Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 59 , Issue 12
Showing 1-50 articles out of 63 articles from the selected issue
  • Yutaka Ikushima, Norio Saito, Kiyotaka Hatakeda, Shota Ito, Takashi As ...
    1986 Volume 59 Issue 12 Pages 3709-3713
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The extraction of some organic substances from freezed-dried mackerel powder was performed using supercritical carbon dioxide (SC–CO2) at 4.9–24.5 MPa and 313 K in a fixed-bed flow extractor. It was found that the rate of extraction was enhanced by raising the pressure. The overall yield of the SC–CO2 extraction was comparable to that of a hot-hexane-extraction from the same material. The SC–CO2 extraction produced glycerides of pharmacologic significance such as icosapentaenoic acid (IPA) and docosahexaenoic acid (DHA) from mackerel. In addition, a kinetic model for extraction with supercritical fluids is described, and is applied to correlate our results obtained in the SC–CO2 extraction of mackerel. This model could express the transport within the solid in the supercritical fluid extraction process.
  • Katsuyoshi Kobayashi, Fumiaki Fujisaki, Toshifumi Yoshimine, Katsumi N ...
    1986 Volume 59 Issue 12 Pages 3715-3722
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The electrochemical behavior of 1,1′-dimethyl-4,4′-bipyridinium dichloride (methyl viologen, MV) is complicated with the strong adsorption of both the oxidized (MV2+) and the reduced (MV) forms of MV on a mercury electrode. MV2+ adsorbs on the electrode with a flat orientation at more positive potentials than the potential of zero charge of the mercury electrode. MV adsorbs on the electrode with a vertical orientation at more negative potentials than the formal potential of the MV2+⁄+· couple, (E0′)MV. It is probable that the change in the orientation of the adsorbed MV from flat to vertical with the increase in the MV concentration in the vicinity of the (E0′)MV leads to a strongly attractive interaction between the adsorbed MV molecules and a sharp voltammetric adsorption peak results at higher concentrations of MV2+.
  • Masakatsu Ueno, Yasushi Sakata, Noriaki Tsuchihashi, Kiyoshi Shimizu
    1986 Volume 59 Issue 12 Pages 3723-3727
    Published: 1986
    Released: June 27, 2006
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    The limiting molar conductances, Λ°, of sodium hydroxide were determined at 15, 25, and 40 °C as a function of the pressure up to 1500 kgf cm−2 (1 kgf cm−2=0.9807×105 Pa) from the conductances measured in a dilute concentration range (1×10−3–2×10−2M, 1 M=1 mol dm−3). The excess conductances at an infinite dilution, λ°E, of the hydroxide ion, as estimated by [λ°E(OH)=Λ°(NaOH)−Λ°(NaCl)], were found to increase with an increase in the pressure and temperature, as well as those of the oxonium ion, λ°E(H3O+). However, there was a significant difference in the magnitude of λ°E, itself, and a slight difference in the magnitude of the pressure and temperature dependences of λ°E between hydroxide and oxonium ions. These results may be related to a difference between the proton-jump mechanisms of the hydroxide and oxonium ions.
  • Tatsuo Ishikawa, Naoki Yamagami, Seiichi Kondo
    1986 Volume 59 Issue 12 Pages 3729-3733
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The adsorption behaviors of methyl and propyl iodides, propyl chloride and chlorobenzene were examined on silica gels impregnated with 1,4-diazabicyclo[2.2.2]octane (DABCO), pyperazine (PPZ), hexamethylene tetramine (HMTA), and modified with (3-aminopropyl)triethoxysilane (ATS) and dimethoxybis[3-(rnethylamino)propyl]silane (DAS). The irreversibly adsorbed amount of these halides except chlorobenzene was proportional to the amount of impregnated amines. The molar ratios of irreversible adsorption of the halides to the impregnated amine were less than 2 and in the order of DABCO>PPZ>HMTA>ATS>DAS. The former three amine compounds are less stable than the last two materials against thermal pretreatment.
  • Miki Niwa, Masakazu Iwamoto, Koh-ichi Segawa
    1986 Volume 59 Issue 12 Pages 3735-3739
    Published: 1986
    Released: June 27, 2006
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    The Influence of the experimental conditions of the TPD (Temperature-Programmed Desorption) of ammonia on the measurement of acidity of mordenites and Y zeolites was studied. The results were applicable to the measurements of the strength and the number of acid sites of zeolites. For contact times of the carrier gas from 10−2 to 10−6 g min ml−1 defined as W/F (W, sample weight; F, flow rate of the carrier gas), the peak maximum temperature was related to the parameter (W/F). The relationship was explained on the basis of a theoretical equation derived by Cvetanovic and Amenomiya under the conditions of readsorption. Ammonia is readsorbed on zeolites under these conditions, and one has to use the experimental conditions of the same contact time in order to evaluate the acid strength of zeolite from the peak maximum temperature. On the other hand, the ratio of intensity of low temperature peak (1-peak) to that of the high temperature peak (h-peak) increased with increasing the contact time of the carrier gas. This relation suggested that the 1-peak intensity depended upon the degree of evacuation of the weakly-held ammonia. The 1-peak is ascribable to very weakly or physically adsorbed ammonia on zeolites, and only the h-peak has to be accounted for to measure the number of acid sites.
  • Kazufumi Kato, Harumi Kondo, Kunio Esumi, Kenjiro Meguro
    1986 Volume 59 Issue 12 Pages 3741-3746
    Published: 1986
    Released: June 27, 2006
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    The emulsion polymerization of styrene was carried out in the presence of mixtures of a nonionic surfactant (poly(oxyethylene) hexadecyl ether; BC-20) and an anionic surfactant (sodium dodecyl sulfate; SDS or lithium perfluorooctanesulfonate; LiFOS). The polymerization rate changed with the hydrophile-lypophile balance (HLB) of the BC-n series. The polymerization rate considerably increased on the addition of SDS or LiFOS. However, the further addition of LiFOS caused a gradual depression of the polymerization rate. The polymerization rate was not dependent on the amount of styrene solubilized in the mixed emulsifier solution. The particle sizes decreased remarkably on adding SDS. The molecular weights of polystyrene in latex synthesized in mixed emulsifier solutions were larger than those in a single emulsifier solution. The molecular-weight distributions of polystyrene formed in mixed emulsifier solutions were wider than those of polystyrene formed in a single emulsifier solution. These results may be attributed to properties such as the composition and the charge density of the mixed micelles, and to the solubilized amount of styrene monomer in the mixed nonionic-anionic emulsifier solutions.
  • Tatsuya Hozaki, Mitsunori Kato, Mamoru Sato, Nobuo Tanaka, Yukio Morim ...
    1986 Volume 59 Issue 12 Pages 3747-3753
    Published: 1986
    Released: June 27, 2006
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    A stopped-flow small-angle X-ray scattering method was applied to study the structural change of Taka-amylase A by acid-denaturation. The structural change could be described by two successive steps. The first step is described by a change in the eccentricity of a prolate ellipsoid from 2.0 to 2.4; this was estimated by a comparison between the observed scattering profile and the theoretical scattering function of the prolate ellipsoid. The second step supposes that the X-ray scatterer in a solution comprises two kinds of particles with large and small radii of gyration. The X-ray scatterer with a large radius expands with time. By contrast, the radius of gyration of the small scatterer corresponds to that of a native Taka-amylase A monomer and it remains unchanged. These facts imply that in the denaturation of Taka-amylase A the molecule is prolonged by a partial unfolding of the polypeptide chain and then aggregates with each other.
  • Hironobu Umemoto, Teruo Uchida, Seiko Nakagawa, Shigeru Tsunashima, Sh ...
    1986 Volume 59 Issue 12 Pages 3755-3759
    Published: 1986
    Released: June 27, 2006
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    The temperature dependence of the rate constants for the reactions of ground-state atomic nitrogen with halogens were measured by means of a pulse radiolysis-resonance absorption technique. The rate constants for iodine and bromine were well expressed by the following Arrhenius expressions below 410 K: k(N+I2)=1.1×106 exp(−1170/T); k(N+Br2)=1.1×105 exp(−1490/T), in units of m3 mol−1 s−1. The rate constant for the reaction with chlorine was found to be 1.1×103 m3 mol−1 s−1 at 411 K. Below this temperature, the rate constants for N+Cl2 were too small to be measured. The preexponential factors for the I2 and Br2 reactions were found to be much smaller than the semiempirically calculated ones. These small preexponential factors suggest that the reactions between N(4S) and halogens proceed via nonadiabatic routes.
  • Woo-Sik Jung, Hiroshi Tomiyasu, Hiroshi Fukutomi
    1986 Volume 59 Issue 12 Pages 3761-3764
    Published: 1986
    Released: June 27, 2006
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    Effects of concentrations of perchlorate ion, nitrate ion, uranyl ion, and acid, isotopic substitutions, and temperature on 17O chemical shifts of oxygen in the uranyl ion (uranyl oxygens hereafter) have been studied in aqueous perchlorate media. Insensitivity of the 17O chemical shifts to [ClO4] leads to the conclusion that the perchlorate ion is not coordinated to the uranyl ion. The stability constant (0.10±0.04 m−1 at 25 °C and ionic strength 5.0 m; m=mol kg−1) of a UO2NO3+ complex, has been obtained from the dependence of the 17O chemical shifts on [NO3]. The 17O resonances shift toward the lower field with increasing concentrations of uranyl ion and acid, indicating the possibilities of the dimer formation of the uranyl ion and the protonation of uranyl oxygen atoms in concentrated solution, respectively. Isotope shifts in 17O nuclear magnetic shielding in the uranyl ion are interpreted in terms of the change of mean separation between the ground and lowest excited electronic states upon oxygen and uranium isotopic substitutions. Temperature dependence of 17O chemical shifts is discussed in connection with the isotope effects.
  • Sukeya Kodama, Atsushi Matsumoto, Yutaka Kubokawa, Masakazu Anpo
    1986 Volume 59 Issue 12 Pages 3765-3770
    Published: 1986
    Released: June 27, 2006
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    Photocatalytic activity of CdS and ZnS for the cis-trans isomerization of 2-butene is much higher than that of TiO2 and ZnO, though the double bond shift isomerization to 1-butene hardly proceeds in contrast with the case of the oxides. The addition of O2 or NO molecules leads to the remarkable inhibition of photocatalyzed isomerization of 2-butene, but not to the complete inhibition. Water vapor enhanced the photocatalyzed isomerization. From these results together with the ESR measurements before and after UV irradiation of the sulfide catalyst either in the presence or in the absence of butene, the following conclusions emerge: sulfur radicals such as \dotSn, which are produced by the hole trapping by lattice S2− ions and/or sulfur clusters existing in the catalyst inherently, play a significant role in the weakening of the C=C double bond of 2-butene via the interaction with the molecules; the stability of such sulfur radicals results in the much higher photocatalytic activity of CdS and ZnS catalysts as compared with that of metal oxide catalysts.
  • Makio Iwahashi, Yoko Ohbu, Tadashi Kato, Yumi Suzuki, Kazuhiro Yamauch ...
    1986 Volume 59 Issue 12 Pages 3771-3774
    Published: 1986
    Released: June 27, 2006
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    The conformation of molecules of normal alcohols in their pure liquids is estimated through an analysis of their self-diffusion coefficients, viscosities, and molar volumes. The conformation of molecules of shorter chained alcohols (C1–C3) is approximately of sphere, while that for longer chains is of rodlike shape. In pure liquids of alcohols, rigid rod molecules whose free rotating motions along their rod axes seem to be restricted, are randomly orientated and entangled with one another. The self-diffusion of long-chain alcohols involves a longitudinal translation of rodlike molecules. Large apparent hydrodynamic radii suggest that the transport unit of normal alcohol is a dimer (on an average) of alcohol molecules.
  • Yasukiyo Ueda
    1986 Volume 59 Issue 12 Pages 3775-3779
    Published: 1986
    Released: June 27, 2006
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    Methyl triacontanoate (MT) was deposited on the cleavage face of the KCl crystal in vacuo. The MT film was composed of V-shaped crystals growing along two directions crossing at 32°, and these crystals intersected at right angles to each other. The bisectional direction of the V-shaped crystals corresponds to the [110] direction of the substrate crystal. The electron-diffraction pattern from the film consisted of the reflection spots corresponding to the (hkl)s planes of the subcell and the series of 00l reflections in the small-angle region. The crystal structure of the deposited MT crystal was monoclinic in form. The (110) plane of the MT crystal was oriented parallel to the substrate (001) plane, and its c-axis was parallel to the [110] direction of the substrate crystal. The V-shaped crystal was explained by the molecular arrangement in the epitaxial growing crystals. When the substrate was kept at a higher temperature than the melting point of MT, the deposit coagulated to disk-like crystals whose c-axis was perpendicular to the substrate.
  • Jun-ichi Aihara
    1986 Volume 59 Issue 12 Pages 3781-3789
    Published: 1986
    Released: June 27, 2006
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    A secular determinant for a polycyclic conjugated molecule, combined with a test dipole, is definable as a function of the applied magnetic field. It was found that this determinant can be expanded graph-theoretically into a characteristic polynomial. A secondary magnetic field is brought about by so-called ring currents. A new formula for evaluating the secondary field was derived by applying Newton’s method to this polynomial. This formula indicates that the secondary field at any point in the molecular plane is given exactly as a sum of the contributions of all π-electron circuits. The contribution of each π-electron circuit is expressible in terms of a pure geometric factor and an aromatic stabilization energy assigned to the circuit. The secondary field and then the proton chemical shifts can thus be related to aromaticities of individual π-electron circuits. Magnetotropism of most polycyclic conjugated molecules can be rationalized in this manner. π-Electron circuits which share the conjugated atom nearest to a given proton dominate the chemical shift. In general, a peripheral π-electron circuit contributes modestly to the overall thermodynamic stability of a molecule, but contributes much to the secondary fields at attached protons.
  • Takeshi Sakaizumi, Masahiko Obata, Katsumasa Takahashi, Eiichi Sakaki, ...
    1986 Volume 59 Issue 12 Pages 3791-3795
    Published: 1986
    Released: June 27, 2006
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    The microwave spectra of CH380SeCN, CH378SeCN, CH380Se13CN, CH380SeC15N, sym-CH2D80SeCN, and asym-CH2D80SeCN have been observed. In order to determine the rotational constants of 13CH380SeCN, we used the transition frequencies observed by Landsberg. From these spectra the complete rs coordinates of seven atoms have been calculated using Kraitchman’s equation. The structural parameters (bond lengths in Å(1Å=0.1 nm) and angles in degree) are: r(C1–H1)=1.073(4), r(C1–H2)=1.083(6), r(C1–Se)=1.954(7), r(Se–C2)=1.836(11), r(C2–N)=1.162(9), ∠H1–C1–H2=110.6(6), ∠H2–C1–H2′=111.4(3), ∠H1–C1–Se=105.4(5), ∠H2–C1–Se=109.3(6), ∠C1–Se-C2=96.0(11), and ∠Se–C2–N=179.3(15). It was found from the rs structural parameters that the methyl group is at a staggered position with respect to the cyano group, the methyl group does not show C3v symmetry, the bond length of r(Se–C2) is much shorter than that of r(Se–C1), and the chain bond of Se–C2–N is linear.
  • Noboru Tanaka
    1986 Volume 59 Issue 12 Pages 3797-3802
    Published: 1986
    Released: June 27, 2006
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    The semiempirical method is used to calculate potential energy surfaces. The linear H3 and rectangular H4 systems have been chosen as standard surfaces in order to compare the surface features. Relationships between diatomic constants and topological features along a minimum energy path, and the height and location of the barrier, are demonstrated.
  • Masayuki Matsumoto, Hirofumi Yajima, Takashi Handa
    1986 Volume 59 Issue 12 Pages 3803-3808
    Published: 1986
    Released: June 27, 2006
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    The B–A transition in DL-ABA occurs in the wide range of temperature near its decomposition temperature, and the transition pattern is similar to that of γ–α transition in glycine, whereas the pattern of α–γ transition in DL-NL is different from that in glycine, and the α–γ transition of DL-NL is of the first order. The enthalpy difference between modifications A and B of DL-ABA was nearly equal to the enthalpy of transition determined by DSC.
  • Masamichi Ishikawa, Masami Ichikuni
    1986 Volume 59 Issue 12 Pages 3809-3814
    Published: 1986
    Released: June 27, 2006
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    Crystal defects in calcite containing Na and K ions were investigated by means of a model based on statistical thermodynamics and measurements of thermoelectric power. The varying amount of Na and K ions in the crystal was interpreted on an assumption of ideal solution of the ions as Ca1−xy\squarex+y[Na2x, K2y]CO3, where \square and [ ] means Ca-vacancy and interstitial ion, respectively. In the model, the excess charge of Na and K ions is balanced with Ca-vacancy to form interstitial-vacancy pairs ([Na, K]2\square). Measurements of thermoelectric power in calcite showed the cationic transport which resulted from Na and K interstitials and/or Ca-vacancies. From the ideal mixing of Na and K ions at interstitial sites, the K/Na molar ratio in calcite was correlated with that in aqueous solution at 20 °C and pH 8.5 by the formula,
    \fracKSNaS=0.20\fracKLNaL,
    where S and L refer to solid- and aqueous-phase, respectively.
  • Masashi Hojo, Kazukiyo Nishikawa, Yoshihiro Akita, Yoshihiko Imai
    1986 Volume 59 Issue 12 Pages 3815-3820
    Published: 1986
    Released: June 27, 2006
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    The polarographic behavior of 2-methyl-2-nitropropane ((CH3)3CNO2) was examined at DME in acetonitrile with various supporting electrolytes. The addition of Et4N+ or n-Bu4N+ caused the half-wave potential (E1⁄2) of (CH3)3CNO2 to shift negatively in the presence of a fixed concentration of NaClO4. The negative shift was explained in terms of the interaction between tetraalkylammonium cations and the unreduced molecule of (CH3)3CNO2. The formation of (CH3)3CNO2\ ewdot(Na+)2 was also suggested, and the conditional formation constants of the species were obtained by the positive shift in the E1⁄2 of (CH3)3CNO2 with increasing concentration of Na+ at certain concentrations of Et4N+ and n-Bu4N+. Other nitroalkanes and nitrobenzenes were also examined. The effect of water on the half-wave potentials of the first waves of the nitro compounds suggested the formation of RNO2\ ewdot(H2O)2-type species.
  • Akiko Kobayashi, Yukiyoshi Sasaki, Tokuko Watanabe, Seiichiro Ikehata, ...
    1986 Volume 59 Issue 12 Pages 3821-3827
    Published: 1986
    Released: June 27, 2006
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    The physical properties and the structure of black solids obtained by the high-pressure reaction of CSe2 were examined by IR, X-ray diffraction, scanning electron microscope, electron diffraction, thermal analyses and magnetic experiments. The crystalline solid, which was metallic (σ(RT)≈50 S cm−1) at ambient pressure became superconductor above 20 GPa(Tc(onset)=6 K), while the amorphous solid was insulating. Contrary to the previously proposed one- or two-dimensional polymerization structure of (CSe2)x, it has been revealed that the metallic CSe2 sample have a rather complex structure that is composed of the crystalline hexagonal Se, graphite and some amorphous parts. Thus, the high conductivity and the diamagnetism of the crystalline solid at ambient pressure seems to come from graphite part and the superconductivity seems to come from hexagonal Se part. The superconducting transition behavior depended on the path of the pressure-cooling steps. The superconducting state was observed only when the pressure was increased at the low temperature.
  • Yoshinari Baba, Masanori Ohshima, Katsutoshi Inoue
    1986 Volume 59 Issue 12 Pages 3829-3833
    Published: 1986
    Released: June 27, 2006
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    The equilibrium and kinetic aspects of palladium(II) extraction from hydrochloric acid with triisobutylphosphine sulfide (TIBPS) in toluene were studied, along with the aqueous solubility and interfacial adsorption equilibrium of the extractant. From the equilibrium study, palladium(II) was found to be extracted as a 1:1 Pd:extractant binuclear complex. The extraction rate of palladium(II) was reasonably explained by the interfacial reaction model, assuming that the elementary reactions between the extractant adsorbed at the interface and the aquatrichloro and tetrachloro complexes of palladium(II), [PdCl3], and [PdCl4]2− in the aqueous phase are the rate-determining steps.
  • Yoshinari Baba, Yukihiro Umezaki, Takashi Ueda, Katsutoshi Inoue
    1986 Volume 59 Issue 12 Pages 3835-3839
    Published: 1986
    Released: June 27, 2006
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    The extraction of mercury(II) from hydrochloric acid was compared using five kinds of sulfur-containing extractants. Mercury(II) was extracted most effectively by trialkylphosphine sulfides. Subsequently, the distribution equilibria of mercury(II) from hydrochloric acid with triisobutylphosphine sulfide (TIBPS=\barS) and trioctylphosphine sulfide (TOPS=\barS) in toluene have been measured at 303 K in order to clarify the concentration dependencies of the reactant species. It was found that mercury(II) is extracted according to the solvation reaction by TIBPS or TOPS as a mercury(II): extractant 1:2 complex, HgCl2S2, in the range of low loading ratio of mercury(II) to the extractants, and as a 1:1 binuclear complex, (HgCl2)2S2, in the region of high loading ratios, as follows:
    HgCl2+2\barS\ ightleftharpoons‾HgCl2S2 Ke
    2HgCl2+2\barS\ ightleftharpoons‾(HgCl2)2S2 Ke
    The extraction equilibrium constants, Ke and Ke′, were evaluated as Ke=4.0×105 (dm3 mol−1)2 and Ke′=2.0×108 (dm3 mol−1)3 for TIBPS and as Ke=7.2×106 (dm3 mol−1)2 for TOPS.
  • Kazuaki Ito, Etsuro Iwamoto, Shigehito Suehisa, Hiroyuki Isono, Yuroku ...
    1986 Volume 59 Issue 12 Pages 3841-3846
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The conductances of bis(2,4-pentanedionato)(diamine)cobalt(III) perchlorates ([Co(acac)2(diamine)]ClO4, diamine: en=ethylenediamine, pn=1,2-propanediamine, N,N-dmen=N,N-dimethylethylenediamine, N,N′-dmen=N,N′-dimethylethylenediamine, N,N,N′-trimen=N,N,N′-trimethylethylenediamine, N,N,N′,N′-tmen=N,N,N′,N′-tetrametnylethylenediamine) were measured in isodielectric solvents, 1-propanol (n-PrOH), acetone (Me2CO), and 60 and 80 mol% acetone in 1-propanol (n-PrOH–Me2CO) at 25 °C. In spite of the increase in size of [Co(acac)2(diamine)]+ due to the introduction of N-methyl groups, the Walden products (λ0+·η) of the chelate cations were found to increase in all solvents. The contribution per N-methyl group was large in n-PrOH. The variation in the ionic association constants (Ka) with the number of NH protons in the chelate cations was small in all solvents. The Ka values for [Co(acac)2(N,N′-dmen)]ClO4 were larger than those for other chelate salts in all solvents. These results could be explained in terms of the solvation of the NH protons (diamine in [Co(acac)2(diamine)]+) by oxygen atoms of n-PrOH and Me2CO, and of oxygen atoms (acac) by the OH proton of n-PrOH owing to hydrogen bonding interactions and desolvation resulting from the introduction of the N-methyl groups. For [Co(acac)2(en)]+ in n-PrOH a solvation model to form a six-membered ring was proposed.
  • Akio Yuchi, Kenji Imai, Hiroko Wada, Motoo Shiro, Genkichi Nakagawa
    1986 Volume 59 Issue 12 Pages 3847-3854
    Published: 1986
    Released: June 27, 2006
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    The equilibria were studied in the extraction of divalent transition metal ions (M2+: Co2+, Ni2+, Zn2+, Cd2+) with 8-quinolinol (Hq) from aqueous solutions containing various anions (X) into some organic solvents. The effects of −log[H+] and total concentrations of 8-quiriolinol and metal ions on the distribution were examined in detail. Three species, M2q3(Hq)3X, Mq2(Hq), and M2q4(Hq)2 are responsible for the extraction. The extraction of M2q3(Hq)3X is favorable when hydrophobic anions and polar solvents are used. On the other hand, the extraction constants of Mq2(Hq) are almost the same for each metal ion irrespective of anions and solvents. With increasing the metal ion concentration in the organic phase, Mq2(Hq) dimerizes to form M2q4(Hq)2. The decrease in the distribution ratio by prolonged shaking under certain conditions is reasonably ascribed to the slow precipitation of Mq2·2H2O which has been made supersaturated by the rapid establishment of all the equilibria except the precipitation reaction. An X-ray crystallographic study for Ni2q4(Hq)2 showed that two nickel atoms are surrounded by three bidentate ligands with facial and meridional configurations about their oxygen atoms and these two isomers form a binuclear structure jointed by two strong hydrogen bonds.
  • Hiromichi Yamada, Toshiyuki Okuda, Yukio Fujii, Masateru Mizuta, Motoh ...
    1986 Volume 59 Issue 12 Pages 3855-3858
    Published: 1986
    Released: June 27, 2006
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    The extraction of copper(II) was carried out with lipoic acid in benzene at 25 °C and at a constant ionic strength in the aqueous phase: 0.1 mol dm−3 (NaNO3). The partition constant, KD,HA of lipoic acid between benzene and water, and the dimerization constant, K2,HA of lipoic acid in benzene were determined: logKD,HA=1.17 and logK2,HA=2.51 The dimeric copper(II) lipoate is responsible for the extraction:
    2Cu2++3(HA)2,o\oversetKex(22)\ ightleftharpoons(Cu2A4(HA)2)o+4H+
    with the extraction constant, logKex(22)=−11.00. It was proved that lipoate ion coordinates to copper(II) with the carboxylate group without a remarkable participation of the disulfide moiety in the coordination.
  • Ken-ichi Okamoto, Sen-ichi Aizawa, Takumi Konno, Hisahiko Einaga, Jins ...
    1986 Volume 59 Issue 12 Pages 3859-3864
    Published: 1986
    Released: June 27, 2006
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    The crystal structure and the absolute configuration of the selectively formed title isomer, (+)600CD-[Co{Co(L-cys-N,S)3}2](NO3)2·5H2O, have been determined by X-ray diffraction. In the (+)600CD isomer, the six L-cysteinates coordinate through the nitrogen and sulfur atoms to give two terminal [Co(L-cys-N,S)3] moieties. The central cobalt atom spans the six sulfur atoms in these terminals to form a trinuclear structure. The (+)600CD isomer takes selectively a ΛLLLΛLLL configuration, in which both of the two terminals have a ΛLLL-fac(S) configuration, and the six sulfur donor atoms take an R one. The L-cysteinate chelate rings take a lel conformation along the C3 axis and the carboxyl or carboxylato groups take the axial orientations forming the intramolecular hydrogen bonds. The (−)600CD isomer is assigned to the ΔLLLΔLLL configuration on the basis of the electronic absorption, CD, and 13C NMR spectral behaviors. The selective formation for each of the (+)600CD and (−)600CD isomers is discussed in relation to their reaction conditions.
  • Takumi Oshima, Toshikazu Nagai
    1986 Volume 59 Issue 12 Pages 3865-3869
    Published: 1986
    Released: June 27, 2006
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    2,3-Dichloro-5,6-dicyanobenzoquinone (DDQ) reacted with diazoethane to give stereoisomeric bicyclic diones (3, isomer ratio=3.4) arising from dipolar addition to the C=C bond of DDQ. DDQ reacted with phenyldiazomethane to afford also stereoisomeric bicyclic diones (7) in the ratio of 5:1, together with stilbenes (8). On the other hand, DDQ gave the (ethenyloxy)benzene derivative (14) with 1-phenyldiazoethane. The formation of 8 and 14 was interpreted by considering the participation of 1:1 betaines resulting from addition to the C=O bond. The added methanol captures the betaines, thus giving rise to dimethyl acetals of benzaldehyde and acetophenone, along with 2,3-dichloro-5,6-dicyanohydroquinone. These reactivities of DDQ were discussed in comparison with those of chloranil.
  • Takao Tokumitsu
    1986 Volume 59 Issue 12 Pages 3871-3876
    Published: 1986
    Released: June 27, 2006
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    β-Nitro enamines (1) reacted with isocyanates and isothiocyanates to give β-(substituted carbamoyl) and β-(substituted thiocarbamoyl) β-nitro enamines, respectively. The reaction of 1 with benzoyl isothiocyanate gave β-(benzoylthiocarbamoyl) β-nitro enamines (8) and/or a mixture of 8 and 4(1H)-pyrimidinethione derivatives (9) which were cyclization products of 8. The isolated 8 afforded the corresponding 9 in high yields upon heating in DMF. The reaction of 1 with dimethyl acetylenedicarboxylate gave [2+2] cycloadducts (12) and/or a mixture of 12 and δ-nitro dienamino diesters (13) which were ring cleavage products of 12. Compounds 12 afforded 13 upon heating in toluene or xylene.
  • Yuichiro Haramoto, Yoko Tomita, Hiroyoshi Kamogawa
    1986 Volume 59 Issue 12 Pages 3877-3880
    Published: 1986
    Released: June 27, 2006
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    (+)-2-Methylbutyl p-(5-alkyl-1,3-oxathian-2-yl)benzoate and -cinnamate (7) were synthesized. The mesomorphic behavior of these compounds were measured. Though (+)-2-methylbutyl p-(5-alkyl-1,3-oxathian-2-yl)benzoate did not exhibit any liquid-crystal phase, the corresponding 1,3-dithiane compounds (8-1, 8-2, and 8-3) and compound (7-4) having R’ of a normal alkyl chain exhibited a smectic phase. This must originate in the wider molecular widths of compounds 7-1, 7-2, and 7-3. Though cinnamate of compounds 7 and 8 exhibited an enantiotropic behavior, the corresponding benzoate did not. This must originate from an increase in the length of the conjugated system and the molecular length.
  • Hiyoshizo Kotsuki, Hiroyuki Ohnishi, Yasuhiro Akitomo, Masamitsu Ochi
    1986 Volume 59 Issue 12 Pages 3881-3884
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The endo-Diels–Alder adduct of furan with methyl acrylate was transformed into a bis-γ-lactone derivative which is a well-known precursor for the synthesis of (±)-avenaciolide. The route involves 13 steps and the overall yield was 17.9%.
  • Kin-ichi Tadano, Youichi Iimura, Yukinori Hotta, Chiyoko Fukabori, Tet ...
    1986 Volume 59 Issue 12 Pages 3885-3892
    Published: 1986
    Released: June 27, 2006
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    Two stereoisomers of the indolizidine alkaloid swainsonine, (−)-8-epi-swainsonine (2) and (−)-1,8-di-epi-swainsonine (3), have been synthesized from the known methyl 3-acetamido-2-O-acetyl-4,6-O-benzylidene-3-deoxy-α-D-glucopyranoside and methyl 3-acetamido-2-O-acetyl-3-deoxy-4,6-di-O-mesyl-α-D-glucopyranoside (14), respectively. The key pyrrolidine ring formation was achieved by intramolecular cyclization of a 6-O-tosyl derivative or a di-O-mesyl derivative 14 efficiently. The α-mannosidase inhibitory activity of the synthetic 2 and 3 was also evaluated.
  • Choichiro Shimasaki, Mariko Wakabayashi, Shizuo Yoshida
    1986 Volume 59 Issue 12 Pages 3893-3896
    Published: 1986
    Released: June 27, 2006
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    5-(Hydroxyphenoxymethyl)-2-oxazolidinone (1) and p- or m-bis(2-oxooxazolidin-5-ylmethoxy)benzene (2 or 3) were prepared by the reaction of tris(2,3-epoxypropyl)-1,3,5-triazin-2,4,6(1H,3H,5H)-trione with hydroquinone and resorcinol. These compounds were found by the thermal analysis to be thermally stable. The activation energies of the pyrolysis for 1, 2, and 3 were calculated from the DTA curves to be 142.7, 158.8, and 130.0 kJ mol−1, respectively. The mechanism of the main fragmentation of the linkages between the benzene and oxazolidinone rings by electron impact was found to consist of two processes; a simple cleavage and a rearrangement reaction. Further, each process had the three cleavage modes. In mass spectra of 2 and 3, the fragment ion which corresponded to the molecular ion peak for 1 was detected. High resolution mass spectrometry established the composition of many peaks in the low resolution spectra of the compounds studied.
  • Yoshihiko Inoue, Shigeo Tanimoto, Tatsuo Oida
    1986 Volume 59 Issue 12 Pages 3897-3900
    Published: 1986
    Released: June 27, 2006
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    The reaction of 2,2-diphenyl-1,3-dithiolane S-oxide with lithium diisopropylamide results in fragmentation to thiobenzophenone followed by further conversion leading to alkyl diphenylmethyl sulfide on trapping with alkyl halide. The reaction of 2,2-diaryl-1,3-dithiolane S,S′-dioxides with lithium diisopropylamide proceeded smoothly to afford 1,1-diaryl-N,N-diisopropylmethanesulfinamides in moderate yields via the intermediate diaryl thioketone S-oxides.
  • Kiyoshi Tanaka, Hideyuki Masuda, Keiryo Mitsuhashi
    1986 Volume 59 Issue 12 Pages 3901-3904
    Published: 1986
    Released: June 27, 2006
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    Trifluoroacetonitrile oxide and N-phenyl-C-(trifluoromethyl)nitrilimine cycloadded with norbornenes, resulting in the exclusive formation of the exo-adducts, while the concomitant formation of the endo-adducts was observed in their cycloadditions with norbornadienes. The nitrile oxide was subjected to the cycloaddition with 2,3-disubstituted norbornadienes to evaluate the effect of the substituents on the exo/endo stereoselectivity. The electron-withdrawing substituents tend to favor the formation of the exo-adducts.
  • Akira Sugimori, Tetsuo Yamada, Hiroaki Ishida, Masayuki Nose, Keiko Te ...
    1986 Volume 59 Issue 12 Pages 3905-3909
    Published: 1986
    Released: June 27, 2006
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    Gamma-irradiation of quinoline and its derivatives in alcohols brings about alkylation at the 2- or 4-position of pyridine ring. Hydroxyalkyl radicals play important roles in the radiation-induced alkylation with alcohol. The radiation-induced substitution of CF3CH2– and CF3CH(OH)– for H in pyridine and pyrimidine rings occurs in low yields.
  • Akira Sugimori, Tetsuo Yamada
    1986 Volume 59 Issue 12 Pages 3911-3915
    Published: 1986
    Released: June 27, 2006
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    Quinoline and 4-methylquinoline are efficiently alkylated with alkanoic acid in the presence of iron(III) sulfate upon visible light-irradiation. Iron(III) sulfate not only accelerates the photoreaction but also increases the yield of alkylation. Gamma-irradiation also brings about the alkylation. In the photo- and radiation-induced alkylation with alkanoic acid, alkyl radicals play important roles.
  • Chung-gi Shin, Yoshiharu Nakajima, Toshiya Haga, Yoshiaki Sato
    1986 Volume 59 Issue 12 Pages 3917-3923
    Published: 1986
    Released: June 27, 2006
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    The condensation of 1,4-diacetyl- or 3-substituted 2,5-piperazinediones (PDO) with various salicylaldehyde derivatives in the presence of a base, such as potassium t-butoxide or triethylamine, was found to give two extremely different kinds of products: 1-acetyl-3-arylmethylene-PDO and 3-(acylamino)coumarin derivatives. The former, which has a (Z)-geometric structure, was readily converted to the latter by irradiation. Furthermore, the conversion mechanism and the structural confirmation are discussed.
  • Masayoshi Onishi, Shigero Oishi, Mitoshi Sakaguchi, Isato Takaki, Kats ...
    1986 Volume 59 Issue 12 Pages 3925-3930
    Published: 1986
    Released: June 27, 2006
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    Pyrex-filtered photoirradiation with a high-pressure Hg lamp was performed for a thermally inert hydridocobalt(I) CoH[PPh(OEt)2]4 in the presence of some allylic compounds. Allyl benzoate and allyl phenyl ether showed the cleavage of allylic-O bonds to give propene in a stoichiometric quantity to the complex charged. Photoassisted catalytic double-bond migration occurred for N-allylacetamide, N,N-diethylallylamine, and allylbenzene to afford the respective (E)- and (Z)-1-propenyl derivatives with kinetically controlled E, Z compositions, and the fractions of Z isomers at the initial stage of the reaction proceeding were near 79, 30, and 20%, respectively. Laser flash photolysis study revealed that the double-bond migration was initiated by the coordination of the substrates through C=C double bond rather than nitrogen or oxygen donor-atom to the coordinatively unsaturated species “CoH[PPh(OEt)2]3” photogenerated.
  • Tomokazu Yasuda, Takuzo Aida, Shohei Inoue
    1986 Volume 59 Issue 12 Pages 3931-3934
    Published: 1986
    Released: June 27, 2006
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    Reactivity of the axial aluminum-phenoxyl and -alkoxyl bond (Al-X) of aluminum porphyrin (1, (TPP)AIX, (TPP): (5,10,15,20-tetraphenylporphinato)) toward epoxide, β-lactone, and ε-lactone was examined in relation to the ring-opening polymerization of these cyclic compounds catalyzed by 1. The reactivity of
    (Remark: Graphics omitted.)
    aluminum phenoxide was in the order, epoxide>β-lactone>ε-lactone, while that of the alkoxide, ε-lactone>β-lactone.
  • Hidetoshi Nagamoto, Hakuai Inoue
    1986 Volume 59 Issue 12 Pages 3935-3939
    Published: 1986
    Released: June 27, 2006
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    The hydrogenation of 1,3-butadiene was carried out over a palladium membrane at 100 °C in two ways: (1) by hydrogen permeating the membrane, and (2) by hydrogen premixed in the gas phase. In the reactions using permeate hydrogen, hydrogenation at the higher pressures of butadiene was limited by the hydrogen permeation; namely, the rate was determined by the pressure of hydrogen upstream. The product composition was, at the same time, unchanged by the reaction rate. At the lower pressures of butadiene, the selectivity for butene formation was decreased with the decrease in the butadiene pressure, and the reaction rate was approximately equal to that when the premixed hydrogen was used over the β-phase membrane. The mechanism of the reaction using premixed hydrogen over the α-phase membrane was analyzed quantitatively by obtaining the dissolved hydrogen concentration from the measurement of the hydrogen-permeation rate from the reaction surface. It was elucidated that the reaction was limited by the hydrogen adsorption, the rate of which was affected by the presence of 1,3-butadiene, and that the reaction rate was much smaller than that when permeate hydrogen was used.
  • Yasushi Itoi, Masami Inoue, Saburo Enomoto
    1986 Volume 59 Issue 12 Pages 3941-3943
    Published: 1986
    Released: June 27, 2006
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    The epoxidation of fatty acid esters was carried out with a 30% aqueous hydrogen peroxide in the presence of a molybdenum oxide–tributyltin chloride on a charcoal catalyst in 2-propanol at 50 °C. Such inner olefins as ethyl erucate and ethyl oleate gave good yields of 77 and 76%, respectively. Ethyl elaidate, a trans-form of ethyl oleate, was less reactive (40% yield). Several vegetable oils such as rapeseed oil, olive oil, soybean oil, cottonseed oil, corn oil, and linseed oil were oxidized with the oxirane oxygen contents of 5.3 to 3.5%.
  • Mohamed M. Fahmi Hegazi
    1986 Volume 59 Issue 12 Pages 3945-3950
    Published: 1986
    Released: June 27, 2006
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    The partitions of trichloroacetic and butyric acids between aqueous solutions and various nitrobenzene–toluene mixtures have been carried out at 25.0 and 30.0 °C, respectively. The observed nonlinearities for both acids of the monomer partition constants and the dimerization constants with the nitrobenzene mole fraction are interpreted in terms of the fractionation factors of effective exchangeable solvation sites of the involved species. Butyric acid monomer is concluded to have three sites for the solvation of the carboxylic hydrogen, carboxylate region, and alkyl chain. Desolvation of the former two sites is necessary for the formation of the dimer for which only two sites corresponding to its two alkyl chain are identified. The solvation sites of trichloroacetic acid monomer and dimer are identical and a singly hydrogen-bonded structure for the dimer is deduced. Dimerization of this acid in the organic phase proceeds by desolvation of what is equivalent to the sites of only one monomer.
  • Héctor Jose Marini, Rosa Isabel Antón, Maria Susana Boer ...
    1986 Volume 59 Issue 12 Pages 3951-3955
    Published: 1986
    Released: June 27, 2006
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    The optimum working conditions for the complexing reactions between Ti(IV) and 2-(5-chloro-2-pyridylazo)-5-dimethylaminophenol (5.ClDMPAP) in aqueous alcoholic solutions were studied. When an ethanol solution of 5.ClDMPAP is added to a Ti(IV) aqueous solution, complex species, whose spectral and stoichiometric characteristics depend on pH, develop rapidly. The complex selected for the analytical work forms between pH 4.7 and 5.8 and has a 3:1 ligand-metal molar ratio. The complex fulfils Beer’s law up to a Ti(IV) concentration of 0.7 ppm, working at λmax=580 nm. The optimum concentration range (Ringbom) was between 0.05 and 0.7 ppm of Ti(IV). The molar absorptivity at λmax=580 nm and Sandell index are 4.39×104 dm3 mol−1 cm−1 and 0.0011 μg cm−2, respectively. An absorptiometric method to determine Ti(IV) was developed and the proper ways to reduce interferences produced by some anions and cations are described. The method developed was applied to Ti(IV) determination in optical glass and ceramic materials.
  • José-Gonzalo Rodriguez, Alfonso De Pablo, Pilar Smith-Verdier, ...
    1986 Volume 59 Issue 12 Pages 3957-3961
    Published: 1986
    Released: June 27, 2006
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    The synthesis and analysis by 1H NMR of the methyl substituted naphthazarins were attempted. The chemical shifts of the substituents and of the ring protons were compared with those in their diacetates and were then correlated with the quinonoid or benzenoid nature of the rings. X-Ray diffraction analysis of tetramethylnaphthazarin, 2,3,6,7-tetramethyl-5,8-dihydroxy-1,4-naphthoquinone, has shown that this exists, in solid state, as a centrosymmetric charge-transfer complex with itself. The compound crystallizes in the Ibam space group, with an orthorhombic cell of dimensions a=17.479(1), b=9.983(1), c=6.752(1) Å, and four molecules in the unit cell. The crystal is built from molecules stacked up the c-axis and the interplanar distance between two overlapping molecules is 3.38 Å.
  • Makoto Isihara
    1986 Volume 59 Issue 12 Pages 3963-3964
    Published: 1986
    Released: June 27, 2006
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    The force theorem is generalized by using the spin-specified momentum operator in the hypervirial theorem. A theorem consequent on this concerns a balance in forces acting on up- and down- spin electrons. The theorem is expected to be useful for examining accuracy of approximate wave functions for open-shell molecules.
  • Shunsuke Takenaka, Tetsuya Ikemoto, Shigekazu Kusabayashi
    1986 Volume 59 Issue 12 Pages 3965-3966
    Published: 1986
    Released: June 27, 2006
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    The homologous series of N-[4-(4-n-alkoxybenzoyloxy)benzylidene]-4-(2-methylbutoxy)aniline (1), and N-[4-[4-(2-methylbutoxy)benzoyloxy]benzylidene]-4-n-alkoxyaniline (2), and N-[4-(4-n-alkoxybenzoyloxy)-3-hydroxybenzylidene]-4-(2-methylbutoxy)aniline (3) where the 2-methylbutoxyl group has an S-configuration, have been prepared. Series 1 and 2 form a chiral smectic C (SC*) phase in addition to a cholesteric (Ch) and a chiral smetic G (SG*) phases, and series 3 form (SC*) and Ch phases.
  • Ichiro Okura, Naruhiko Kaji, Shigetoshi Aono, Tsuyoshi Nishisaka
    1986 Volume 59 Issue 12 Pages 3967-3968
    Published: 1986
    Released: June 27, 2006
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    Viologen linked porphyrins, ZnP(CnV)4, with various methylene chain lengths (n=2–5) between the porphyrin and the viologen have been synthesized. These compounds were applied to photoinduced hydrogen evolution in a system containing NADPH–ZnP(CnV)4–hydrogenase under steady state irradiation. On the addition of surfactant to the system, a remarkable rate increase of hydrogen evolution was observed in the case of ZnP(C5V)4.
  • Hideta Ishihara, Koji Yamada, Tsutomu Okuda
    1986 Volume 59 Issue 12 Pages 3969-3970
    Published: 1986
    Released: June 27, 2006
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    Temperature dependences of 69Ga and 81Br NQR frequencies showed that phase transitions take place at 98 and 137 K in [(CH3)4N]2Ga2Br6 and that the C3 reorientation of the GaBr3 group occurs in [(C2H5)4N]2Ga2Br6 around room temperature.
  • Yuusuke Katsuragi, Osamu Neda, Kotaro Yamauchi, Takahiro Masuda
    1986 Volume 59 Issue 12 Pages 3971-3972
    Published: 1986
    Released: June 27, 2006
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    Rate constants of reactions of dibromide anion radical with some aliphatic dipeptides or unsaturated compounds including pyrimidine bases have been determined by flash photolysis. Difference in activation energy between, dibromide and dichloride anion radicals has been estimated by comparing rate constants obtained for common substrates.
  • Yoshio Takasu, Yuichi Fujii, Yoshiharu Matsuda
    1986 Volume 59 Issue 12 Pages 3973-3974
    Published: 1986
    Released: June 27, 2006
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    A cyclic voltammetry study of a platinum-glassy carbon model catalyst-electrode (Pt/GC) in an aqueous solution of H2SO4 revealed that the peak potentials for the anodic oxidation of methanol shifted a little to the negative potential and that the current densities decreased greatly with the decrease in the size of the platinum particles.
  • Sigeru Torii, Hideo Tanaka, Toshiyuki Ohshima, Michio Sasaoka
    1986 Volume 59 Issue 12 Pages 3975-3976
    Published: 1986
    Released: June 27, 2006
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    An efficient electroreductive conversion of 3′-chlorocephalosporins and their analogues into the corresponding 3-methylenecephams has been performed in an aqueous THF–LiClO4–(Pb cathode) and/or aqueous MeCN–EtOH–LiClO4–NH4ClO4 (Pb cathode) system.
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