Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 57 , Issue 3
Showing 1-50 articles out of 69 articles from the selected issue
  • Takehiko Mori, Akiko Kobayashi, Yukiyoshi Sasaki, Hayao Kobayashi, Gun ...
    1984 Volume 57 Issue 3 Pages 627-633
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Based on the extended Hückel molecular orbital calculations, the relation between the anisotropy of the band structure and the arrangement of the organic molecules is investigated for two organic donors, tetrathiafulvalene (TTF) and bis(ethylenedithio)tetrathiafulvalene (BEDT–TTF). The intermolecular overlaps of their HOMO are calculated while the intermolecular arrangements are varied. The maps of the overlaps thus obtained are then used to estimate the band-structure parameters of (TMTTF)2X and (BEDT–TTF)2ClO4(C2H3Cl3)0.5. The Fermi surface of (TMTTF)2X is quasi-one-dimensional and not closed. On the contrary, (BEDT–TTF)2ClO4(C2H3Cl3)0.5 is regarded as a two-dimensional semimetal.
  • Kumiko Sato, Makoto Iwai, Hirotoshi Sano, Michiko Konno
    1984 Volume 57 Issue 3 Pages 634-638
    Published: 1984
    Released: June 27, 2006
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    The structures of both the crystal and the plastic phases of formylferrocene have been determined to be orthorhombic by single-crystal X-ray diffraction. The structural change proposes a mechanism of the transition that postulates the translational molecular motion along the a-axis. Mössbauer spectra observed in the plastic phase show little fluctuation of the electric field gradient ascribed to the orientational disorder between x, y, and z axes of the molecule.
  • Takeo Ozawa
    1984 Volume 57 Issue 3 Pages 639-643
    Published: 1984
    Released: June 27, 2006
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    Fundamental kinetic equations for nonisothermal crystal growth from preexisting nuclei are derived, by introducing a concept of reduced time. A method of kinetic analysis of thermoanalytical data of these processes is proposed, and all kinetic parameters can be estimated by the method, so that the process proceeding under various temperature changes can also be predicted.
  • Yukio Tanaka, Norio Ohtomo, Kiyoshi Arakawa
    1984 Volume 57 Issue 3 Pages 644-647
    Published: 1984
    Released: June 27, 2006
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    The structure factor Sm(Q) for liquid methyl alcohol (CD3OD) at room temperature was obtained by means of the LINAC-TOF neutron diffraction method. An analysis of the diffraction data was carried out, and the molecular structure of CD3OD in liquid phase was determined as: the O–D, C–O, and C–D bond lengths are 0.990±0.010, 1.435±0.005 , and 1.085±0.005 Å, respectively. The O–D and C–D lengths were found to be longer than those values determined in gaseous phase.
  • Kenji Kano, Ichiro Tokimitsu, Tokuji Ikeda, Mitsugi Senda
    1984 Volume 57 Issue 3 Pages 648-651
    Published: 1984
    Released: June 27, 2006
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    The effect of temperature on the polarographic catalytic hydrogen evolution current (Brdicka current) produced by ribonuclease-A in an ammoniacal buffer containing cobalt salt has been studied using the theoretical equation of Brdi\`{c}ka current. With increasing temperature, the Brdicka current at −1.3 V increased between 10 and 30 °C then fell off above 30 °C, whereas the currents at −1.4 and −1.5 V decreased continuously. Analysis showed that the initial increase of the Brdicka current at −1.3 V was only apparent and that the Brdicka current constant, kB, which represents the catalytic activity of the protein, always decreased with increasing temperature in the potential range of −1.3 to −1.5 V. Further analysis has revealed that the intrinsic catalytic activity of the protein-cobalt(0) complex, which is transiently formed on the electrode surface and which catalyzes the hydrogen evolution, increases with increasing temperature whereas the life time of the complex decreases and the latter decrease cancels the former increase, resulting in the decrease of the kB value with increasing temperature.
  • F. Scott Howell, Cornelius T. Moynihan, Pedro B. Macedo
    1984 Volume 57 Issue 3 Pages 652-661
    Published: 1984
    Released: June 27, 2006
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    The dielectric constant ε′ and the electrical conductivity σ were measured as a function of frequency (0.1–2 MHz) and temperature for an electrolyte-polar solvent system: lithium chloride in glycerol. Mole fractions of LiCl were 0, 1, 2, 5, 10, 20, and 33.3%. Data were analysed in terms of an inverse complex permittivity(electrical modulus). At lower mole fractions, two separate modulus relaxations were observed, one due to the ionic diffusion and the other to the dipole reorientation. These two relaxation processes converged with increasing LiCl mole fraction and were not distinguishable at 20%. The moduli isotherms at 33.3% were characteristic of a fused salt. Average relaxation times and distributions for both processes were determined by computer fits to a Gaussian distribution in the logarithms of these times. Their temperature and mole fraction dependences are discussed. The conductivity relaxations became slightly broader than single at 10%; this shows the influence of the charge concentration on the structural relaxation process.
  • Toshio Ogawa, Motoo Yasuda, Kiyoshi Mizutani
    1984 Volume 57 Issue 3 Pages 662-666
    Published: 1984
    Released: June 27, 2006
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    Apparent molal volumes (φV) and apparent molal adiabatic compressibilities (φKS) at 25 °C have been obtained for the following amino acids in water and in urea-water mixtures (up to 8 mol kg−1 urea for φV and at 3 mol kg−1 for φKS) from measurements of density and ultrasonic velocity: glycine, L-alanine, β-alanine, α-aminoisobutyric acid, L-valine, L-serine, and L-threonine. The limiting values φVo and φKSo were calculated by a linear extrapolation using the least-squares method. These data were used to derive the volumes of transfer and the adiabatic compressibilities of transfer of the amino acids from water to aqueous urea solutions. Both of these transfer functions were positive. The results were interpreted in terms of structure-breaking interaction of urea upon water.
  • Yasushi Miyata, Masamichi Akimoto, Nobukazu Ooba, Etsuro Echigoya
    1984 Volume 57 Issue 3 Pages 667-672
    Published: 1984
    Released: June 27, 2006
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    The yield and selectivity to hydrocarbons in the Kölbel-Engelhardt (KE) reaction over a Fe2O3 catalyst at 548–593 K under atmospheric pressure were as low as 0.6–2.2% and 2.0–3.8%, respectively, but the observed four characteristic features of the reaction, i.e., the distribution of produced hydrocarbons following the Schulz-Flory plot, the decrease in propagation probability with increasing reaction temperature, nearly the same value of propagation probability irrespective of a great change in contact time of the reaction, and the remarkable decrease in the yield ratio of olefins to paraffins with increasing contact time of the reaction agreed with the common features of the synthesis of hydrocarbons by the Fischer-Tropsch reaction. The catalyst was composed of Fe3O4 with a low concentration of χ-type carbide (Fe5C2) during the KE reaction, and the results of the effect of contact time on the reaction revealed that formation of hydrocarbons took place following the water-gas shift (WGS) reaction. Furthermore, both the rates of formation of hydrocarbons in the reactions of carbided iron catalyst (Fe5C2) with H2O and with H2 at 573 K were smaller by a factor of >5 than the rate of formation of hydrocarbons in the KE reaction at a steady state at 573 K. Thus, it is concluded that a much greater portion of hydrocarbons produced in the KE reaction was via a sequential reaction pathway involving the WGS reaction followed by the Fischer-Tropsch reaction, not via the decomposition of carbided iron catalyst with H2O and its reduction with H2. Based on the observed increase in the catalytic activity of Fe2O3 upon addition of a small amount of such metal oxides as Cu, Pt, Co, Ni, and Rh oxides, the mechanical mixture of a WGS reaction catalyst and a Fischer-Tropsch reaction catalyst is proposed to be an effective catalyst for the production of hydrocarbons and one illustration of this view is presented.
  • Javier Lopez, Jun Yamauchi, Keiichi Okada, Yasuo Deguchi
    1984 Volume 57 Issue 3 Pages 673-677
    Published: 1984
    Released: June 27, 2006
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    The electron nuclear double resonance (ENDOR) spectra of benzothiazolone azine cation radicals were observed by means of an ENDOR spectrometer equipped with a TM110 mode cavity. Highly diluted solutions of the radicals and a high radiofrequency power of 300 W facilitated the ENDOR observation. The obtained ENDOR values are different from the previously published results determined only from the ESR data, especially for the substituted alkyl groups. The assignment of the hyperfine coupling constants was made on the basis of the molecular orbital calculations as well as the re-examination of the ESR spectrum simulation. Good agreement between the calculated and the measured spectra is obtained if one assumes that the hyperfine coupling constants of the two different sets of nitrogen nuclei are equal as has been pointed out earlier.
  • Takayuki Sano, Masako Yamamoto, Hiroka Hori, Tatsuya Yasunaga
    1984 Volume 57 Issue 3 Pages 678-680
    Published: 1984
    Released: June 27, 2006
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    Kinetic studies of complex formation in the system consisting of cyclodextrin, iodine, and iodide have been made by the temperature-jump method. By addition of α-cyclodextrin to the iodine–iodide solution, a new relaxation in addition to that due to I62−, formation was observed, but not in the case of addition of β-cyclodextrin. The reciprocal relaxation time is independent of the iodine concentration, but increases with increase of both iodide and α-cyclodextrin concentration, with a tendency to reach a constant value at their high concentrations. From these concentration dependences of the relaxation time, the observed relaxation was assigned to the conformational change of the complex between α-cyclodextrin and iodide ion, and the rate constants were estimated to be 5.9×105 and 1.2×105s−1 for the forward and backward processes, respectively. A rationalization for the difference between α-cyclodextrin and β-cyclodextrin in this complex formation is proposed in terms of the molecular structure of cyclodextrin.
  • Yo-ichi Ishikawa, Shigeyoshi Arai
    1984 Volume 57 Issue 3 Pages 681-686
    Published: 1984
    Released: June 27, 2006
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    Time-resolved infrared emission spectra have been measured in the infrared multiple-photon decomposition of CClF2CH2Cl. The spectra were composed of emissions attributable to vibrationally excited HF* and HCl*. The emission yield of HF* increased rapidly with an increase in the fluence, while the yield of HCl* showed a maximum at 20 J cm−2. These results suggest that the HF and HCl molecular elimination channels compete with each other in the unimolecular decomposition of highly vibrationally excited parent molecules. The stochastic trajectory calculations provided a satisfactory description of the fluence dependences of the HF and HCl yields observed here for CClF2CH2Cl and previously for CHClFCHClF.
  • Nobuhito Imanaka, Gin-ya Adachi, Jiro Shiokawa
    1984 Volume 57 Issue 3 Pages 687-691
    Published: 1984
    Released: June 27, 2006
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    Sodium sulfate doped with NaVO3 and Ln2(SO4)3 (Ln=Eu, Pr, and Y) show higher electrical conductivity for Na+ ions and maintains a high temperature phase, Na2SO4–I, without showing phase transformation. The electromotive force (EMF) using solid solutions, Na2SO4–NaVO3–Ln2(SO4)3 (Ln=Pr and Y), as solid electrolytes exhibits good agreement with the calculated value, the temperature as low as 673 K which is approximately 300 K lower than pure sodium sulfate can be.
  • Yoko Ohga, Mamoru Nakanishi, Masamichi Tsuboi
    1984 Volume 57 Issue 3 Pages 692-695
    Published: 1984
    Released: June 27, 2006
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    The kinetics of acid denaturation of muscle aldolase were examined by stopped-flow fluorescence and stopped-flow light scattering measurements. The denaturation reaction was found to consist of three distinguishable steps—step I with fluorescence increase only, step II with both fluorescence increase and light scattering decrease, and step III with fluorescence decrease alone. Circular dichroism and sedimentation equilibrium measurements were also made at different pH’s in the course of the acid denaturation. It was concluded that in the acid denaturation of this enzyme a rearrangement of the secondary or tertiary structures takes place rapidly (4 s−1 at 21.5 °C and at pH 3.4), and then the subunit dissociation occurs more slowly (0.04 s−1 at 21.5 °C and at pH 3.4), with further conformational change. The subunit dissociation was found to be caused by two H+ per tetramer.
  • Kazuki Oka, Hiroshi Maeda, Shoichi Ikeda
    1984 Volume 57 Issue 3 Pages 696-700
    Published: 1984
    Released: June 27, 2006
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    The β-form was induced by the addition of CrCl3, FeCl3, and LaCl3 to the salt-free solutions of fully ionized poly(S-carboxymethyl-L-cysteine) (poly[Cys(CH2COOH)]) and poly[S-(2-carboxyethyl)-L-cysteine] (poly[Cys(CH2CH2COOH)]). The induction occurred below the equivalent point in both polypeptides. The inducing powers of the three trivalent cations were rather similar. They were weaker than Cu2+ ions in the case of poly[Cys(CH2COOH)], while they were comparable with Cd2+ ions in the case of poly[Cys(C2H4COOH)]. Cu2+ and Cd2+ ions were the most effective species among divalent cations in the induction of the β-form of poly[Cys(CH2COOH)] and Poly[Cys(C2H4COOH)], respectively.
  • Nobuatsu Watanabe, Saburo Katoh, Tsuyoshi Nakajima
    1984 Volume 57 Issue 3 Pages 701-705
    Published: 1984
    Released: June 27, 2006
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    A study was made of the yield and crystallinity of graphite fluoride using a vertical vibrating reactor, which made it possible to prepare much graphite fluoride. The yield of graphite fluoride decreased beyond 500 °C for natural graphite and petroleum coke heat-treated at 2800 °C, and beyond 300 °C for calcined petroleum coke. The crystallinity of graphite fluoride was improved through the decomposition and refluorination process in these temperature ranges where the yield decreased. It was found that a sublimative solid by-product was formed together with gaseous fluorocarbons. It was a white solid fluorocarbon with 5–9 cyclohexane rings.
  • Hisao Degawa, Noriko Shinozuka, Shigeo Hayano
    1984 Volume 57 Issue 3 Pages 706-711
    Published: 1984
    Released: June 27, 2006
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    A tubular flow-through electrode system for measuring the response time curves under the step change of concentration using an ammonium ion-selective poly(vinyl chloride) membrane electrode was described. The response time data are analyzed by the curve fitting method using two theoretical equations, which are an exponential type equation based on an assumption of the film diffusion and a square root type one based on that of the diffusion within the membrane, and a semiempirical equation of hyperbolic type. A method of curve fitting in which the equilibrium potential is regarded as an unknown parameter was described in detail. The initial part of the response time curves, where the potential change is large, was fitted by the exponential type equation, while the following part close to the equilibrium potential was fitted by the square root type one. The semiempirical equation could also be fitted to the wide range of the curves. The dependence of the time constant of the exponential type equation upon the flow rate of sample solution is examined; the results firmly supports both the film diffusion as a determining process for the initial part of the curve and the reliability of the present experimental system.
  • Yasushi Inoue, Yoshimune Yamada
    1984 Volume 57 Issue 3 Pages 712-715
    Published: 1984
    Released: June 27, 2006
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    A monohydrate (Phase II) and three anhydrous phases prepared by the thermal treatment (at 250, 700, and 900 °C respectively for Phases III, IV, and V) of disodium zirconium(IV) bis(orthophosphate) trihydrate were studied from the sodium isotopic exchange rate between them and aqueous solutions. In Phases III and IV, which had been sufficiently adapted in water in advance, the rate was found to be controlled by the diffusion of sodium ions along the direction perpendicular to the layers consisting of zirconium atoms and the diffusion constants, and their activation energies (for Phases III and IV, 57 and 52 kJ/mol) were evaluated. When these phases were used as dried, the rate was governed by the irreversible dissociation of sodium in the solid phases. In Phase II, used as dried, and in Phase V, used as dried and wetted, the rate was controlled by neither particle diffusion, film diffusion, nor chemical reaction alone. This behavior was attributed to the complex behavior of phase transformation as the isotopic exchange proceeded.
  • Hisako Itoh, Naomi Itoh, Yasuo Suzuki
    1984 Volume 57 Issue 3 Pages 716-718
    Published: 1984
    Released: June 27, 2006
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    The stability constants of scandium complexes with some carboxylate ligands were determined potentiometrically at 25.0 and 40.0 °C and at an ionic strength of 0.10 with potassium nitrate as supporting electrolyte. The constants of the scandium complexes were appreciably greater than those of the corresponding lanthanoid complexes, as expected. The changes in free energy, enthalpy, and entropy for the formation of the scandium complexes were calculated from the stability constants at two temperatures.
  • Shin-ichi Kamiyama, Akira Kasahara
    1984 Volume 57 Issue 3 Pages 719-724
    Published: 1984
    Released: June 27, 2006
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    [3](1,1′)[3](3,3′)- and [4](1,1′)[4](3,3′)Ruthenocenophanes were synthesized via cyclization of the propionic acid derivatives of [3](1,1′)- and [4](1,1′)ruthenocenophanes with polyphosphoric acid or trifluoroacetic anhydride, respectively. The 1H NMR, IR, and electronic spectra of these dibridged ruthenocenes were measured and compared with those of monobridged ruthenocenes.
  • Masahiro Minabe, Y\={o}ji Yamamoto, Masaaki Yoshida, Katsuko Nakada, K ...
    1984 Volume 57 Issue 3 Pages 725-728
    Published: 1984
    Released: June 27, 2006
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    The catalytic hydrogenation of 4H-cyclopenta[def]phenanthrene over Raney nickel afforded 8,9-dihydro-4H-cyclopenta[def]phenanthrene and 1,2,3,3a-tetrahydro derivative. Under these conditions, di- and tetrahydro compounds were reduced into two diastereomers, cis-3a-cis-9a- and trans-3a-cis-9a-1,2,3,3a,8,9,9a,9b-octahydro-4H-cyclopenta[def]phenanthrene. The reduction over palladium gave a dihydro compound and a platinum catalyst provided products analogous with those obtained over Raney nickel.
  • Rikuhei Tanikaga, Yoshihito Nozaki, Masaharu Nishida, Aritsune Kaji
    1984 Volume 57 Issue 3 Pages 729-733
    Published: 1984
    Released: June 27, 2006
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    Thermal reaction of ethyl (2E)-2-phenylsulfinyl-2-alkenoates (E-2) prepared from aldehydes and ethyl 2-phenylsulfinylacetate have been investigated. Refluxing of E-2 or their Z-isomers in xylene resulted in the formation of ethyl (2E,4E)-2,4-alkadienoates accompanied by ethyl (2E)-4-hydroxy-2-alkenoates. Ethyl 2-cycloalkylidene-2-phenylsulfinylacetates were found to be more susceptible to pyrolysis. The enoate esters (2) undergo migration of their carbon-carbon double bond and then [2,3]sigmatropic rearrangement to benzene-sulfenate esters, followed by thermolytic extrusion of a benzenesulfenic acid probably via ethyl (2E)-4-phenyl-sulfinyl-2-alkenoates to afford ethyl (2E,4E)-2,4-alkadienoates.
  • Hiroshi Yoshida, Mikito Nakajima, Tsuyoshi Ogata, Kiyoshi Matsumoto
    1984 Volume 57 Issue 3 Pages 734-738
    Published: 1984
    Released: June 27, 2006
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    This study treats the reactions of methylthio-, ethylthio-, or benzylthiodiphenylcyclopropenium ion (1) with 5-, 6-, and 7-membered cyclic 1,3-diketones, giving either 2-alkylthio-2H-pyrans or dienone derivarives. Treatment of 1 with 1,3-cyclopentanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 4-hydroxy-6-methyl-2-pyrone, 4-hydroxycoumarin, and 1,3-cycloheptanedione in the presence of triethylamine afforded 2-alkylthio-2H-pyrans. The structure of the products was elucidated on the basis of their elemental analyses, IR, 1H-NMR, 13C-NMR, and mass spectroscopic data, as well as chemical transformations. 2-Alkylthio-2H-pyrans with mercury(II) chloride in an alcohol underwent conversion to the corresponding 2-alkoxy-2H-pyrans. The 1H- and 13C-NMR data of these compounds clearly show that the equilibrium lies completely on the side of the 2H-pyran. In contrast, the reaction of 1 with 1,3-indandione yielded the ring-opened dienone derivative as a mixture of E and Z isomers.
  • Masanobu Yatagai, Masanobu Zama, Takamichi Yamagishi, Mitsuhiko Hida
    1984 Volume 57 Issue 3 Pages 739-746
    Published: 1984
    Released: June 27, 2006
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    New chiral diphosphinites were prepared starting from (+)-diethyl tartrate. The asymmetric hydrogenation of dehydroamino acids, itaconic acid and dehydrodipeptides was studied using Rh(I)-diphosphinite catalysts. In the hydrogenation of dehydroamino acid derivatives, an introducion of ω-(dimethylamino)alkyl group in the ligands did not raise the optical yield. By the use of Rh(I)-diphosphinite having 3-(dimethylamino)propyl group, the inversion of the preferred product was observed. Itaconic acid can be hydrogenated in a good optical yield (76% e.e.) by use of the diphosphinite having 2-(dimethylamino)ethyl group. The diphosphinites having ω-dimethylamino group gave high optical yields in the case of dehydrodipeptides with a chiral center. Especially Rh(I)-catalysts coordinated by diphosphinites with 4-methyl or 4-methoxyl group on the phenyl ring of the ligand gave excellent stereoselectivities (more than 98% d.e.) in the case of Ac–ΔPhe–(S)-Phe–OH. The effect of these new chiral diphosphinites on the asymmetric hydrogenation of dehydroamino acids, itaconic acid and dehydrodipeptides was discussed in terms of the stereocontrol induced by electrostatic interaction between the dimethylamino group of the ligand and the substrate and by the steric interaction between the ligand and the substrate.
  • Takashi Matsumoto, Sachihiko Imai, Katsumi Nishizaki, Fumio Kurihara, ...
    1984 Volume 57 Issue 3 Pages 747-751
    Published: 1984
    Released: June 27, 2006
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    Methyl (+)-12-benzoyloxy-11,14-dioxo-8,12-abietadien-18-oate was converted into methyl 11,12,14-trimethoxy-8,11,13-abietatrien-18-oate (8). The Grignard reaction of 8 with phenylmagnesium bromide, followed by oxidation with lead tetraacetate, afforded 11,12,14-trimethoxy-19-norabieta-4(18),8,11,13-tetraene. This was then converted into 3α-bromo-11,12,14-trimethoxy-18-norabieta-8,11,13-trien-2-one (15) by a series of reactions: selenium dioxide oxidation, catalytic hydrogenation, dehydration, hydroxybromination, and Jones oxidation. Acetalization of 15 with 1,2-ethanediol, followed by oxidation with Jones reagent and then with oxygen in the presence of potassium t-butoxide, afforded 3-bromo-2,2-ethylenedioxy-6-hydroxy-11,12,14-tri-methoxy-18-norabieta-5,8,11,13-tetraen-7-one, which was converted into (−)-coleon B tri-O-methyl ether (4) by hydrolysis and dehydrobromination. Another conversion of 15 into 4 was also achieved by a series of reactions: debromination, acetalization, Collins oxidation, oxygen oxidation, hydrolysis, and dehydrogenation.
  • Kenichi Sanechika, Takakazu Yamamoto, Akio Yamamoto
    1984 Volume 57 Issue 3 Pages 752-755
    Published: 1984
    Released: June 27, 2006
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    Palladium compounds such as Pd(PPh3)4 and Pd(OAc)2 catalyze polycondensation between dihalo aromatic compounds, X–Ar–X (Ar=p-phenylene, 2,5-thiophenediyl, 9,10-anthracenediyl, 2,6-pyridinediyl, p-benzenedicarbonyl, p-xylene-α,α′-diyl), and acetylenic compounds (p-C6H4(C≡CH)2 or p-C6H4(C≡CMgBr)2). The polymers obtained have high thermal stabilities and most of them show fluorescence. One of the polymers is converted into semiconductors by doping with electron acceptors.
  • Kunio Takei, Kazuo Sugihara, Hitoshi Hagiwara, Seisuke Nakamura
    1984 Volume 57 Issue 3 Pages 756-758
    Published: 1984
    Released: June 27, 2006
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    Powder of mercury(II) iodide thiocyanate (HgISCN) gives a weak electron spin resonance (ESR) signal at g=2.003 in the dark. When the powder is irradiated, the ESR-signal intensity increases during the exposure. When the light is turned off, the intensity decreases. The ESR-signal may be due to electrons trapped by lattice defects.
  • Tetsuya Osaka, Takashi Kitai
    1984 Volume 57 Issue 3 Pages 759-762
    Published: 1984
    Released: June 27, 2006
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    An electrochemical anion doping-undoping process of cis-polyacetylene, (CH)x, was investigated in 1 mol dm−3 LiClO4 or LiBF4 in propylene carbonate by the FFT impedance measurement. This could be applied to the system with time-variation because of its high speed measuring duration. The doping-undoping process of the anion was represented by the Randles-type equivalent circuit, considering the corrective term concerned with surface roughness. The impedance behavior of the doping-undoping process was pursued by the variation of resistive component, Rr. The value of Rr was mainly reflected by the dopant concentration at the surface. The variation of Rr indicated that rapid or strong-drive doping produces non-uniformity of dopant distribution in the film and high dopant concentration at the surface.
  • Kaoru Iwai, Fukuo Takemura, Masaoki Furue, Shun-ichi Nozakura
    1984 Volume 57 Issue 3 Pages 763-767
    Published: 1984
    Released: June 27, 2006
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    In the electron-transfer reaction from the fluorescent intramolecular exciplexes of a copolymer containing phenanthrene and N,N-dimethylaniline moieties, and of a model compound to electron acceptors, the reactivity of the exciplexes was studied kinetically in polar and nonpolar media. The copolymer was poly(9-vinylphenanthrene-co-p-dimethylaminostyrene) and the model compound was N,N-dimethyl-4-[3-(9-phenanthryl)propyl]aniline. The oxidation potential of the exciplex was evaluated by the relation of the exciplex-quenching rate constants to the reduction potentials of electron-accepting quenchers according to the equations of Rehm and Weller. It was found that the electron-donating ability of these intramolecular exciplexes resembled with each other and was larger than that of excited phenanthrene. In polar media the donating ability was very close to that of the phenanthrene anion radical.
  • Toshie Harazono, Shin Sato, Hiroshi Fukutomi
    1984 Volume 57 Issue 3 Pages 768-770
    Published: 1984
    Released: June 27, 2006
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    ESR spectra of radicals produced in the uranyl ion-photosensitized decomposition of ethanol have been measured in the rigid matrix at 77 K. At high concentrations of uranyl ions (>1 mol dm−3), methyl radicals were observed. With decreasing concentrations of uranyl ions, CH3\dotCHOH radicals became important, as expected from the previous studies. This result suggests that the charge transfer mechanism is important in the ethanol rigid matrix, although the hydrogen atom abstraction mechanism is accepted as the main initial process.
  • Ikuo Naito, Wolfram Schnabel
    1984 Volume 57 Issue 3 Pages 771-775
    Published: 1984
    Released: June 27, 2006
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    The laser-flash photolysis of propanone, butanone, and 2-pentanone were carried out in dichloromethane (265 nm, 15 ns flash duration). The emission spectra (fluorescence, phosphorescence, and P-type delayed fluorescence) and the transient absorption spectra (triplet state and acetyl radical) were recorded. From the decays of the emission and the absorption, the unimolecular (triplet decay) and bimolecular (T–T annihilation and self quenching) reaction-rate constants were determined. Oxygen quenched the triplet states with a diffusion-controlled rate constant (kO2=ca. 3×10 dm3mol−1 s−1).
  • Eishun Tsuchida, Hiroyuki Nishide, Makoto Yuasa, Mikiya Sekine
    1984 Volume 57 Issue 3 Pages 776-780
    Published: 1984
    Released: June 27, 2006
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    Oxygen- and carbon monoxide-binding affinity (P1⁄2) of the [α,α,α,α-meso-tetrakis(o-pivalamidophenyl)porphinato]iron(II)-mono(1-dodecyl-2-methylimidazole) complex incorporated in liposome of phosphatidylcholine (abbreviated as liposomal heme) were measured in pH 7.0 aqueous solution at 15–37 °C. The P1⁄2(O2) and P1⁄2(CO) values at 37 °C were 49 and 0.02 mmHg, respectively. Enthalpy and entropy changes for the reversible bindings were similar to those of hemoglobin. The relationship between temperature and P1⁄2 for the dimyristoylphosphatidylcholine-liposomal heme had a breaking point at ca. 24 °C, which agreed with the phase transition temperature of the liposomal heme.
  • Alauddin Ahmed, Nagahiro Taniguchi, Hirohiko Fukuda, Hideki Kinoshita, ...
    1984 Volume 57 Issue 3 Pages 781-786
    Published: 1984
    Released: June 27, 2006
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    3-(5-Nitro-2-oxo-1,2-dihydro-1-pyridyl)-1,2-benzisothiazole 1,1-dioxide(BID-NPy), readily prepared from 3-chloro-1,2-benzisothiazole 1,1-dioxide and 5-nitro-2-pyridone, proved to be a very useful condensing reagent. A variety of esters, dipeptides, and lactones were obtained in excellent yields. Furthermore, BID-NPy was successfully employed for the lactonization step in a new synthesis of a naturally occurring (±)-(E)-8-dodecen-11-olide, recifeiolide.
  • Tomio Shimizu, Yoshiyuki Hayashi, Toshiyuki Nishio, Kazuhiro Teramura
    1984 Volume 57 Issue 3 Pages 787-790
    Published: 1984
    Released: June 27, 2006
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    C-Ethoxycarbonylnitrilimines treated with monosubstituted olefins predominantly gave 5-substituted 3-ethoxycarbonyl-2-pyrazolines. From the analysis of the relative rate and regioselectivity of a variety of monosubstituted olefins for the cycloaddition, the nitrilimine is shown to have reactivity and regioselectivity similar to the throughly studied diphenylnitrilimine. The cycloaddition regioselectivity is discussed in terms of frontier orbital energies and coefficients.
  • Yo Miyagi, Kazuhiro Maruyama, Nobuo Tanaka, Mamoru Sato, Toshinori Tom ...
    1984 Volume 57 Issue 3 Pages 791-795
    Published: 1984
    Released: June 27, 2006
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    Upon irradiation a regio- and stereoselective cycloaddition occurred intramolecularly between two acyl-1,4-benzoquinone moieties connected by a polymethylene bridge. The regio- and stereoselectivities are different from those of the corresponding intermolecular cycloaddition; this was interpreted in terms of the Diels-Alder reaction between an acyl-1,4-benzoquinone moiety and a photochemically produced dienol.
  • Kunio Mochida
    1984 Volume 57 Issue 3 Pages 796-801
    Published: 1984
    Released: June 27, 2006
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    Conformational analyses of a series of neopentyl- and trimethylsilylmethyl-substituted germyl radicals by electron spin resonance (ESR) were investigated on the basis of the modified cos2θ rule. Dimethylneopentylgermyl radical has the conformations with the neopentyl group rotating freely. On the other hand, dimethyl(trimethylsilylmethyl)germyl radical has the preferred conformations with trimethylsilylmethyl group eclipsing with the singly occupied orbital on a germanium atom. The ESR spectra of dineopentylmethylgermyl and bis(trimethylsilylmethyl)methylgermyl radicals showed the existence of two kinds of methylene protons due to the nonplanar geometries and the slow inversion of these germyl radicals. Conformations of trineopentylgermyl and tris(trimethylsilylmethyl)germyl radicals are also discussed.
  • Sadao Tsuboi, Eiichiro Amano, Akira Takeda
    1984 Volume 57 Issue 3 Pages 802-805
    Published: 1984
    Released: June 27, 2006
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    A key intermediate of 2-(2,2-dichloroethenyl)-3,3-dimethylcyclopropanecarboxylic acid, 3-alkoxycarbonyl(or acyl)-4-(2,2-dichloroethenyl)-5,5-dimethyltetrahydro-2-furanone was prepared by the base-catalyzed condensation of 2-methyl-3,5,5-trichloro-4-penten-2-ol with acetate derivatives such as malonic esters, acetoacetic esters, and benzoylacetate. The reactivity of 3-acetyl-4-(2,2-dichloroethenyl)-5,5-dimethyltetrahydro-2-furanone to an excess amount of thionyl chloride in ethanol was also examined. An analog, 5-butyl-4-(2,2-dichloroethenyl)-3-ethoxycarbonyl-5-methyltetrahydro-2-furanone was also prepared in 31% yield.
  • Hiroo Inoue, Toshiki Origuchi, Katsumi Umano
    1984 Volume 57 Issue 3 Pages 806-809
    Published: 1984
    Released: June 27, 2006
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    The morphan skeleton was prepared from 2-phenylsulfonyl-2-azabicyclo[3.2.1]oct-6-ene (2), derived from norbornadiene, through the addition of dichlorocarbene to the monoene 2 and the subsequent thermal isomerization of the adduct obtained. The isomerization products, 2-phenylsulfonyl-6,7-dichloro-2-azabicyclo[3.3.1]non-7-ene and 2-phenylsulfonyl-7,8-dichloro-2-azabicyclo[3.3.1]non-6-ene, which are mutually convertible in the presence of lithium chloride, were converted into various morphans by reductive dechlorination and alkylation. Furthermore, the 6,7-pyridazino-annelated morphan was synthesized by the cycloaddition of dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate to 2-phenylsulfonyl-2-azabicyclo[3.3.1]non-6-ene.
  • Osamu Itoh, Takayoshi Nagata, Isamu Nomura, Tetsuya Takanaga, Toshio S ...
    1984 Volume 57 Issue 3 Pages 810-814
    Published: 1984
    Released: June 27, 2006
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    Ethyl dichloro(ethoxy)acetate (1) and methyl dichloro(methoxy)acetate (2) were characterized. The reaction of 1 and 2 with aromatics in the presence of AlCl3 gave a considerable yield of aromatic α-keto ester. The aromatics included mono- and polymethylbenzene and anisol. The reaction was studied under various conditions and the results were compared with the acylation by ethoxalyl or methoxalyl chloride. The reaction mechanism was also discussed.
  • Ichizo Miyake, Katsushige Kouge, Hidenori Kanehisa, Hideo Okai
    1984 Volume 57 Issue 3 Pages 815-818
    Published: 1984
    Released: June 27, 2006
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    In order to elucidate the relationship between taste exhibition and chemical structure of bitter peptide BPIa, di–BPIa, Gly–Gly–BPIa, BPIa–Gly–Gly, and Gly–Gly–BPIa–Gly–Gly were synthesized. All of the peptides possessed a strong bitter taste of the same level as that of BPIa. In addition, the CD curves of the peptides were similar to that of BPIa. The results suggested that their spatial structures are essentially similar and that the whole molecular shape of BPIa contributes to its bitterness.
  • Hidenori Kanehisa, Ichizo Miyake, Hideo Okai, Haruhiko Aoyagi, Nobuo I ...
    1984 Volume 57 Issue 3 Pages 819-822
    Published: 1984
    Released: June 27, 2006
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    In order to ascertain the validity of the structure of bitter peptide BPIa (H–Arg–Gly–Pro–Pro–Phe–Ile–Val–OH) isolated from casein hydrolyzate by Minamiura et al., the C-terminal octapeptide of β-casein (H–Arg–Gly–Pro–Phe–Pro–Ile–Ile–Val–OH) determined by Ribadeau Dumas et al., which is assumed to correspond to BPIa, was synthesized and compared with the synthetic BPIa which was confirmed to be identical with the natural one. The two synthesized peptides, however, did not match on thin-layer chromatography. The result indicates that the structure of BPIa need not be converted to Ribadeau Dumas’ formula. The octapeptide possessed an extremely bitter taste, with a threshold value of 0.004 mM (1 M=l mol dm−3). It is the most bitter peptide.
  • Masanobu Yatagai, Takamichi Yamagishi, Mitsuhiko Hida
    1984 Volume 57 Issue 3 Pages 823-826
    Published: 1984
    Released: June 27, 2006
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    In the hydrogenation of dehydrodipeptides, the effect of chiral center of the substrate ((S) or (R)) on the asymmetric induction was examined using the catalysts of Rh(I)–chiral diphosphinite containing pyrrolidine moiety (POP). The catalysts with POP’s having the ω-(dimethylamino)alkyl group indicated an extremely large double asymmetric induction to give (S,S)- or (R,R)-product in high stereoselectivities, depending on the chiral center of the substrates. This result was ascribed to the electrostatic interaction between the ligand and substrate. POP’s without ω-(dimethylamino)alkyl group gave (R,R)-product for (R)-substrate in a high stereoselectivity by the steric effect between the ligand and substrate, while for (S)-substrate, (S,S)-product was obtained in a low stereoselectivity.
  • Masahiro Kato, Isao Kuwajima
    1984 Volume 57 Issue 3 Pages 827-830
    Published: 1984
    Released: June 27, 2006
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    1-(Trimethylsilyl)propargyl alcohols have been prepared by treating acyltrimethylsilanes with magnesium acetylides, and their base-induced reactions involving rearrangement of silyl group have been examined. Treatment of the alcohol with an equimolar amount of butyllithium in hexane followed by addition of tetrahydrofuran has allowed to generate the lithiated 3-trimethylsiloxy-1,2-propadiene, which reacts with an alkyl iodide to afford the alkylated 1-trimethylsiloxy-1,2-propadiene in high yield. Further, a catalytic amount of butyllithium also effects an efficient conversion of the alcohol to the corresponding 1-siloxy-1,2-propadiene through a similar rearrangement process.
  • Masahiko Abe, Mitsuo Ohsato, Nobuyuki Suzuki, Keizo Ogino
    1984 Volume 57 Issue 3 Pages 831-835
    Published: 1984
    Released: June 27, 2006
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    The interactions between 4 anionic surfactants and 3 azo oil dyes have been studied by a spectrophotometer. The spectrographic behavior of these solutions was dependent on the kinds of hydrophilic groups in each surfactant and the kind of auxochrome in the azo oil dyes. In particular, a sulfate and two sulfonates including strongly hydrophilic groups interacted strongly with the oil dyes (4-NH2) which have an amino group at 4-position of naphthalene. At lower concentrations, an isosbestic point was recognized; this occurred because of the formation of the hydrophobic dye–surfactant complex (1:1). In the neighborhood of the cmc region, the spectrum with a peak at 520 nm changed with temperature into another one with a 440 nm band; this is the so-called thermochromism. This may be attributed to the fact that, in the presence of surfactant micelles, the 4-NH2 exhibits an azo form at higher temperature, but a resonance stabilized azonium form is found at lower temperature.
  • Akira Kai
    1984 Volume 57 Issue 3 Pages 836-839
    Published: 1984
    Released: June 27, 2006
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    The structure of the nascent fibril produced by Acetobacter xylinum was examined by electron microscopy and resistance to alkali. It was found that the inner part of the fibril after production is stained uniformly with sodium tungstophosphate. This suggests that the nascent fibril is in an amorphous state. Moreover, the fact that in the amorphous fibril microscopic fibrils with closely similar widths always appear in the course of time and that the X-ray diffraction diagram of the never-air-dried fibril treated with 11 wt% aqueous NaOH solution show cellulose I not cellulose II diffraction patterns, indicate that the arrangement of cellulose chains in its cross section can transform easily to that of chains in ellulose I crystalline. For such an arrangement, it must be presumed that in the nascent fibril cellulose chains are in the form of sheets of monomolecular layers corresponding to the (1\bar10) plane of cellulose I crystalline.
  • Mikio Miyake, Masayuki Sukigara, Masakatsu Nomura, Sh\={o}ichi Kikkawa
    1984 Volume 57 Issue 3 Pages 840-843
    Published: 1984
    Released: June 27, 2006
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    A series of butylated Y\barubari coals were prepared by an improved reductive alkylation method, and detailed structural parameters of respective solution products in pentane (PS) and benzene (BS) were estimated; this experimental procedure is likely to offer more insight into chemical structures of products and important factors effective for solubilization than any analyses on a single product. The PS and BS have average molecular weights of 700–800 and 1500–2050 and are composed of about two and more than five structural units, respectively. These values suggest that the BS molecule is quite large compared with the corresponding products obtained by other methods such as hydrocracking. On the other hand, the ring sizes of one structural unit of the respective products are roughly the same (about three rings). The BS materials are coal macromolecules with stackings loosened by introduction of alkyl groups, while the PS materials are products through cleavage of bonds connecting the structural units and through addition of so many alkyl groups as to increase the affinity for the solvent. In addition, an absence of intermolecular hydrogen bonds mainly due to OH groups contributes to quite a high solubility of the alkylated coals. Increase in BS yield accompanies an increase in aliphatic carbon ratio and polymerization degree and a decrease in size of aromatic ring systems. These results may be ascribed to the heterogeneity of coal constituents.
  • Rafie Hassan Abu-Eittah, Maher Mohamed Hammed
    1984 Volume 57 Issue 3 Pages 844-851
    Published: 1984
    Released: June 27, 2006
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    The electronic absorption spectra of three groups of furan derivatives: 2-formyl, 2-acetylfuran, and 2-furoic acid, N-(2-furylmethylene)amines and phenylfurans were investigated. The predominant conformation as well as the polarity of the molecule could be predicted from its spectrum. The investigated molecules were proved to be “all planar” configuration which led to substantial interaction between the electronic states of the subsystems. The preferred conformations of N-(2-furylemthylene)methylamine and N-(2-furylemthylene)aniline were predicted with the aid of molecular orbital calculations.
  • Vinay P. Shedbalkar, Subray N. Bhat
    1984 Volume 57 Issue 3 Pages 852-855
    Published: 1984
    Released: June 27, 2006
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    The iodine complexes of benzene, toluene, o-, m-, p-xylene and mesitylenes in cyclohexane are studied by using constant activity method. The association constants and the other thermodynamic parameters of the complexes are determined and the results are compared with those obtained by using conventional spectral methods. The blue shifted iodine band maxima are determined directly.
  • Rolf Gleiter, Peter Bischof, Michael C. Böhm, Roger Guilard, Hiro ...
    1984 Volume 57 Issue 3 Pages 856-861
    Published: 1984
    Released: June 27, 2006
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    Using a helium discharge lamp with an energy of 21.21 eV (He(I)α line) the photoelectron (PE) spectra of the heterotropones 17 have been investigated and compared with the PE spectra of benzologue tropones and with the PE data of thiophene, furan and pyrrole. The first five ionization events in the PE spectra of 1 to 7 could be assigned to electron ejections from 2a2(π), 4b1(π), 9b2(n), 3b1(π), and 1a2(π) orbitals. This assignment has been deduced by means of experimental correlation techniques and using ZDO calculations of the LCBO and HMO type as well as semiempirical SCF versions (MINDO/3 and PPP).
  • Jagdish Prasad Rawat, Balbir Singh
    1984 Volume 57 Issue 3 Pages 862-865
    Published: 1984
    Released: June 27, 2006
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    Ion exchange equilibria of alkali metal ions (Li+, Na+, K+ and Rb+)/H+ systems have been studied at 30, 40, 50, and 60 °C on iron(III) antimonate as a cation exchanger. The exchange isotherms have been measured for both forward and backward reactions with solutions of ionic strength 0.1 by the batch technique. The isotherms showed S-shaped curves for each exchange system except Li+/H+. Selectivity coefficients vary with the equivalent fraction (\barXM) of the alkali metal ions in the exchanger and give linear functions against \barXM in the range from 0–0.40. The selectivity sequence shows Na+<Li+<K+<Rb+. The overall thermodynamic data are evaluated.
  • Ghirma Moges, Demirew Assefa, Bhagwan Singh Chandravanshi
    1984 Volume 57 Issue 3 Pages 866-868
    Published: 1984
    Released: June 27, 2006
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    N1-Hydroxy-N1,N2-diphenylbenzamidine (HDPBA) reacts with iron(III) in the presence of azide to give a violet-coloured complex insoluble in water. The mixed ligand complex having a composition of 1:2:2 (Fe:HDPBA:N3) is quantitatively extracted into chloroform at pH 2–5. The violet-coloured complex has an absorption maximum at 530 nm with a molar absorptivity of 4900 l mol−1 cm−1. On the basis of this sensitive colour reaction, a highly selective method has been developed for the extraction and spectrophotometric determination of microgram quantities of iron(III). The effect of foreign ions and several experimental variables have been studied. The method is simple, rapid, precise, and free from the regid control of experimental parameters.
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