, it was found that the vibronic method used in this work leads to more appropriate values than those obtained from the polarizability theory which was used in the previous paper.
  • Katsuhiko Miyoshi, Toshiaki Taura, Chiyori Shimada, Hayami Yoneda
    1975 Volume 48 Issue 6 Pages 1783-1785
    Published: 1975
    Released: March 27, 2006
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    Solubility of tris(1,10-phenanthroline)iron(II) perchlorate was determined at 25°C by spectrophotometry in aqueous solutions of sodium halides, sulfate, acetate, and trichloroacetate up to ionic strength of 0.5. It was found that the solubility is higher in the presence of water-structure breaking anions but is lower in the presence of water-structure making anions than is expected from the change in activity coefficients with ionic strength. This was interpreted in terms of compatibility and incompatibility of the influence of the complex cation on the water structure with that of added anions, and the hydrophobic nature of the complex cation was noted.
  • Kiyoshi Hasebe, Tsukasa Ohtsuki, Tomihito Kambara
    1975 Volume 48 Issue 6 Pages 1786-1789
    Published: 1975
    Released: March 27, 2006
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    A new method for the solvent extraction-polarographic determination of cadmium has been proposed. The quaternary complex formed by the tris(2,2′-bipyridine)iron(II) cation and the tetraiodocadmate(II) anion can be readily extracted into benzyl alcohol. The extracted complex shows a well-defined reduction wave in the ternary electrolyte-solvent mixture, composed of benzyl alcohol, an aqueous electrolyte solution, and methyl cellosolve. The available range of the present method covers from 5.7×10−6 to 91.4×10−6 M of cadmium(II) in the aqueous phase. The optimum pH range for extraction is 3–9, and the extracted species is stable in the ternary solvent mixture for 5hr. Zinc (II), bromide, and chloride ions do not interfere, but copper (II), mercury (II), and iron(III) do interfere.
  • Hideki Tanaka, Genzo Hashizume
    1975 Volume 48 Issue 6 Pages 1790-1794
    Published: 1975
    Released: March 27, 2006
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    The present method was developed as a way of modifying intensity using the mass-absorption coefficient of the matrix, which is itself obtained from the measurement of the intensity at an arbitrary scattered wavelength. This modification, derived from the simplified equation by the utilization of the known matrix composition, has been empirically demonstrated, and it has been applied to various river-sediment samples. Repeated analyses on copper and zinc in representative sediments were carried out, and the average (\barx) and the coefficient of the variation (c.v.) obtained by the present method and by the atomic-absorption method were compared. In the former method, \barx=1,550 μg/g, c.v.=4.25% on copper, \barx=4,400 μg/g, and c.v.=7.11% on zinc; in the latter method, \barx=1,500 μg/g, c.v.=9.87% on copper, \barx=4,330 μg/g, and c.v.=13.03% on zinc.
  • Isao Sanemasa
    1975 Volume 48 Issue 6 Pages 1795-1798
    Published: 1975
    Released: March 27, 2006
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    The solubility of mercury vapor in water has been measured by means of atomic absorption spectrophotometry over the temperature range of 5–60°C under atmospheric pressure. The aqueous solubility obeys Henry’s law at each temperature. The solubilities and the Henry coefficients are reported. From the solubility data, the heat of the solution of mercury vapor in water is found to be −5.3 kcal/mol. The relationship between the Henry coefficient, k, and the solution temperature, T, is expressed by logk=−1078×1⁄T+6.250. From this equation, the solubilities at 70–100°C are estimated. The solubility of the mercury vapor in sea water has also been measured over the temperature range of 5–30°C. A salting-out effect on the solubility is observed. The practical application of the aqueous solubility of the mercury vapor is discussed from the analytical point of view.
  • Tadaaki Mizoguchi, Taijiro Okabe
    1975 Volume 48 Issue 6 Pages 1799-1805
    Published: 1975
    Released: March 27, 2006
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    The cyanolysis and photometric determination of thiosulfate, trithionate and tetrathionate have been investigated under the various conditions. The cyanolysis of thiosulfate catalyzed by cupric ions proceeded quantitatively in the presence of acetate buffer solution of pH 4.5, while the degree of cyanolysis of trithionate and that of tetrathionate were 0.3 and 0.6%, respectively. The degree of cyanolysis of trithionate was not so depressed as to a negligible extent by the methods previously proposed, but was depressed to 0.7% or less by the addition of such organic solvents as acetone, methanol, etc. The determination of thiosulfate, trithionate and tetrathionate in the concomitant presence of them could be made with a high accuracy.
  • Tadashi Sugihara, Noboru Kimizuka, Takashi Katsura
    1975 Volume 48 Issue 6 Pages 1806-1808
    Published: 1975
    Released: March 27, 2006
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    The standard Gibbs energies of the reaction of EuFeO3 and Fu3Fe5O12 were determined to be −63300±200 cal and −297800±600 cal respectively at 1200°C by means of following reactions: Fe+1/2 Eu2O3+3/4 O2=EuFeO3 and 5 Fe+3/2 Eu2O3+15/4 O2=Eu3Fe5O12, based on the phase equilibria in the Fe–Fe2O3–Eu2O3 system.
  • Takashi Katsura, Kenzo Kitayama, Tadashi Sugihara, Noboru Kimizuka
    1975 Volume 48 Issue 6 Pages 1809-1811
    Published: 1975
    Released: March 27, 2006
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    The standard Gibbs energy of formation of \barCFeO3(\barC=La, Nd, Sm, Eu, Gd, Tb, and Dy) from metallic iron, \barC2O3, and oxygen has been determined at temperatures from 1473 to 1673 K. Based on the free-energy data, the heat of reaction and the entropy change resulting from the reaction have been calculated. The values of the heat of reaction of LaFeO3, NdFeO3, SmFeO3, EuFeO3, and GdFeO3 (the first group) were identical, −107 kcal/mol, at the present temperature interval. However, the values of the heat of reaction of TbFeO3 and DyFeO3 (the second group) decreased with an increase in the temperature. The entropy change of each reaction in the first group was constant, independent of the temperature, and each value decreased in the sequence from LaFeO3 to GdFeO3. The entropy change of the second group decreased with an increase in the temperature. The change of the standard Gibbs energy was intimately related to the ionic radii of \barC-ions, and the relationship between the Gibbs energy and the tolerance factor has been clarified.
  • Kunihiro Watanabe, Ky\={o}z\={o} Kawagaki
    1975 Volume 48 Issue 6 Pages 1812-1815
    Published: 1975
    Released: March 27, 2006
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    A method for the fluorometric determination of gallium in aluminum metal is presented which involves extraction with the methyl isobutyl ketone (MIBK) of the gallium 8-quinolinethiolate complex. The extracted complex has a greenish-yellow fluorescence, with an emission maximum at 505 nm. The maximum fluorescence intensity is obtained at a pH of the initial aqueous phase of around 3.3; the fluorescence remains stable for at least 2 hr. When 50 ml of a sample aqueous solution containing gallium and 0.2 ml of a 0.2% 8-quinolinethiol solution is subjected to extraction with 10 ml of MIBK, the quantity of gallium which can be present for determination in the sample solution amounts to 1 to 30 μg. For the removal of the interfering effects of zinc, cadmium, copper, and nickel on the fluorometric determination, gallium was extracted with isopropyl ether from a 7 M HCl solution. The relative error of this method was 5% for 0.019% gallium in aluminum metal.
  • Hideki Monma, Takafumi Kanazawa
    1975 Volume 48 Issue 6 Pages 1816-1819
    Published: 1975
    Released: March 27, 2006
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    The reactions of fluor-, hydroxy-, and chlorapatites with silica in the presence of water vapor have been studied under various conditions−i.e., various amounts of added silica, various temperatures (up to 1300°C), and various heating times and water-vapor pressures (0.6–760 mmHg). As the pressure increased, the decomposition rate of hydroxyapatite with silica decreased considerably. Fluorapatite and chlorapatite were found to be decomposed with silica after being partially defluorinated or dechlorinated. In the case of fluorapatite, no effect of silica addition was recognized under a low water-vapor pressure (0.6 mmHg). This effect was observed under a high water-vapor pressure (760 mmHg), accompanied by rapid increases in the fluorine volatility and the destruction rate of the apatite in their time-dependence plots. In the reaction using chlorapatite, a similar effect was found under both low and high pressures. The results for the defluorination and dechlorination could mostly be interpreted by assuming the following changes: (1) halogen-oxyapatite formation, (2) the substitution of hydroxyl ions for halogen ions, and (3) the decomposition of apatite with silica.
  • Noriyuki Sotani
    1975 Volume 48 Issue 6 Pages 1820-1825
    Published: 1975
    Released: March 27, 2006
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    The hexagonal hydrate (I) of molybdenum trioxide, which has been newly found and reported, was studied by X-ray diffraction analysis, IR and NMR spectroscopies, and by other methods. Also studied was the change in (I) on heat treatments in air, in hydrogen, and in a hydrogen–thiophene mixture. The crystal was found to belong to a hexagonal system. The air-dried sample has about 0.46 mol of water. This water is included as a water molecule, not as hydroxyl. By the dehydration of (I), anhydrous molybdenum trioxide (I′), which has the same crystal structure as (I), is obtained. Another new form of (I′) is the hexagonal trioxide, which is hygroscopic and which easily absorbs water when standing in air. This (I′) is metastable and is irreversibly transformed to rhombic molybdenum trioxide(II) at 420–430 °C. In hydrogen and in a hydrogen-thiophene mixture, reduction and sulfurization occur in addition to transformation, which can be shown schematically as: (Remark: Graphics omitted.). Transformation in hydrogen and in the hydrogen–thiophene mixture proceeds faster than in air. Reduction occurs more quickly in the hydrogen–thiophene mixture than in hydrogen.
  • Masaaki Okunaka, Gen-etsu Matsubayashi, Toshio Tanaka
    1975 Volume 48 Issue 6 Pages 1826-1829
    Published: 1975
    Released: March 27, 2006
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    PdX(But2NO)L (L=PPh3, AsPh3, P(OPh)3; X=Cl, Br, I) was isolated by the reactions of [PdCl(But2NO)]2 with L and by the halogen exchange reactions of the chloro complexes with LiBr·H2O or NaI. PMR and IR spectra revealed that PdX(But2NO)(PPh3) and PdX(But2NO)(AsPh3) exist as only one geometrical isomer with the halogen atom trans to the oxygen atom of the nitroxide ligand, while two isomers of PdX(But2NO)[P(OPh)3] coexist in solution. The reaction of PdX(But2NO) (PPh3) (X=Cl, I) with triphenylphosphine was found to give Pd(PPh3)4 together with Pd X2(PPh3)2 and Bu2NO·. A similar reaction proceeded between PdCl(But2NO)[P(OPh)3] and triphenylphosphite to yield Pd[P(OPh)3]3, while a not well-defined complex [PdCl(AsPh3)2]n was obtained in the reaction of PdCl(But2NO)(AsPh3) with triphenylarsine.
  • Mitsutomo Tsuhako, Kazuko Hasegawa, Tsuneo Matsuo, Itaru Motooka, Masa ...
    1975 Volume 48 Issue 6 Pages 1830-1835
    Published: 1975
    Released: March 27, 2006
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    In the reaction of Al2O3 or Al(OH)3 with phosphoric acid, the conditions of the formation of the I and II types of aluminum dihydrogen tripolyphosphate, AlH2P3O10, and the A and B types of aluminum tetrametaphosphate, Al4(P4O12)3, were established. The I and II types of AlH2P3O10 were chiefly obtained at 300 °C; the formation of the I type predominated when the water content of the primary product was 15–30%, while the II type was more readily formed at a water content of 10–15%. Also, the I and II types were easily formed at vapor pressures of 1–5 atm. Al4(P4O12)3 was produced when the water content was less than 10% or more than 30%. On the other hand, the A and B types of Al4(P4O12)3 were easily formed at 500 °C; the A type was chiefly formed when the water content was below 10% or above 25%, while the B type was produced at the water content of 10–25%. The water content of the primary product is presumably due to the dehydration caused by the condensation of the P–OH. Thus water, effective for the formation of aluminum phosphates, is the structural water (P–OH). Further, the B type was liable to be formed on rapid dehydration, while the A type was more readily produced on slow dehydration. Accordingly, the formation of aluminum phosphate has been confirmed to be greatly dependent on the water content of the primary product and on the vapor pressure in the secondary heat treatment.
  • Hiroshi Ogino, Junnosuke Fujita
    1975 Volume 48 Issue 6 Pages 1836-1841
    Published: 1975
    Released: March 27, 2006
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    New cobalt (III) complexes, [Co(en)2(H2N(CH2)nNH2)]X3 (n=4, 10, 12 and 14), [Co2(en)4(H2N(CH2)nNH2)2]X6 (n=4, 5, 6, 8, 10 and 12), [Co(en)2(H2N(CH2)4NH3)2]X5 and [CoCl(en)2(H2N(CH2)12NH3)]X3 were isolated from the products of reactions between [CoCl2(en)2]Cl and 1,ω-diaminoalkane in dimethylsulfoxide, with the aid of SP-Sephadex column chromatography. For n=5, 6 and 8, no monomeric [Co(en)2(H2N(CH2)nNH2)]3+ was observed. This result is compatible with instability of the medium size rings in organic compounds. The elution behaviors on Sephadex column and the visible and ultraviolet absorption spectra of the new complexes were also described.
  • Kikuko Hayamizu, Makoto Murata, Osamu Yamamoto
    1975 Volume 48 Issue 6 Pages 1842-1847
    Published: 1975
    Released: March 27, 2006
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    13C nuclear magnetic resonance studies of pyridine solutions containing paramagnetic Ni (II), Co(II), Cu(II), or Mn(II) acetylacetonate are made by observing the induced chemical shift, the line width, and the spin-lattice relaxation time due to the paramagnetism of these metals. The origin of the paramagnetic effects on the 13C spectra induced by Ni, Co, or Cu acetylacetonate is mainly the contact interaction, while the 13C spectra of the pyridine–Mn(AA)2 system can not be interpreted by the same interaction. The 13C spectra of quinoline and isoquinoline containing Mn(AA)2 are also studied; the results indicate that the predominant mechanism is the dipole-dipole interaction.
  • Sanyo Hamai, Hiroshi Kokubun
    1975 Volume 48 Issue 6 Pages 1848-1851
    Published: 1975
    Released: March 27, 2006
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    The photochromism of 2-hydroxy-2′,4,4′-trimethoxytriphenylmethanol (HTMM) in acetonitrile differs from that of other 2-hydroxytriphenylmethanol derivatives in some aspects. The colored form, 2′,4,4′-trimethoxy-o-fuchsone (TMF), of HTMM partly converts to 2-hydroxy-2′,4,4′-trimethoxytriphenylmethyl cation (Cat) at an early stage of the bleaching reaction. At a later stage a slow bleaching of TMF to HTMM becomes the main decay process. Bleaching of the produced Cat is so slow that Cat remains even after complete disappearance of TMF. The formation of Cat was concluded to be a reaction between adsorbed TMF and water on the cell surface. The rate determining step is not a diffusion process since the activation energy found is much larger than that of viscosity. Cat decays by the reaction with water, not with hydroxide ion.
  • Chikatoshi Utsunomiya, Tsunetoshi Kobayashi, Saburo Nagakura
    1975 Volume 48 Issue 6 Pages 1852-1856
    Published: 1975
    Released: March 27, 2006
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    The photoelectron spectra (PES) of 1- and 2-substituted naphthalenes (naphthols, aminonaphthalenes, N,N-dimethylaminonaphthalenes, acetylnaphthalenes, and cyanonaphthalenes) were measured in the region from 6 to 20 eV. The observed PES were assigned with the aid of the CNDO/2 calculations and the substituent effect. The lower energy bands of the compounds with the electron-donating group were found to be due to the ionization from the orbitals caused by the interaction of the highest three occupied π orbitals of the naphtha ene ring with the nonbonding orbital of the substituent group. The second bands of the 1-substituted naphthalenes are commonly assigned to π orbitals almost completely localized on the naphthalene ring. The dimethylammo group of 1-dimethylaminonaphthalene was found to be twisted to a great extent from the ring plane.
  • Norimichi Kawashima, Kenjiro Meguro
    1975 Volume 48 Issue 6 Pages 1857-1861
    Published: 1975
    Released: March 27, 2006
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    α-Copper phthalocyanine and calcium carbonate were mixed and ground with a grinder, and then the surface properties of the mixtures were investigated in comparison with the grinding time by means of X-ray diffraction analysis, electron-micrograph observation, and the specific surface area as obtained by the B.E.T. method. In the grinding process, the crystal decays of both α-copper phthalocyanine and calcium carbonate were observed. Particularly, the calcite-aragonite transformation occurred in the case of calcium carbonate. However, the addition of some α-copper phthalocyanine to calcium carbonate interfered with the transformation of calcium carbonate. As a conclusion, it was evident that the surface of calcium carbonate was covered with α-copper phthalocyanine and that the grinding of calcium carbonate was interfered with by the lubricating action of α-copper phthalocyanine.
  • Sakuya Tanaka, Masaya Okano, Shigeo Tanimoto
    1975 Volume 48 Issue 6 Pages 1862-1864
    Published: 1975
    Released: March 27, 2006
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    The reaction of N-alkyl- or N-aryl-carbonimidic dihalides with Grignard reagents afforded α-elimination products, isocyanides, rather than substitution ones. Two kinds of alkyl or aryl halides were produced concomitantly in this reaction: one kind consisted of halides generated from the Grignard reagents used, and the other, of halides the halogens of which had been derived from the dihalides. The ease of formation of these halides was found to decrease in the order: iodide>bromide>chloride, regardless of which substrate served as the source of a halogen atom. A probable reaction mechanism is proposed.
  • Takamasa Kinoshita, Kouichi Miyano, Toshio Miwa
    1975 Volume 48 Issue 6 Pages 1865-1867
    Published: 1975
    Released: March 27, 2006
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    The reduction of 3-furoic acid with sodium and 2-propanol in liquid ammonia gave 2,3-dihydro-3-furoic acid, which was isolated as a methyl ester (1) in 85% yield. The acid-catalyzed addition of methanol, ethanol, or 2-propanol to the ester 1 yielded 5-alkoxytetrahydro-3-furoate ester, 2, 3, or 4, respectively, in a quantitative yield. When methanol or ethanol was used as a proton source in the reduction, work-up of the reaction mixture gave 5-alkoxytetrahydro-3-furoic acid, which was isolated as the methyl ester, 2 or 3, in 87 or 92% yield, respectively. A mechanism for the Birch reduction of aromatic carboxylic acids is proposed.
  • Eiichi Ibuki, Shigeru Ozasa, Kazue Murai
    1975 Volume 48 Issue 6 Pages 1868-1874
    Published: 1975
    Released: March 27, 2006
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    Seven linear sexiphenyls were synthesized by the Ullmann reaction of iodobiphenyl and diiodobiphenyl. Infrared studies indicated that the fine structure in the 780–810 cm−1 region suggests the presence of consecutive m-phenylene units, and that the positions of the strong or medium bands in the 820–840 cm−1 region indicate approximately the number of continuous p-phenylene units. The electronic spectra commonly displayed a prominent E-band in the narrow region of 192–207 nm. The intense K-band above 260 nm was considered to be an indication of the presence of one or more p-phenylene units.
  • Kyoko Nishizawa, J. Yasuo Satoh
    1975 Volume 48 Issue 6 Pages 1875-1877
    Published: 1975
    Released: March 27, 2006
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    The reaction of cyclohexanones with copper(II) bromide gave polybrominated cyclohexanediones in all cases except for the case of 3,5-dimethylcyclohexanone. Moreover, in this reaction, a pyrocatechol and a phenol derivative were obtained from 4-methyl- and 3,5-dimethylcyclohexanone respectively. The mechanism of this reaction was discussed.
  • Fukiko Yamada, Tomihiro Nishiyama, Hiroshi Samukawa
    1975 Volume 48 Issue 6 Pages 1878-1883
    Published: 1975
    Released: March 27, 2006
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    Proton magnetic resonance spectroscopy has been used to investigate the conformations of a series of 3-aryl-1,2,3-oxathiazolidine 2-oxides. Their conformations were assigned on the basis of the vicinal coupling constants between four methylene protons at the C-4 and C-5 positions. The oxathiazolidine 2-oxides prefer twist-envelope forms, and their conformations vary with both the situation and the nature of the ring substituent. Postulated collision complexes based on the data of the observed solvent-shifts can also be explained in terms of the differences in the conformations.
  • Hiroshi Hirota, Yoshihiko Moriyama, Takahiko Tsuyuki, Yoshiaki Tanahas ...
    1975 Volume 48 Issue 6 Pages 1884-1888
    Published: 1975
    Released: March 27, 2006
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    High resolution mass spectra of shionane and friedelane derivatives were measured and characteristic fragmentation patterns were described.
  • Yuzuru Uchida, Seizi Kozuka
    1975 Volume 48 Issue 6 Pages 1889-1891
    Published: 1975
    Released: March 27, 2006
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    Aroyl alkyl carbonates were treated with isocyanates with or without addition of sodium methoxide and alkyl N-aroylcarbanilates were obtained as the major products. Based on 18O tracer study and catalytic effect of alkoxide ion, a base catalyzed ionic reaction process was confirmed for the mechanism of the carbanilate formation.
  • Masao Ohashi, Tadashi Takahashi, Seiichi Inoue, Kikumasa Sato
    1975 Volume 48 Issue 6 Pages 1892-1896
    Published: 1975
    Released: March 27, 2006
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    A new synthesis of 2-hydroxy-3-methyl-2-cyclohexen-1-one (1) is described. The Mannich reaction of cyclohexane-1,2-dione (2) or 2-morpholino-2-cyclohexen-1-one (3) with morpholine and formalin gave a Mannich base (4), which was then hydrogenolized to afford 1. However, the Mannich reaction of 1 merely gave a bis-Mannich base (22), which was then similarly hydrogenolized to afford 3,6-dimethyl-2-hydroxy-2-cyclohexen-1-one (7) along with 3,6-dimethyl-2-hydroxy-6-morpholinomethyl-2-cyclohexen-1-one (26); 2-hydroxy-3,6,6-trimethyl-2-cyclohexen-1-one could not be obtained under these conditions. The Mannich reaction of other alicyclic α-diketones and the hydrogenolysis of their Mannich bases are also described.
  • Haruhiko Aoi, Michihiro Ishimori, Teiji Tsuruta
    1975 Volume 48 Issue 6 Pages 1897-1901
    Published: 1975
    Released: March 27, 2006
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    An optically active Co(I)(salen) type complex, lithium N,N′-bis-(salicylaldehyde)-1(R),2(R)-1,2-trans-cyclohexanediiminatocobaltate (I), was prepared by reducing the Co(II) complex, N,N′-bis-(salicylaldehyde)-1(R),2(R)-1,2-trans-cyclohexanediiminatocobalt(II), with butyllithium. The structure of the Co(I) complex was determined by means of its absorption and circular dichroism (CD) spectra. D-Propylene oxide was found to react preferentially (e.g., <<D/D+L>>=68% in a dioxane solution) in a kinetic resolution of DL-propylene oxide using the above Co(I) complex as a catalyst. On the contrary, L-propylene oxide reacted selectively when Lewis acids were added to the system of the lithium Co(I) complex. The Lewis acids were demonstrated to interact with the Co(I) complex and to play a significant role in the asymmetric selectivity of the Co(I) species.
  • Tetsuo Shiba, Yasuo Mukunoki, Hitoshi Akiyama
    1975 Volume 48 Issue 6 Pages 1902-1906
    Published: 1975
    Released: March 27, 2006
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    An amino acid composition of the pep tide antibiotic longicatenamycin was investigated. Four new amino acids, i.e., thero-β-hydroxy-L-glutamic acid, L-2-amino-5-rnethylhexanoic acid, L-2-amino-6-methylheptanoic acid, and L-2-amino-7-methyloctanoic acid, which were reported by Shoji et al., were reconfirmed by comparison with the synthetic specimens. Racemic forms of the latter three amino acids were synthesized through acetaminomalonate method. Furthermore, 5-chloro-D-tryptophan was newly isolated from the hydrolyzate of the antibiotic. This structure was assigned by NMR, MS and ORD. A steric configuration of this amino acid was certified by degradation to D-aspartic acid through ozonization. 5-Chloro-DL-tryptophan was synthesized from 3-cyanopropionaldehyde and p-chlorophenylhydrazine by Fischer’s indole synthesis.
  • Masao Nakazaki, Koichiro Naemura, Sigeyuki Harita
    1975 Volume 48 Issue 6 Pages 1907-1913
    Published: 1975
    Released: March 27, 2006
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    (+)-Tricyclo[4.3.0.03,8]nonane (“twist-brendane”) was synthesized via (+)-tricyclo[4.3.0.03,8]nonan-9-one from (+)-endo-2-carboxybicyclo[2.2.2]oct-5-ene. Optically active derivatives of twist-brendane with two functional groups such as (−)-2,9-twist-brendanedione and (−)-9-methylenetwist-brendan-2-one were synthesized from (−)-endo-2-carboxybicyclo[2.2.2]oct-5-ene. Absolute configurations of the compounds were established and their chiroptical properties were discussed.
  • Seiji Shinkai, Reiko Ando, Toyoki Kunitake
    1975 Volume 48 Issue 6 Pages 1914-1917
    Published: 1975
    Released: March 27, 2006
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    An effect of micelles on the acid-catalyzed modification reaction of two dihydropyridines is reported in connection with the NADH function bound to alcohol dehydrogenase, and the hydration equilibrium of dihydronicotinamides was found to be quite susceptible to the ionic environment. The absorption maximum at 357 nm of 1-benzyl-1,4-dihydronicotinamide(NBzNH) was not affected by the presence of cationic micelles, while that of 1-lauryl-1,4-dihydronicotinamide(NLaNH) shifted by 5–6 nm to shorter wavelengths, probably due to the neighboring cationic charge. The hydration rates for dihydronicotinamides were prompted by NaLS micelle and retarded by CTAB micelle. The rate augmentation in the NaLS micelle, compared with the non-micellar system, was 1.7-fold for NBzNH and 33-fold for NLaNH. On the other hand, CTAB micelle pronouncedly depressed the hydration rate of NLaNH, which is 414-fold slower than in NaLS. The micelle of 1-lauryl-3-carbamoylpyridinium(NLaN), which forms the charge transfer complex with NLaNH, was found to inhibit the acid-catalyzed hydration more efficiently (1400-fold slower). Thus, it is suggested that the ammonium ion adjacent to the dihydronicotinamide group in alcohol dehydrogenase–NADH complex performs some biological functions.
  • Seiji Shinkai, Kiyoshi Tamaki, Toyoki Kunitake
    1975 Volume 48 Issue 6 Pages 1918-1921
    Published: 1975
    Released: March 27, 2006
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    The micelle of 1-lauryl-3-carbamoylpyridinium bromide(NLaN) and poly-1-(p-vinylbenzyl)-3-carbamoylpyridinium chloride (PVCG) were shown to form charge transfer complexes with dihydronicotinamides and several aromatic compounds in aqueous media. A broad charge transfer absorption at longer wavelengths was easily detected, and the association constant of 1 : 1 complexes which was estimated from the CT band was enhanced by 6.2–220 times in the NLaN micelle and by 14–66 times in the polymeric system, compared with non-micellar, monomeric system. The enhancement of the interaction between NLaN and its reduced from (NLaNH) was similar in the CTAB micelle and in a nonionic micelle. The increased electron-acceptabilities of the pyridinium group in micellar and polymeric systems were discussed in reference to NAD coenzyme.
  • Hiroharu Suzuki, Masayasu Ohashi, Kenji Itoh, Isamu Matsuda, Yoshio Is ...
    1975 Volume 48 Issue 6 Pages 1922-1924
    Published: 1975
    Released: March 27, 2006
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    N,N′-Bis(trimethylsilyl)-1,2-diamines gave imidazolidine derivatives accompanied with the elimination of hexamethyldisiloxane in excellent yields by condensation reactions with carbonyl compounds under mild conditions. These reactions are regarded as the typical addition-elimination reaction of group IV organometallics.
  • Sakae Uemura, Akio Toshimitsu, Masaya Okano, Katsuhiko Ichikawa
    1975 Volume 48 Issue 6 Pages 1925-1928
    Published: 1975
    Released: March 27, 2006
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    Substitution of thallium moiety in organothallium(III) compounds by selenocyanate is reported. Arylthallium (III) compounds react with KSeCN and CuSO4·5H2O or with Cu(SeCN)2 in dioxane to give aryl selenocyanates in good yields. Alkoxythallates of styrene react smoothly with KSeCN in methanol to afford 1-alkoxy-1-phenyl-2-selenocyanatoethanes almost quantitatively. The oxyselenocyanation of terminal oleflns is conducted by the in situ oxythallation of olefins, followed by the reaction with KSeCN.
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