Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 50 , Issue 10
Showing 1-50 articles out of 77 articles from the selected issue
  • Michiya Itoh, Shu-ichi Furuya, Toshihiko Okamoto
    1977 Volume 50 Issue 10 Pages 2509-2511
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The exciplex (at room temperature) and EDA complex (at low temperature) fluorescence was observed in 3-methylpentane solution of 1,4-dicyanonaphthalene with several alkylbenzenes and alkylnaphthalenes. The fluorescence behavior provides evidence for an identical fluorescent state of the exciplex and EDA complex.
  • Kazuyori Konishi, Kensuke Takahashi
    1977 Volume 50 Issue 10 Pages 2512-2516
    Published: 1977
    Released: April 19, 2006
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    The 13C and 1H NMR spectra of 2-pyridylmethyl (α-picolyl), 2-pyridylamino, 2-pyridyloxy, and 2-pyridylthio anions were observed in polar solvents with lithium as a counter ion. The chemical shifts are compared with the electron densities calculated using the PPP and CNDO/2 MO methods. A linear relationship was obtained between the 13C chemical shifts and π-electron densities. The charge distributions on the anions are discussed, and it is found that the 2-pyridylamino anion and its methyl derivatives can be regarded as delocalized anions with the same significance as a series of picolyl anions.
  • Kou Hatada, Yoshio Ono
    1977 Volume 50 Issue 10 Pages 2517-2521
    Published: 1977
    Released: April 19, 2006
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    Synthetic zeolites were found to be effective catalysts for the synthesis of 1-substituted 2-pyrrolidinone by the reaction of γ-butyrolactone with amines. 1-Propyl-2-pyrrolidinone was obtained in the equilibrium yield with practically 100% selectivity over copper exchanged Y-zeolite at 280 °C. The effects of reaction temperature, contact time and partial pressures of the reactants were examined. A reaction mechanism is proposed for the ring transformation based on the kinetic studies of the reaction of γ-butyrolactone with propylamine.
  • Aritada Hatta
    1977 Volume 50 Issue 10 Pages 2522-2527
    Published: 1977
    Released: April 19, 2006
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    Infrared dichroism of nematic liquid N-(p-methoxybenzylidene)-p-butylaniline (MBBA) was measured using a conventional transmission method and an ATR method. In the former, KBr windows were used as substrates. The degree of orientation order of the homogeneous structure, which was achieved by a rubbing procedure, was obtained to be S=0.40. Using the measured dichroic ratios, the angles between the transition moments and the long axis of the molecule were calculated. The calculated values are in satisfactory agreement with the molecular conformation already suggested. In the ATR method, In2O3-coated glass plates were used as substrates. Rubbing of the In2O3 surface gave a uniform homogeneous orientation with an S value of 0.57. An In2O3 surface treated with dimethyldichlorosilane gave a homeotropic texture with an S value of 0.53. The directions of the transition moments relative to the long axis of the molecule closely agreed with those obtained from transmission spectra.
  • Takayasu Miura, Masao Nakamura
    1977 Volume 50 Issue 10 Pages 2528-2532
    Published: 1977
    Released: April 19, 2006
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    The heats of mixing of nonionic surfactants, poly(oxyethylene) dodecyl ethers C12H25(OC2H4)nOH (n=0—5) with a nonpolar liquid, dodecane were measured directly with a twin conduction microcalorimeter. A discontinuity appears on the heat of mixing vs. concentration curve except for n=0, the concentration of which decreases exponentially with n. This was regarded as the critical micelle concentration. It was deduced from the heat of solution at infinite dilution, Δsh2\ominus, that the poly(oxyethylene) chain is in a cyclic state in dodecane due to intramolecular hydrogen bonding of the terminal OH group with an oxygen atom in the chain. In addition, the energy of the solute-solvent interaction, Δiu2\ominus, was estimated from Δsh2\ominus, and the heat of evaporation of the solute, Δeh0. As a consequence, the interaction energies of the OH group with nonpolar hydrocarbon are similar, regardless of whether or not the OH group is intramolecularly hydrogen bonded.
  • Michio Matsumura, Yoichi Nomura, Hiroshi Tsubomura
    1977 Volume 50 Issue 10 Pages 2533-2537
    Published: 1977
    Released: April 19, 2006
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    The dye-sensitized photocurrents generated from the electrochemical systems <zinc oxide|aq solution|platinum> have been studied. The action spectra for the photocurrent, its dependence on the concentration of the dye solution and other experimental results have revealed that the photocurrent is caused by the dye adsorbed on the electrode, not from that dissolved in the liquid phase. From the analysis of the decay of the photocurrent with the time of illumination, the quantum yield for the electron injection from the excited dye has been determined. Rose Bengal showed the quantum yield of 22%. The influence of halide ions on the photocurrent has also been studied.
  • Tsunetaka Sasaki, Misako Yasuoka, Hitoshi Suzuki
    1977 Volume 50 Issue 10 Pages 2538-2541
    Published: 1977
    Released: April 19, 2006
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    Equations are derived which are used to calculate the intermicellar concentration (Cs) of a surfactant from measurements of the elution volumes of micelles, the elution front and the intermicellar monodisperse molecules or ions. These quantities are obtained by the gel filtration of a surfactant charged in band form through a gel column previously filled with the same surfactant at a lower concentration. The Cs values found are not constant, but increase and the increase becomes less pronounced with the concentration (C) of the surfactant, both for sodium dodecyl sulfate and α-dodecyl-ω-hydroxyhexa(oxyethylene). This confirms that the concentration CCs of the micelles which move during the gel filtration is smaller than the usually-employed concentration CCm of micelles in a stationary state, where Cm denotes the critical micelle concentration.
  • Gohsuke Sugihara, Mitsuru Tanaka, Ryohei Matuura
    1977 Volume 50 Issue 10 Pages 2542-2547
    Published: 1977
    Released: April 19, 2006
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    Primary micelles form secondary, polymer-like aggregates in a capillary flow of aqueous solution of sodium deoxycholate (SDC). The formation of the polymer-like aggregate is promoted by mechanical action, degradation being simultaneously caused by shearing stress. The viscosity of the SDC solution in the capillary flow attains equilibrium value between polymerization and degradation. The viscosity changes a great deal with the time of observation and pH. Under given conditions the SDC solution behaves as a non-Newtonian fluid obeying a power-law.
  • Tetsutaro Yoshinaga, Hiroshi Hiratsuka, Yoshie Tanizaki
    1977 Volume 50 Issue 10 Pages 2548-2553
    Published: 1977
    Released: April 19, 2006
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    The electronic absorption spectra of eighteen aromatic condensed ring compounds (C2v or D2h) were studied by means of comparison between the calculated and experimental results in terms of three fundamental factors: the electronic transition energy, the direction of the electronic transition moment, and the oscillator strength. The three experimental factors were obtained from the component spectra polarized to the long and short axes of the molecule, which were determined by means of the dichroism analysis technique. The calculated oscillator strengths were obtained by the dipole-length, dipole-velocity, and mixed-dipole methods. From the comparison between experimental and calculated results, it was found that the mixed-dipole method gives the best fit of the values to the experimental ones.
  • Yoshihiko Kambara, Hiroshi Yoshida, Bengt Rånby
    1977 Volume 50 Issue 10 Pages 2554-2557
    Published: 1977
    Released: April 19, 2006
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    A reinterpretation was made of the electron spin resonance spectrum of semiquinone intermediates during the photolysis of a flowing solution of tetrachloro-p-benzoquinone (chloranil) in ethanol. The photoinduced spectrum with a width of 0.06 mT with an unresolved hyperfine structure was found to be identical with the spectrum of the semiquinone anion generated by reducing chloranil in an alkaline ethanol solution. This and other observations indicated that the photoinduced spectrum was due to the chloranil semiquinone anion formed primarily by the one-electron transfer to chloranil from the solvent ethanol, rather than to the semiquinone radical. The photoinduced one-electron transfer reaction was found, though qualitatively, to proceed more efficiently for chloranil and fluoranil, with a larger electron affinity, than for p-benzoquinone and dichloro-p-benzoquinones.
  • Toshio Kamata, Hisae Nakahara, Shigeru Hattori
    1977 Volume 50 Issue 10 Pages 2558-2563
    Published: 1977
    Released: April 19, 2006
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    Light-scattering photometers were partially modified in order to measure light scattering by low molecular-weight molecules. Corrections to the molecular weights were then theoretically estimated, when the light scattering due to fluid density fluctuations were approximated by that due to the density fluctuations of a pure solvent. The molecular weight of benzene was determined, in an ethyl methyl ketone solvent, using the light-scattering method prior to the determination of the molecular weights of oligostyrene molecules. Measurements of light scattering by oligostyrene molecules with molecular weights from 600 to 20000 were then carried out. The weight-average molecular weight observed by the light-scattering method was compared with the number-average molecular weights which were determined by the vapor-phase osmometric and NMR methods. The molecular-weight heterogeneity of the specimen is discussed. The second virial coefficient, in the ethyl methyl ketone solvent system, was found to change from negative to positive with increasing molecular weight. It is also shown that the molecular optical anisotropy changes markedly in the range of molecular weights between 2000 and 3000, the change being considered to reflect the conformational changes of oligostyrene molecules.
  • Takao Iijima, Shuzo Tsuchiya, Masao Kimura
    1977 Volume 50 Issue 10 Pages 2564-2567
    Published: 1977
    Released: April 19, 2006
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    The gas-phase molecular structure of dimethyl sulfide, (CH3)2S, has been investigated by means of electron diffraction. By a joint analysis of the diffraction results and the spectroscopic moments of inertia by Pierce and Hayashi, the structure parameters, the distances in rg and the angles in \varphiav, were determined (with parenthesized limits of error) to be as follows: S–C=1.807(2) Å, C–H=1.116(3) Å, ∠CSC=99.05(4)°, and ∠HCH=109.3(5)°. A tilt of 2.35° and the local C3v symmetry of the methyl groups were assumed. The isotope effects of deuterium substitution were examined, and the DCD angle was found to be larger than HCH in the zero-point average structure.
  • Takao Iijima, Schigenori Seki, Masao Kimura
    1977 Volume 50 Issue 10 Pages 2568-2572
    Published: 1977
    Released: April 19, 2006
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    The gas-phase molecular structure of 2-chloropropane, (CH3)2CHCl, has been investigated by means of electron diffraction and by a joint analysis of the diffraction results and the spectroscopic moments of inertia. The structure parameters, distances in rg and angles in \varphiav, were determined (with parenthesized limits of error) to be as follows; C–Cl 1.812(1) Å, C–C 1.527(1) Å, C···Cl 2.720(2) Å, C–H 1.104(4) Å, ∠CCC 112.7(4)° and ∠HCH 108.5(8)°. The CCHsec angle was assumed to be 109.8(20)°. The present results, together with the data for other molecules, confirmed a systematic elongation of the C–Cl rg-distance in the series of methyl, ethyl, isopropyl, and t-butyl chlorides.
  • Minoru Ohki, Akio Takenaka, Hirotaka Shimanouchi, Yoshio Sasada
    1977 Volume 50 Issue 10 Pages 2573-2578
    Published: 1977
    Released: April 19, 2006
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    The crystal structure of 3-(adenin-9-yl)propiontryptamide (3-(adenin-9-yl)-N-[2-(3-indolyl)ethyl]propionamide) has been investigated as a model for adenine-tryptophan interaction. The space group of the crystal is P21/c, with dimensions a=8.512(2), b=16.884(3), c=12.405(3) Å, β=105.54(2)°, and Z=4. The structure was solved by the direct method and refined by a block-diagonal least-squares method. A slight overlapping between adenine and indole moieties is found, but it may not be sufficient to produce a strong π-π interaction. The adenine base is paired with that related by the centre of symmetry through two N(6)H···N(1) hydrogen bonds, and also with the other centrosymmetrically related adenine base through two N(6)H···N(7) hydrogen bonds. Adenine and indole are bound through a hydrogen bond between N(7) of adenine and imino nitrogen of indole.
  • Mamoru Ai
    1977 Volume 50 Issue 10 Pages 2579-2583
    Published: 1977
    Released: April 19, 2006
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    The oxidation of cis-2-butene, butadiene, and acetic acid was carried out by using a series of V2O5–XnOm (atomic ratio=9 : 1) catalysts with more than twenty metal oxides (XnOm). The results were compared with the dehydration activity for isopropyl alcohol (IPA), as a measure of acidity, and with the ratio, dehydrogenation activity for IPA/dehydration activity for IPA, used as a measure of the basicity of catalyst. The activity for the oxidation of butadiene and that for the isomerization of butene are correlated with the acidity, and the activity for the oxidation of acetic acid with the basicity of the catalyst. The selectivity to maleic anhydride from butene and butadiene is scarcely influenced by the introduction of metal oxides. Butene is mainly oxidized to acetic acid as a result of C–C fission. The selectivity to acetic acid is enhanced when the catalyst is highly acidic, decreasing with increase in basicity. It is concluded that the introduction of metal oxides into V2O5 modifies the acid-base properties of the catalyst, inducing a change in oxidation activity and selectivity.
  • Kiyotoshi Inenaga, Akira Yamauchi, Hideo Kimizuka
    1977 Volume 50 Issue 10 Pages 2584-2588
    Published: 1977
    Released: April 19, 2006
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    The membrane potential and conductance of the cation-exchange membrane-aqueous quaternary tetraalkylammonium chloride systems have been measured by using NH4+, tetramethyl-(Me4N+), tetraethyl-(Et4N+), tetrapropyl-(Pr4N+), and tetrabutylammonium ions (Bu4N+). The potential change in the concentration cell with these salts was about 58 mV for a tenfold change of concentration. The membrane conductance in the concentration cell increased with the concentration. The membrane permeability, as estimated from the potential and conductance data, was in the order of NH4+>Me4N+>Et4N+>Pr4N+>Bu4N+; it is proportional to the geometric mean of the activities of exterior solutions. The effective pore size of the membrane was deduced from the conductance data and found to be ca. 10 Å. The selective permeation coefficient has been determined from the potential data of the two- and multi-ionic systems. The selectivity data obtained with the two-ionic system were in agreement with those obtained with the multi-ionic system. The selectivity increased with the chain length of the cation, in contrast to the reversed order of the membrane permeability in the concentration cell. This was attributed to the decreasing mobility with the increasing chain length.
  • N. Manohara Murthy, S. V. Subrahmanyam
    1977 Volume 50 Issue 10 Pages 2589-2593
    Published: 1977
    Released: April 19, 2006
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    The effect of isomeric butyl alcohols on the temperature of sound velocity maximum in water (TSVM) was studied using a variable path interferometer working at 3 MHz. The structural contribution to the shift in TSVM, [ΔTstr]exp was evaluated for the butyl alcohols and the results are compared with those obtained from studies on the effect of these solutes on the temperature of adiabatic compressibility minimum and density maximum of water. The results indicate that the butyl alcohols enhance the hydrogen-bonded structure of water at low concentrations and at any given concentration, the order of increasing structural contribution to the shift in TSVM being t-butyl>s-butyl>isobutyl>butyl alcohols. The structural propensities of the butyl alcohols as revealed by TSVM studies are in line with the information obtained from the temperature of adiabatic compressibility minimum and density maximum studies. The results of the present study indicate that TSVM studies are useful in understanding the solution structure in aqueous mixtures.
  • P. L. Yadav, N. K. Jha, V. Ramakrishna
    1977 Volume 50 Issue 10 Pages 2594-2596
    Published: 1977
    Released: April 19, 2006
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    The ultraviolet spectra of o- and p-(halomercurio)phenols, o- and p-OHC6H4HgX(X=F, Cl, Br, or I) have been recorded in ethanolic solution and λmax and logεmax have been recorded. The spectra of these compounds have been interpreted in terms of the correlation with the spectra of benzene. HgX group is shown to be having electron-withdrawing effect on the benzene ring. Variation in the values of λmax and logεmax on changing from o- to p-derivative for a particular (halomercurio)phenol and on changing the halogen attached to mercury has been explained.
  • Shawky M. Hassan, G. M. Panchenkov, O. I. Kuznetsov
    1977 Volume 50 Issue 10 Pages 2597-2601
    Published: 1977
    Released: April 19, 2006
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    The propylene conversion process has been studied in the presence of synthetic zeolites of different types and metal ions. The NiX zeolite is selective for the oligomerization of propylene. On the zeolites of different other metal ions, the hydro-oligomerization process took place. It has been found that the obtained 3-methylpentenes are primary products of the propylene oligomerization. A scheme mechanism has been proposed assuming an intermediate of a cyclobutane derivative. The mechanism explains the formation of all the obtained products of propylene conversion on the synthetic zeolites.
  • Inam Jawed
    1977 Volume 50 Issue 10 Pages 2602-2605
    Published: 1977
    Released: April 19, 2006
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    Hydrogen bonding between a number of para-substituted phenols and nitriles was studied by means of infrared spectroscopy using a longer cell. Thermodynamic quantities were determined and found to be the functions of the electronegativity and inductive effect of the phenol and nitrile substituents respectively except for the complexes of t-butyl cyanide for which the −ΔH values were lower than expected. Some correlations among thermodynamic quantities were also established. Both the sample and the reference cells were heated simultaneously by means of a special heating arrangement which minimized the base line errors and made the intensity measurements more accurate.
  • H. D. Purohit, H. S. Sharma
    1977 Volume 50 Issue 10 Pages 2606-2608
    Published: 1977
    Released: April 19, 2006
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    The permittivity ε′ and dielectric loss ε″ of octanoyl, undecanoyl, and lauroyl chlorides have been measured in benzene for five different concentrations varying from 0.02 to 0.10 wt fraction at three different microwave frequencies, viz. 3.31, 9.83, and 26.90 GHz at 35 °C. The static permittivity ε0 at 100 kHz and the high frequency limiting permittivity ε have also been measured at the same temperature. The permittivity and dielectric loss at different frequencies have been plotted against concentration and their slopes have been used to draw normalised complex plane plots between (a′–a)/(a0a) and a″/(a0a) for these compounds. Such plots show a skewed arc dielectric behaviour. The values of distribution parameter β, characteristic relaxation time τ0, average relaxation time τav, and dipole moment μ have been reported for the first time. The relaxation mechanism in these three molecules has been explained on the basis of multiple relaxation processes.
  • Yuki Fujii, Mitsuo Sano, Yoshiharu Nakano
    1977 Volume 50 Issue 10 Pages 2609-2614
    Published: 1977
    Released: April 19, 2006
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    A series of mixed ligand cobalt(III)–Schiff base complexes with the general formula of [Co(sal2-(S,S)-chxn)(aa)] (aa=gly, L- and D-ala, L- and D-val, L- and D-leu, L- and D-thr, or L- and D-trp) were newly prepared from [Co(sal2-(S,S)-chxn)] and amino acids by air oxidation. All the complexes were found to take, stereoselectively, the Λ-cis1(fac)-structure, irrespective of the configuration of the amino acids. On the other hand, the reactions of [Co(sal2-(S,S)-chxn)] with an excess of DL-amino acids in open air gave [Co-sal2-(S,S)-chxn) (aa)], in which L-amino acids were selectively coordinated except for proline. These stereospecificities were found from the opticalpurity measurement of the unreacted amino acids which had been separated from the reaction solutions by extracting the formed complex with chloroform. The configuration and the optical purities of the unreacted amino acids recovered from 1 : 2 reaction solutions (complex: DL-amino acid) were as follows: ala, (D, 6–10%); leu, (D, 6–8%); met, (D, 6–8%); ser, (D, 10–12%); thr, (D, 27–30%); asp, (D, 16–18%); glu, (D, 6–8%); phe, (D, 29–31%); trp, (D, 41–43%); pro, (L, 48–50%). These stereoselectivities and stereospecificities were explained in terms of the thermodynamic origin and the stereochemical requirement of the complexes.
  • Hiroaki Wada
    1977 Volume 50 Issue 10 Pages 2615-2617
    Published: 1977
    Released: April 19, 2006
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    Favorable synthesis conditions for greigite are examined in FeSO4·(NH4)2SO4–Na2S–Na2Sx systems at about 100 °C. It has been found that greigite formation is influenced by the pH adjustment and by the addition of sulfur. When the final pH is about 6.0 and the dissolved iron concentration is in the 10−3–10−1.5 M range, greigite is synthesized as a single phase. The unit-cell dimensions of greigite range from 9.840 to 9.877 Å, corresponding to variations in compositions between 45.4 and 42.9 atomic % Fe. The formula of synthetic greigite is represented as Fe3+xS4 (x=0–0.4).
  • Toshikazu Nishide, Kazuo Saito
    1977 Volume 50 Issue 10 Pages 2618-2623
    Published: 1977
    Released: April 19, 2006
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    Reactions of (S)-2-amino-1-propanol (S-praH) with the tricarbonatocobaltate(III) solution gave binuclear complexes bridged by carbonates, or carbonate and hydroxide. The carbonate was replaced by oxalate (ox2−) to give binuclear complexes [(S-praH)2Co(ox)2Co(S-praH)2]2+ and uninuclear trans(N)cis(O)-[Co(ox)(S-pra)(S-praH)]. Another uninuclear complex [Co(ox)(S-praH)2]+ was obtained by direct synthesis from S-praH and cobalt(II) acetate by oxidation with lead dioxide. Column chromatography with SP-Sephadex C-25 was useful for separating the geometrical isomers, which were identified by PMR, IR, visible, and UV absorption spectra. Their circular dichroism (CD) spectra changed depending on pH of the aqueous solution. All the S-pra chelates have δ-conformation, which is characterized by an intensive plus CD component in the 25000 cm−1 region, regardless of the skeletal structure of the complexes.
  • Kiyoshi Yamasaki, Jinsai Hidaka, Yoichi Shimura
    1977 Volume 50 Issue 10 Pages 2624-2631
    Published: 1977
    Released: April 19, 2006
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    The trans dianiono type complexes of cobalt(III) containing (1R,2R)-1,2-cyclohexanediamine, trans-[Co(X)2(R,R-chxn)2]+, and -[Co(X)(X′)(R,R-chxn)2]+ (X and X′=N3, NCS, or NO2) were prepared and their circular dichroism (CD) spectra measured in the visible and ultraviolet regions. The CD and absorption behaviors in the so-called specific absorption band region are compared with those of cis-type bis(ethylenediamine) complexes and discussed in relation to the origin of the specific band. In addition, three isomers of the [Co(NCS)(NH3) (R,R-chxn)2]2+ complex are assigned on the basis of their CD spectra.
  • Tomoharu Ama, Matsutake Higa, Norio Koine, Takaji Yasui
    1977 Volume 50 Issue 10 Pages 2632-2637
    Published: 1977
    Released: April 19, 2006
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    Three geometrical isomers of the bis(β-alaninato)(oxalato)cobaltate(III) and of the (β-alaninato)(glycinato)(oxalato)cobaltate(III) complexes have been prepared and resolved into their optical isomers. Their structures were assigned on the basis of the electronic absorption, 1H NMR and 13C NMR spectra. The circular dichroism spectra of these complexes have been measured and compared with those of the bis(glycinato)(oxalato)cobaltate(III) complexes.
  • Yasuyoshi Torii, Kanemitsu Hasegawa
    1977 Volume 50 Issue 10 Pages 2638-2642
    Published: 1977
    Released: April 19, 2006
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    A new ternary oxide Bi1.34CrNbO6 was prepared and characterized. The unit cell is face-centered cubic with a=10.455 Å. The structure is assumed to be of the pyrochlore type based on the space group Fd3m and was refined by trial and error to a reliability factor R of 0.0564. This pyrochlore phase was confirmed to have vacancies at the A sites and also at the special oxygen sites, and may be considered to be a rare case in this respect. The Cr3+ and Nb5+ ions are bonded octahedrally to six oxygen atoms at 2.03 Å, while the Bi3+ ions are bonded to six oxygen atoms at 2.56 Å. The structure consists of bismuth tetrahedra, the centers of which are vacant. The highly polarizable Bi3+ ion plays an important role in the formation of the defect pyrochlore structure. Related pyrochlores were also prepared.
  • Kazuaki Yamanari, Jinsai Hidaka, Yoichi Shimura
    1977 Volume 50 Issue 10 Pages 2643-2649
    Published: 1977
    Released: April 19, 2006
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    Two cobalt(III) complexes containing terdentate thioethers, bis[(2-aminoethylthio)acetato]cobalt(III)(1+), and bis[3-(2-aminoethylthio)propionato]cobalt(III)(1+) were prepared and separated into five and six geometrical isomers, respectively, by ion-exchange column chromatography. The isomers were identified on the basis of their electronic absorption and NMR spectra. The circular dichroism spectra of optically resolved isomers were measured and discussed in relation to the absolute configurations.
  • Akiko Kobayashi, Yukiyoshi Sasaki
    1977 Volume 50 Issue 10 Pages 2650-2656
    Published: 1977
    Released: April 19, 2006
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    X-Ray crystal structure analyses of [(C4H9)4N]2[Ni(mnt)2] (I) and [(C2H5)4N][Ni(mnt)2] (II) {mnt: 1,2-dicyanovinylene-1,2-dithiolato C4N2S22−} have been carried out from the viewpoint of one-dimensional system. Crystals of (I) belong to triclinic system: a=12.360(6), b=11.138(12), c=9.833(9) Å, α=118.43(9), β=92.05(6), γ=91.91(6)°, space group P\bar1 with Z=1. The compound (II) forms monoclinic crystals, P21/a: a=20.018(18), b=16.079(9), c=7.118(6) Å, β=110.43(6)°, Z=4. Both structures, solved by the heavy-atom method, have been refined anisotropically by least-squares procedure to R=0.049 and 0.050 for (I) and (II), respectively. The bond distances of diamagnetic Ni(mnt)22− anion and paramagnetic Ni(mnt)21− anion are compared. A columnar structure was found in the structure of (II). The Ni(mnt)21− ions form a diadic unit, that is a repeating unit of two anions, within the columns. The electrical conductivity data are measured along the direction parallel to the Ni(mnt)21− stacks in the temperature range from room temperature to 373 K. This compound behaves as a semiconductor in this temperature range.
  • Masayuki Dokiya, Tetsuya Kameyama, Kenzo Fukuda, Yoshihide Kotera
    1977 Volume 50 Issue 10 Pages 2657-2660
    Published: 1977
    Released: April 19, 2006
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    The thermal decomposition of sulfuric acid is used as a step in the oxygen evolution in some thermochemical water-splitting cycles. The catalytic activity of metal oxides was studied in an attempt to find some suitable catalysts for sulfuric acid decomposition. The catalytic activity of SiO2, Al2O3, ZnO, CuO, NiO, CoO, Fe2O3, MnO, Cr2O3, V2O5, TiO2 was measured at high temperatures (800–870 °C and at atmospheric pressure. Iron(III) oxide was found to have the highest activity as a catalyst. Low catalytic activity was observed for the oxides (Al2O3, ZnO, NiO, CoO, MnO) which change to their sulfates under the present reaction conditions. Since the reaction conditions were very severe (more than 800 °C and in the presence of steam), a rapid decrease in both the specific surface area and the catalytic activity was observed. In order to avoid these disadvantages and in order to prepare practically useful catalysts, iron(III) oxide was pelletized and sintered (1000 °C, 6 h). Upon this procedure, this catalyst showed an almost constant activity for 120 hours’ reaction.
  • Tooru Tamura, Kunio Ohzeki, Tomihito Kambara
    1977 Volume 50 Issue 10 Pages 2661-2664
    Published: 1977
    Released: April 19, 2006
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    The conversion of cobalt(II) and nickel(II) ions collected on the ion exchange resin into the chelate compounds with trifluoroacetylacetone (Htfa) has been studied in various solvents. In the presence of pyridine, cobalt and nickel ions were quantitatively extracted from the resin into organic phase in the form of the base adducts [Co(tfa)2(py)2] and [Ni(tfa)2(py)2], respectively. The thermogravimetric and gas chromatographic behaviors of these compounds have been investigated. A gas chromatographic separation of [Ni(tfa)2] from [Co(tfa)2] was successfully performed.
  • Yayoi Ida, Shuhei Fujinami, Muraji Shibata
    1977 Volume 50 Issue 10 Pages 2665-2671
    Published: 1977
    Released: April 19, 2006
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    Five bis (dicarboxylato)bis(pyridine)-type complexes, trans-[CoCO3ox(py)2], trans- and cis-[Co(ox)2(py)2], and trans- and cis-[Co(mal)2(py)2], have been isolated as crystals and characterized on the basis of the absorption spectra, the PMR spectra, etc. The trans isomers of the carbonatooxalato and bis(oxalato) complexes reveal spectra similar to that of the trans-[Co(CO3)2(py)2] complex synthesized previously; the splittings of the absorption bands are not observed in the I bands, but are observed in the II bands. On the other hand, the trans isomer of the bis(malonato) complex reveals no splittings in either the I band or the II band. The assignment of these absorption bands has been made from considerations based on the Angular Overlap Model.
  • Miho Fujita, Hideo Yamatera
    1977 Volume 50 Issue 10 Pages 2672-2673
    Published: 1977
    Released: April 19, 2006
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    The hydrogen-deuterium exchange rates of Λ- and Δ-[Co(en)3]3+ were measured in D2O solutions containing (+)-tartrate ions. From the kinetic data, the ion-association constants of the Λ- and Δ-isomers with (+)-tartrate ions were determined to be 40 and 32 (I=0.1) respectively. Similar measurements with fumarate resulted in the association constant of 16 (I=0.1).
  • Hitoshi Ohtaki, Kenji Cho
    1977 Volume 50 Issue 10 Pages 2674-2677
    Published: 1977
    Released: April 19, 2006
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    Complex formation of silver(I) ion with 1,3-propanediamine and 1,4-butanediamine has been studied poten-tiometrically at 25 °C in 3 mol dm−3 LiClO4 aqueous solution. Some additional experiments have been carried out in the system of silver-1,2-ethanediamine of large diamine/Ag ratios, the system having been examined in a previous work at small diamine/Ag ratios. Over the pH range of 6—10.4, the emf data obtained in the silver-diamine solutions could be explained in terms of the formation of the following complexes (L denotes the free diamine molecule): In a solution of low pH (pH=6—8), the AgHL2+ and AgH2L23+ complexes are formed. In an alkaline solution, the AgL+, Ag2L22+, and AgL2+ complexes are formed, and the relative amounts of the complexes depend on the concentrations of the metal and ligand (L) and also the ratio of these concentrations. The Ag(OH)L complex becomes a main species at the highest pH examined. In some cases the formation of the AgHL22+, Ag2HL23+, and Ag2L2+ complexes is suggested from the graphical or computer analysis of the data, but the formation constants of the complexes are rather uncertain. Over the whole pH range examined, the AgHL2+, AgH2L23+, AgL+, and Ag2L22+ complexes are predominant in all the systems.
  • A. F. M. Fahmy, N. F. Aly, A. Nada, N. Y. Aly
    1977 Volume 50 Issue 10 Pages 2678-2681
    Published: 1977
    Released: April 19, 2006
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    N-(Arylsulfonyloxy)phthalimides undergo base-catalyzed Lossen rearrangement with amines, and amino acids to give N,N′-diaryl ureas and amine salts. They behave similarly with phenylhydrazine in alcohol to give a mixture of N-hydroxyphthalimide and phenylhydrazine salts. However, N-(arylsulfonyloxy)phthalimides undergo isomerization followed by Beckmann rearrangement to give a mixture of 4-aryl-1H-2,3-benzoxazin-1-ones and diarylsulfones.
  • Masatoshi Miura, Fumihiko Akutsu, Shigeo Hirose, Yoshiyuki Ikeno, Kuni ...
    1977 Volume 50 Issue 10 Pages 2682-2685
    Published: 1977
    Released: April 19, 2006
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    Polymers containing dicyclopentadiene units in their main chain were prepared by the polycondensation of dicyclopentadienedicarbonyl dichloride with bis(p-hydroxyphenyl) ether or 2,2-bis(p-Khydroxyphenyl)propane. Thermal analysis showed that the dicyclopentadiene units dissociate reversibly. The results of thermal degradation in a nitrobenzene solution indicate that a reversible degradation occurs at 10% concentration of the polymer, and an irreversible one at concentration below 1%. The activation energy of the dissociation of dicyclopentadiene units in the main chain of the polymer was estimated to be 30 kcal/mol.
  • Shizunobu Hashimoto, Isao Furukawa, Takao Tatsumi
    1977 Volume 50 Issue 10 Pages 2686-2688
    Published: 1977
    Released: April 19, 2006
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    The reactions of phenacyl benzoates, X–C6H4COCH2OCOC6H4–Y (1ai), with trialkyl phosphites (2ac) giving dialkyl 1-arylvinyl phosphates (3ad) in high yields were studied kinetically using the GLC technique. The overall reactions are second order, and exhibit a moderate solvent effect and catalysis upon the addition of certain organic acids. The activation energy, Ea=16.5 kcal/mol, and entropy, ΔS\ eweq=−38.5 e.u., were obtained from the reaction of 1a with 2b, and the ρ value obtained using σ for reactions of the two series of 1a with 2b was ρx=3.4 and ρY=1.0, respectively. The reactivity of 2 in this reaction is markedly increased in the order, Me<Et<i-Pr. These and other data accumulated support a mechanism for this reaction involving a ratedetermining addition of phosphorus atoms in 2 to the carbonyl carbon of the phenacyl group followed by rearrangement of the phosphorus moiety to the carbonyl oxygen of the phenacyl group.
  • Osamu Makabe, Hiroshi Suzuki, Sumio Umezawa
    1977 Volume 50 Issue 10 Pages 2689-2693
    Published: 1977
    Released: April 19, 2006
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    Several D-arabino- and 2′-deoxy-D-ribonucleosides of 1,2,3-triazolecarboxamides were synthesized by two methods, one involving acid-catalyzed fusion reactions of 1-O-acetyl derivatives (3, 5) of the corresponding sugars and 1,2,3-triazole-4-carboxylate (1), and the other by glycosylation of the trimethylsilyl derivative (2) of 1 with glycosyl halides (4, 6). Evidence for the N-glycosylation sites and anomeric configurations of the resulting nucleosides is presented.
  • Hisaji Taniguchi, Toshikazu Ikeda, Yoshihiro Yoshida, Eiji Imoto
    1977 Volume 50 Issue 10 Pages 2694-2699
    Published: 1977
    Released: April 19, 2006
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    The 1,3-dipolar cycloadditions of phenylglyoxylonitrile oxide, benzonitrile-N-phenylimine, or N-phenyl-C-p-nitrophenylnitrone to norbornadiene, 2,3-dicyanonorbornadiene, and 2,3-bis(methoxycarbonyl)norbornadiene give the endo-adducts, together with the exo-adducts. These findings show that the 1,3-dipolar cycloadditions to norbornadienes do not follow the “exo rule.” It is suggested that the present 1,3-dipolar cycloadditions are kinetically controlled reactions. The endo-side of norbornadienes is found to be homoconjugated by their NMR spectra. The homoconjugation must be responsible for the observed phenomenon.
  • Sh\={o}ichi Kikkawa, Masakatsu Nomura, Noritaka Hosokawa
    1977 Volume 50 Issue 10 Pages 2700-2703
    Published: 1977
    Released: April 19, 2006
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    The glow-discharge reactions of pyrrole, pyrrolidine, and butylamine were carried out. Pyrrolidine produces a complex mixture of products, the most prevalent of which is (Remark: Graphics omitted.) (R: H, CH3, and C2H5), and butylamine yielded primarily CH3(CH2)3N=CHR (R: CH3, C2H5, and C3H7) along with CH3(CH2)3NHCH2CN, whereas pyrrole afforded a mixture of acrylonitrile, crotononitrile, benzene, α-methylpyrrole and β-methylpyrrole, together with large amounts of HCN. The formation of characteristic products, α-(1-pyrrolidinyl) nitrile derivatives with pyrrolidine, and the yield of butylaminoacetonitrile with butylamine can be explained by considering the formation of a resonance-stabilized α-cyanoalkyl radical as the most probable intermediate which attacks a nitrogen atom of pyrrolidine and that of butylamine or which recombines with pyrrolidine-N-radical and butylamine-N-radical.
  • Makoto Takagi, Masato Tazaki, Tsutomu Matsuda
    1977 Volume 50 Issue 10 Pages 2704-2713
    Published: 1977
    Released: April 19, 2006
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    Durohydroquinone mono(p-substituted benzoate)s (1a1e) were oxidized by DDQ, in CH3OH/CH2Cl2 at room temperature. The products were duroquinone dimethyl acetal 4 and p-substituted benzoic acids (5a5e). None of the methyl esters 3 was formed. The details of the mechanism of a series of reactions, which start with the one-electron oxidation of 1, is elucidated by the isolation and characterization of the intermediates as well as by a kinetic study in an acetonitrile solution. The relation between the mode of oxidation, whether it is a one-electron or two-electron process, and the activation of the acyl group was explicitly discussed in terms of the mechanism. Two-electron oxidation is suggested to offer a better chance for acyl activation. Some generalization of the mechanism is made for other oxidation-induced acyl, phosphoryl and sulfuryl activating systems.
  • Tadashi Sato, Shigeo Yoshiie, Takashi Imamura, Kazumi Hasegawa, Masayu ...
    1977 Volume 50 Issue 10 Pages 2714-2730
    Published: 1977
    Released: April 19, 2006
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    α,β-Unsaturated carbonyl compounds and esters, cyclopropyl ketones, β-diketones, Schiff’s bases, and nitriles were irradiated in several alcohols in the presence of titanium(IV) chloride or uranyl chloride. In the titanium(IV) chloride-catalyzed reactions, the α-carbon atom of the primary alcohols underwent a bond formation, generally with the C=X (or C≡N) carbon atom of the substrates, while the bond formation occurred on a C=C carbon atom of the substrates in the uranyl chloride-catalyzed reactions. The reactions were examined under several conditions, and a possible scheme for the reactions was suggested.
  • Jitsuo Kiji, Akira Matsumura, Tomoyuki Haishi, Satoshi Okazaki, Junji ...
    1977 Volume 50 Issue 10 Pages 2731-2733
    Published: 1977
    Released: April 19, 2006
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    The reaction of carbon monoxide with triphenyl(phenylimino)phosphorane proceeded at room temperature in the coordination sphere of palladium to give a mixture of phenyl isocyanide and carbonyl complexes of palladium. Triphenyl (t-butylimino)phosphorane gave bis(t-butyl isocyanide)palladium chloride in a low yield. Benzophenone triphenylphosphazine and triphenyl(p-tolylsulfonylimino)phosphorane failed to react with carbon monoxide.
  • Takeo Konakahara, Yukio Takagi
    1977 Volume 50 Issue 10 Pages 2734-2740
    Published: 1977
    Released: April 19, 2006
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    The pyrolyses and thermal stabilities of 2,5-dialkylpyrazines (1ae), 2,5-diethoxypyrazine (2), chloropyrazine (3), alkoxypyrazines (4ac), alkylthiopyrazines (5a, b), and alkylaminopyrazines (6ad) were studied by means of a mass spectrometer, by which the pyrolysates in the sample reservoir were analyzed. The temperature dependence of the molecular ions and/or fragment ions was also discussed. The thermal dehydrogenation from two α-methine groups makes the 1d molecule thermally sensitive. The other 2,5-dibutylpyrazines were more stable than it, except for the t-butyl derivative, 1e. Hydroxy- and aminopyrazine, 4a and 6a, were very stable. The alkoxypyrazines, 4b and 4c, and alkylthiopyrazines, 5, underwent the thermal elimination of olefine to yield hydroxy- and mercaptopyrazine respectively. The latter disproportionated to form dipyrazinyl sulfide (11). At 280 °C, no analogous reactions of alkylaminopyrazines 6bd could be observed. The relative thermal stabilities of the compounds were as follows:
    2, 4a, 6a, 4b>1c>1e>1b>6c, 5a>3>6b>1d>1a>6d, 5b>4c
  • Kentaro Takagi, Naomi Hayama, Tadashi Okamoto, Yasumasa Sakakibara, Sh ...
    1977 Volume 50 Issue 10 Pages 2741-2743
    Published: 1977
    Released: April 19, 2006
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    RhCl(PPh3)3 has been proved to be an effective catalyst for the reaction of various diorganomercurials to give such coupling products as conjugated diyne, conjugated diene, biaryl, and alkane in good yields under mild conditions. A probable mechanism including the oxidative addition of organomercurials to a rhodium complex and the subsequent reaction of two oxidative-addition adducts to yield the product was presented.
  • Takashi Sugimoto, Keiko Shibata, Sadao Matsuura
    1977 Volume 50 Issue 10 Pages 2744-2747
    Published: 1977
    Released: April 19, 2006
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    The synthesis of imidazo[1,2-c]pteridine and its alkyl derivatives is described. The reaction of 4-aminopteridine with chloroacetaldehyde gave the ring-opened 2-formamido-3-(2-imidazolyl)pyrazine and the isomeric 2-amino-3-(1-formyl-2-imidazolyl)pyrazine but no imidazopteridine. 4-Amino-2-methylpteridine and chloroacetaldehyde similarly gave 2-acetamino-3-(2-imidazolyl)pyrazine in high yield. Hydrolysis of these compounds gave 2-amino-3-(2-imidazolyl)pyrazine, which was used as the key intermediate for the synthesis of the title compounds. Thus it reacted with triethyl orthoformate and homologues to give respectively the parent imidazo-[1,2-c]pteridine and its 6-methyl and 6-ethyl homologues. Their 2,3-dimethyl derivatives were prepared likewise from 2-amino-3-(2-imidazolyl)-5,6-dimethylpyrazine, which in turn was prepared from 4-amino-6,7-dimethyl- or 4-amino-2,6,7-trimethylpteridine.
  • Yoshihiro Nakagawara, Kiyoshi Kikukawa, Makoto Takagi, Tsutomu Matsuda
    1977 Volume 50 Issue 10 Pages 2748-2750
    Published: 1977
    Released: April 19, 2006
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    The preparation of π-allylic and related organopalladium(II) complexes with amino acid anions as bidentate ligands is described. The complexes were characterized by means of 1H NMR.
  • Kazuhiko Kimura, Hiroaki Niwa, Shinichi Motoki
    1977 Volume 50 Issue 10 Pages 2751-2753
    Published: 1977
    Released: April 19, 2006
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    The reactions of ketone derivatives containing carbon-nitrogen double bond such as oximes (3), N-alkyloximes (nitrones, 11), oxime O-alkyl ethers, phenylhydrazones and semicarbazones with thiocarboxylic acids were studied for the purpose of preparing thioketones. Both 3 and 11 reacted with thiocarboxylic acids to give thioketones in good yields. The reaction did not proceed in the cases of other ketone derivatives, the starting materials being recovered. The reaction of benzophenone oxime with thiobenzoic acid gave thiobenzophenone, dibenzoyl disulfide and ammonium benzoate, while that of benzophenone-N-methylnitrone with thioacetic acid gave thiobenzophenone and N-acetyl-N-methylhydroxylamine. The mechanisms of these reactions are presented.
  • Tetsuo Suami, Shigeru Nishiyama, Hikaru Ishikawa, Hiroshi Okada, Takes ...
    1977 Volume 50 Issue 10 Pages 2754-2757
    Published: 1977
    Released: April 19, 2006
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    Condensation of 1,3-bis-N-(benzyloxycarbonyl)actmamine (2) with 2-O-chloroacetyl-4,6-dideoxy-3-O-p-nitrobenzoyl-α-D-xylohexopyranosyl chloride (8), followed by deacylation and catalytic hydrogenation afforded 5-O-(4,6-dideoxy-β-D-xylohexopyranosyl)actinamine (11). Compound 11 was found to be identical with one of the four tetrahydrospectinomycins. 1H and 13C NMR spectra were determined and analyzed.
  • Kunisuke Fukui, Tateo Nomoto, Shin’ichi Nakatsuji, Shuzo Akiyama ...
    1977 Volume 50 Issue 10 Pages 2758-2761
    Published: 1977
    Released: April 19, 2006
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    It was found that dienyne ketones such as 2,2-dimethyl-7-t-butyl-4,6-nonadien-8-yn-3-one, 2,2-dimethyl-7-phenyl-4,6-nonadien-8-yn-3-one and 1,5-diphenyl-2,4-heptadien-6-yn-l-one give the corresponding tetrasubstituted 14-membered cyclic glycols on treatment with a suspension of potassium hydroxide in liquid ammonia. Reactions of the cyclic glycols with tin(II) chloride in organic solvent saturated with hydrogen chloride afforded strongly diatropic tetrasubstituted bisdehydro[14]annulenes.
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