Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 56 , Issue 4
Showing 1-50 articles out of 69 articles from the selected issue
  • Shunichi Fukuzumi, Jay K. Kochi
    1983 Volume 56 Issue 4 Pages 969-979
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The rates of arene and alkene brominations and mercurations, Diels-Alder cycloaddition as well as alkylmetal cleavages by electrophiles, electron acceptors and free atoms can be quantitatively analyzed in terms of the driving force for electron transfer. The single, unified free energy relationship for all of these rather disparate chemical processes relates the activation free energy to the standard free energy change for electron transfer and the work term for ion-pair formation. The latter is evaluated from charge transfer spectral data of the electron donoracceptor complexes formed as transient intermediates. The large variations in the apparent Brönsted slopes from unity to even negative values in these systems can be readily attributed to changes in the work terms arising from steric effects in ion-pair formation.
  • Hironobu Kunieda, K\={o}z\={o} Shinoda
    1983 Volume 56 Issue 4 Pages 980-984
    Published: 1983
    Released: June 27, 2006
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    A three-phase region consisted of a water (W), a surfactant (D) and an oil (O) phases was found in a sodium taurocholate (NaTC)/brine/co-surfactant (monoglyceride or its model compound)/oil (triglyceride) system. A required concentration of cosurfactant to produce the three-phase region was decreased with increasing salinity. The three-phase region becomes narrower and finally vanishes with decreasing salinity at constant temperature or with the rise in temperature at constant salinity in a NaTC/brine/glycerol mono (2-ethylhexyl) ether/glycerol tris (2-ethylhexanoic) ester system. Since the critical end points of O–D and D–W phases approach and coincide in the system, the three-phase region disappears at a tricritical point at which three coexisting liquid phases become identical. According to the phase rule, there is a line of tricritical points in the space of T and compositions in this five-component system and it moves toward higher temperatures with the increase in salinity. Therefore, the three-phase region exists at temperatures below the tricritical temperature at constant salinity.
  • Tooru Inoue, Toshihiro Yamase
    1983 Volume 56 Issue 4 Pages 985-990
    Published: 1983
    Released: June 27, 2006
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    Polypyrrole films prepared on Pt or SnO2 through electrochemical oxidative polymerization of pyrrole were characterized with respect to electroconductivity by photoelectrochemical measurements. Redox reactions of solution species such as methyl viologen, hydroquinone, oxygen, Cu2+, I, and Br occur on these electroconductive films. Light excitation of the film with wavelengths shorter than 550 nm results in observable cathodic photocurrent at the potential region more negative than 0.0 V vs. Ag. The polypyrrole film is a p-type semiconductor with a bandgap energy of ca. 2.2 eV and is stable during redox reactions.
  • Tadaaki Kakutani, Toshiyuki Osakai, Mitsugi Senda
    1983 Volume 56 Issue 4 Pages 991-996
    Published: 1983
    Released: June 27, 2006
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    Potential-step chronoamperometry, cyclic voltammetry, and chronopotentiometry have been applied to the study of the transfer of the tetramethylammonium (TMA+) ion across the interface between a 0.1 mol dm−3 lithium chloride aqueous solution and a 0.1 mol dm−3 tetrabutylammonium tetraphenylborate nitrobenzene solution. An analysis of the current-time and current-potential curves obtained by means of potential-step chronoamperometry indicates that the transfer of the TMA+ ion across the water/nitrobenzene interface is a reversible diffusion-controlled process, which can be explained by the theory of the chronoamperometry of a reversible charge transfer at the electrode surface. The values of the diffusion coefficient of the TMA+ ion in the aqueous phase and of the reversible half-wave potential of the TMA+ ion transfer, as determined by means of potential-step chronoamperometry, agreed well with those determined by means of cyclic voltammetry and chronopotentiometry.
  • Kunio Furusawa, Hidetoshi Sakai, Noribumi Watanabe, Norio Tomotsu
    1983 Volume 56 Issue 4 Pages 997-1001
    Published: 1983
    Released: June 27, 2006
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    The adsorption behavior of poly(L-lysine) and poly(L-glutamic acid) on negatively and positively charged latices was examined in combination with their stabilizing effects on the latex dispersion. It was realized that the polypeptide adsorption was, to a large extent, determined by the coulombic interaction between the polypeptide and the charged surface, and by the conformational change (helix-coil transition) in the polypeptide in the solution. The flocculation behavior of the dispersion in the presence of polypeptide was also explained reasonably by taking account of the results of electrophoretic measurements of the polypeptide-coated particles.
  • Ikuo Abe, Katsumi Hayashi, Mutsuo Kitagawa, Tsuneaki Hirashima
    1983 Volume 56 Issue 4 Pages 1002-1005
    Published: 1983
    Released: June 27, 2006
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    A method is presented for predicting the adsorbability of a wide variety of organic compounds from aqueous solution onto an activated carbon. The method, which is based on the linear free-energy relationship, requires only the solute’s molecular refraction and the number of hydrophilic functional groups. The molecular refraction represents the free energy contribution by the solute-adsorbent interaction and the number of hydrophilic functional groups represents that by the solute-solvent interaction.
  • Kazunori Matsuki, Hideo Fukutome
    1983 Volume 56 Issue 4 Pages 1006-1011
    Published: 1983
    Released: June 27, 2006
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    The UV absorption spectra of monolayers of 12-(9-anthrylcarbonyloxy)octadecanoic acid (12-AS), 2-(9-anthrylcarbonyloxy)hexadecanoic acid (2-AP), and 2-octadecylamino-6-naphthalenesulfonic acid (ONS) were measured at normal incidence and the polarized spectra at 45° incidence. New peaks which were absent in the spectra of their solutions were observed in the polarized spectra at 45° incidence. The orientation of their chromophores in the monolayers were investigated by means of the dichroic ratios obtained from their polarized spectra. These monolayers were found to consist of H-aggregates where chromophores are oriented nearly perpendicularly to the monolayer plane and molecules in a monomer-like state where the chromophores are rather randomly oriented. The molecular axes of 12-AS, 2-AP, and ONS were found to be oriented uniaxially against the normals of their monolayer planes in the ranges 0–7°, 0–21°, and 0–34°, respectively.
  • Nariyoshi Kawabata, Eisuke Natsuhara, Ichiro Higuchi, Jun-ichi Yoshida
    1983 Volume 56 Issue 4 Pages 1012-1015
    Published: 1983
    Released: June 27, 2006
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    Selective ion-exchange adsorption of a series of alkylbenzenesulfonate ions (CnBS) on a series of crosslinked poly(N-alkyl-4-vinylpyridinium bromide) (CmVP) and crosslinked poly(N-benzyl-4-vinylpyridinium bromide) (BVP) was investigated based upon the selectivity coefficient of the resins for CnBS relative to Br which was expressed as KBrCnBS. In the adsorption of CnBS of n<8, the selectivity coefficient linearly increased with the number of carbon atoms of the alkyl chain, n, of CnBS, which was ascribed to the hydrophobic interaction between the alkyl chain of CnBS and the resin. In the adsorption of CnBS of n>8, however, the selectivity coefficient did not increase with n, which was explained in terms of a steric effect. The selectivity coefficient also increased with the number of carbon atoms of the alkyl chain, m, of CmVP, but saturation was also observed for the adsorption on CmVP of m>12. In the adsorption of CnBS of n<8 on BVP, significant influence of the degree of quaternization was not observed. In the adsorption of C12BS, however, BVP of lower degree of quaternization showed a much larger selectivity than that of BVP of higher degree of quaternization. The observation indicated that steric repulsion between CnBS ions adsorbed on the surface of the resin played a crucial role.
  • Hiroshi Sakai, Tomochika Matsuyama, Hitoshi Yamaoka, Yutaka Maeda
    1983 Volume 56 Issue 4 Pages 1016-1020
    Published: 1983
    Released: June 27, 2006
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    The 129I Mössbauer spectra at 16 K have been measured for the π-σ charge transfer complexes of iodine with benzene, coronene, perylene, and poly(p-phenylene). It is suggested that the benzene-iodine complex in benzene prepared by slow cooling consists of alternate benzene and iodine molecules with the six-fold axial symmetry. The Mössbauer spectrum for the coronene-iodine complex (1:1) shows only one chemical state of iodine. The acceptor orbital is described by only the σu-antibonding molecular orbital of iodine. The extent of charge transfer in the complex is estimated to be 0.06e in the electronic ground state. In the poly(p-phenylene)-iodine complex the iodine exists as almost a free molecule, indicating that the interaction between the phenylene ring and iodine is very weak.
  • Morihide Higo, Satsuo Kamata, Teiichiro Ogawa
    1983 Volume 56 Issue 4 Pages 1021-1024
    Published: 1983
    Released: June 27, 2006
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    The Balmer-α, β, γ lines of the excited hydrogen atoms (n=3, 4, 5) produced in e-HCl and DCl collisions have been measured in the energy range of 30–300 eV. The average translational energies of H* and D* are 4–5 eV at higher electron energies and 2–2.5 eV at lower electron energies; no appreciable isotope effect is found for the translational energy. The relative emission cross section of D* and H* shows an isotope effect and this effect is larger in the lower electron energy range; σD⁄σH’s are 0.74 for n=3, 0.71 for n=4 and 0.78 for n=5 at 30 eV. These results show that there are two groups of the excited hydrogen atoms and their relative cross sections vary with the electron energy. The existence of the isotope effect indicates a competing decay process in the repulsive excited states of HCl.
  • Hiroyoshi Kanai, Nobuyuki Hiraki, Shigeki Iida
    1983 Volume 56 Issue 4 Pages 1025-1029
    Published: 1983
    Released: June 27, 2006
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    A new method for the synthesis of cyclopropane derivatives is described. It involves treatment of electrondeficient olefins with dibromomethane in the presence of Ni(0) complex/zinc/Lewis acid (or alkali halide) systems. Ni(PPh3)4/Zn/ZnBr2 system was effective for the cyclopropanation of methyl acrylate and acrylonitrile, but was ineffective for that of methyl vinyl ketone and acrylaldehyde. Ni(COD)2/Zn/NaI system was applicable to the cyclopropanation of methyl vinyl ketone as well as to that of methyl acrylate and acrylonitrile. Alternative catalytic systems which were easy to handle were exploited, involving in situ generated Ni(0) complexes prepared from NiBr2(PPh3)2 and zinc, or nickel bromide, sodium iodide, zinc, and an olefin. Catalytic amounts of nickel compounds are sufficient for the cyclopropanation of methyl acrylate, acrylonitrile, and methyl vinyl ketone, but a 1 : 2 nickel : acrylaldehyde mole ratio results in the best yield. A mechanism is proposed which involves metallacyclobutane as an intermediate.
  • Tsutomu Masujima, Kiwamu Yamaoka, Jin-ichiro Hori
    1983 Volume 56 Issue 4 Pages 1030-1036
    Published: 1983
    Released: June 27, 2006
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    Intrinsic viscosity, [η], and far-UV circular dichroism, CD, were measured at 25 °C for poly(α-L-glutamic acid), poly(Glu), solutions in 7.5 mM and 150 mM NaCl in the presence and the absence of copper(II) ions over the pH range 4–7, where poly(Glu) undergoes two conformational transitions. The first is the well-known helixcoil transition and the second, which is followed by completion of the helix, was attributed to the formation of aggregates. The pH dependence of [η] and molar ellipticity was analyzed with the two-state model. The helixcoil transition can not be represented by the all-or-none process. The aggregation mode of helices is predominantly the side-by-side type in 7.5 mM NaCl, but probably a mixture of the side-by-side and the head-to-tail types in 150 mM NaCl. The hydrodynamic shapes of poly(Glu) and its Cu(II)-complexes were calculated with ellipsoid, cylinder, and straight chain element models. The so-called random-coil form is an extended-coil in 7.5 mM NaCl at higher pH. The poly(Glu) helix is probably slightly shortened as compared with the α-helix.
  • Kunio Takeda
    1983 Volume 56 Issue 4 Pages 1037-1040
    Published: 1983
    Released: June 27, 2006
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    Stopped-flow measurements were made on the conformational change of bovine serum albumin induced by sodium dodecyl sulfate in a buffer solution containing 3.33 mmol/dm3 NaH2PO4 and 3.56 mmol/dm3 Na2HPO4 (pH 7.0, μ=0.014). The protein adopted a conformation with a smaller helical content than the original native state (helix to coil transition) upon the addition of the surfactant. The rate of transition depended strongly on the surfactant concentration. The results were compared with those of conformational changes of other proteins, in which a helical structure increased in the surfactant solution (coil to helix transition). It is noticeable that the value of the activation entropy is negative in the helix to coil transition, as compared with its positive and large values in the coil to helix transition. It seems that the binding of the surfactant to the protein causes the transition to only a particular conformation of the protein via each individual process.
  • Shi-aki Hyodo, Unpei Nagashima, Tsunetake Fujiyama
    1983 Volume 56 Issue 4 Pages 1041-1044
    Published: 1983
    Released: June 27, 2006
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    By considering the charge distribution function around the ion, the effect of the finite size of the solvent molecule can be introduced in the homogeneous dielectric continuum model. A very simple and useful model is presented. The results of this model are compared quantitatively with the experimental Walden products of some simple cations in water, methanol, ethanol, acetone, and acetonitrile solutions, and found to be satisfactory.
  • Yoko Sugawara, Yoshiaki Hamada, Masamichi Tsuboi
    1983 Volume 56 Issue 4 Pages 1045-1050
    Published: 1983
    Released: June 27, 2006
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    Taking advantage of the Fourier transform infrared (FTIR) spectrophotometry in accumulating a very weak available radiation, which comes out from a multiple-reflection-type gas-cell (17 m), we have been able to record the infrared absorption spectrum of formamide (HCONH2 or DCONH2) at room temperature, where its vapor pressure is only 0.1 Torr (1 Torr≈133.322 Pa) in the order of magnitude. From an analysis of the rotational structure (resolution 0.5 cm−1) of the C–H stretching band, a revised set of parameters has been obtained. A Q-branch analysis was made for the v=2←0 and v=3←1 bands (resolution 0.24 cm−1) of the amino wagging vibration, where v is its vibrational quantum number. The rotational constants AB were determined to be 2.0269 cm−1 for the v=2 state and 1.9990 cm−1 for the v=3 state, and the transition frequencies 657.75 cm−1 for v=2←0 and 769.85 cm−1 for v=3←1. On the basis of these new parameter values, a discussion was made of the amino wagging coordinate of this molecule.
  • Yoshihisa Yamamoto, Hiroko Kudo, Eiko Toyota
    1983 Volume 56 Issue 4 Pages 1051-1056
    Published: 1983
    Released: June 27, 2006
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    In the 1H and 13C NMR spectra of trans- or cis-dichloro(quadridentate amine)cobalt(III) chloride hydrates, [CoCl2L]Cl·nH2O (L: 2,2,2-tet(trien) (1a), 2,3,2-tet (1b), 3,2,3-tet (1c), and 3,3,3-tet (1d)), the signals of their methylene protons and methylene carbons have been assigned to the individual methylene protons and methylene carbon of the coordinated quadridentate amine ligands. The order of 1H and 13C chemical shift of their methylene protons and methylene carbon is as follows:
    (Remark: Graphics omitted.)
    Thus, the signal of the center methylene protons (or carbon) of the coordinated quadridentate amine ligands appears at higher field than that of the NH-side methylene protons (or carbon). cis1-Salicylato(3,7-diazanonane-1,9-diamine)cobalt(III) chloride hydrate, cis1-[Co(sal)(2,3,2-tet)]Cl·H2O (3b), and cis2-salicylato(quadridentate amine)cobalt(III) chloride hydrates, cis2-[Co(sal)L]Cl·nH2O (L: 2,3,2-tet (4b), 3,2,3-tet (4c) and 3,3,3-tet (4d)) have been isolated from a reaction mixture of sodium salicylate or salicylic acid and 1bd. The properties of 3b and 4b are similar to those of the previously reported complexes 3a (L: 2,2,2-tet, β1-form) and 4a (L: 2,2,2-tet, β2-form), respectively. Those of 4c are similar to those of 4d. Complex 4d is the most unstable complex among 4ad. This property is attributable to the center methylenes of the coordinated quadridentate amine ligands.
  • Junzo Otera, Torn Yano, Kazunori Kusakabe
    1983 Volume 56 Issue 4 Pages 1057-1059
    Published: 1983
    Released: June 27, 2006
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    Di-t-butyltin bis(chelates) were prepared and characterized in comparison with dimethyltin analogs. 119Sn NMR spectra show a six-coordinate configuration for the acetylacetonate, tropolonate, and oxinate; a nonchelating structure is partially involved in the 2-methyloxinate and dialkyldithiocarbamates. Di-t-butyltin dichloride gives no isolable adducts with monodentate ligands; however, the Job’s continuous variation method using 119Sn NMR spectra has revealed that complexations with 2 : 1 and/or 1 : 1 donor/Sn molar ratios occur in ether. It has been concluded that t-butyl group reduces the acceptor property of tin by means of both inductive and steric effects.
  • Yasuhisa Ikeda, Hiroshi Tomiyasu, Hiroshi Fukutomi
    1983 Volume 56 Issue 4 Pages 1060-1066
    Published: 1983
    Released: June 27, 2006
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    The exchange reactions of dimethyl sulfoxide (DMSO) with UO2(acac)2dmso and UO2(dbm)2dmso (acac=acetylacetonate, dbm=dibenzoylmethanate) have been studied by the NMR method in CD3COCD3 and CD2Cl2. In CD3COCD3, rates of DMSO exchange for these complexes are independent of the free DMSO concentrations. Rate constants (s−1) at 25 °C and activation parameters ΔH\ eweq (kJ mol−1) and ΔS\ eweq (J K−1 mol−1) are 2.36×102, 45.8±0.8, −46.6±2.9 for UO2(acac)2dmso, and 3.92×102, 44.5±0.4, −46.2±2.1 for UO2(dbm)2dmso, respectively. In CD2Cl2, the exchange rates are dependent on the free DMSO concentration. For UO2(acac)2dmso, rate=(kd+kIKOS[DMSO])[UO2(acac)2dmso]/(1+KOS[DMSO]), where kd(25 °C=1.02×102 s−1, ΔH\ eweq=47.9±5.2 kJ mol−1, and ΔS\ eweq=−46.6±11.2 J K−1 mol−1, and kI(25 °C)=1.01×103 s−1, ΔH\ eweq=35.4±12.4 kJ mol−1, and ΔS\ eweq=−69.7±20.5 J K−1 mol−1, and KOS(10 °C)=4.6±2.1 M−1 (M=mol dm−3). For UO2(dbm)2dmso, rate=(k1+k2[DMSO]) [UO2(dbm)2dmso], where k1(25 °C)=1.74×102 s−1, ΔH\ eweq=29.6±2.2 kJ mol−1, ΔS\ eweq=−104±9 J K−1 mol−1, and k2(25 °C)=1.62×103 M−1 s−1, ΔH\ eweq=34.9±0.6 kJ mol−1, and ΔS\ eweq=−67.2±2.4 J K−1. The D and I mechanisms are proposed for the DMSO exchange in these complexes.
  • Isamu Kinoshita, Yasuno Yokota, Keiji Matsumoto, Shun’ichiro Ooi ...
    1983 Volume 56 Issue 4 Pages 1067-1073
    Published: 1983
    Released: June 27, 2006
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    Green trans-dichlorocobalt(III) complexes with a variety of achiral and chiral (2-aminoalkyl)phosphines have been prepared and characterized. The crystal structures of [CoCl2{(2-aminoethyl)diphenylphosphine}2]1/2[CoCl4] and [CoCl2{(R)-(2-aminoethyl)butylphenylphosphine}2]ClO4 have been determined by X-ray analyses. Both complex cations have a distorted octahedral coordination with two Cl atoms in the trans positions and two P (and N) atoms in the cis positions. The Co–N distances (2.02–2.05 Å) are 0.05–0.07 Å longer than the usual Co(III)–N distance, and the P–Co–P angles are widened (99.4 and 103.1°) on account of bulky substituents on the phosphorus atoms. The circular dichroism spectra of [CoCl2{(2-aminoethyl)diphenylphosphine}2]ClO4 (space group P3221) in Nujol mull and the complexes with chiral (aminoalkyl)phosphines in methanol solutions have been recorded and compared with those of related complexes.
  • Hiroaki Tao, Yasuo Iwata, Tetsuya Hasegawa, Yukihiro Nojiri, Hiroki Ha ...
    1983 Volume 56 Issue 4 Pages 1074-1079
    Published: 1983
    Released: June 27, 2006
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    A simple and convenient analytical method for simultaneous multielement determination of soil and rock samples has been investigated by inductively coupled plasma emission spectrometry. Spectral interferences due to major elements were examined in detail, and the correction coefficients for minor and trace elements were estimated for correction of matrix effects. The determinations of minor and trace elements as well as major elements could be performed without matrix matching of the standard solutions. The present method investigated has been applied to the analysis of various soil and rock samples, and the analytical results have been compared with those obtained by atomic absorption spectrometry.
  • Hideo Suganuma, Itsuhachiro Hataye, Yoshimasa Takashima
    1983 Volume 56 Issue 4 Pages 1080-1083
    Published: 1983
    Released: June 27, 2006
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    A cation-exchange method was used for determining the average cationic charge of polonium species present in hydrolytic equilibrium in solutions. This method is based on measurements of the distribution ratio of polonium at a constant internal hydrogen-ion concentration of the cation-exchanger phase. In 1.0 mol dm−3 (H,Na)ClO4 and 1.0 mol dm−3 (H,Na)NO3 solutions at −log[H+]=1.0, tracer concentrations of polonium(IV) were found to exist in the mean chemical forms of Po(OH)3.430.53+ and Po(OH)2.83(NO3)0.600.57+, respectively. The formation of cationic polymerized species was also estimated in region of 4−log[H+] in a 1.0 mol dm−3 (H,Na)ClO4 solution.
  • Kenzo Kitayama, Takashi Katsura
    1983 Volume 56 Issue 4 Pages 1084-1088
    Published: 1983
    Released: June 27, 2006
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    Phase equilibria in the Tm2O3–V2O3–V2O5 system were established at 1200 °C; the oxygen partial pressure was varied −0.68 (air) to −12.50 atm in terms of log Po2. In this system, VnO2n−1 (n=2–7), VO2, Tm2O3, TmVO3, TmVO4, Tm8V2O17 (4Tm2O3·V2O5), Tm7V3O16 were stable under the present experimental conditions. The pattern of the phase diagram is different from those of other Ln2O3–V2O3–V2O5 systems (Ln=Sm, Lu, Er, Gd, La, and Nd) that were already established. Compounds TmVO3, TmVO4, Tm8V2O17, Tm7V3O16, V2O3, and VO2 have nonstoichiometric compositions. On the basis of the established phase diagram, the Gibbs energies of the reactions,
    (1) 2Tm2O3+3TmVO3+1⁄2O2=Tm7V3O16
    (2) TmVO3+1⁄2O2=TmVO4
    (3) 5⁄3Tm2O3+2⁄3Tm7V3O16+2⁄3O2=Tm8V2O17
    (4) Tm7V3O16+O2=5⁄3TmVO4+2⁄3Tm8V2O17
    were determined to be −132, −119, −157, and −228 kJ, respectively. The relationship between the ionic radius and ΔG° of the reactions, LnVO3+1/2 O2=LnVO4, is linear, provided that lanthanum and the lanthanoid can be divided into two groups.
  • Shinji Masuda, Tadashi Nakajima, Sohei Suga
    1983 Volume 56 Issue 4 Pages 1089-1094
    Published: 1983
    Released: June 27, 2006
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    Alkylations of benzene with both (−)-2-chloro-1-phenylpropane (1) and (+)-1-chloro-2-phenylpropane (2) in the presence of Lewis acid gave the same products: (−)-1,2-diphenylpropane (3), 1,1-diphenylpropane, and polymeric materials. In these reactions, (−)-3 was obtained in 45–100% optical yield and was not racemized under the conditions used. These results reveal that the reaction from 1 to 3 proceeds with retention of configuration and that from 2 to 3 with inversion. The stereochemistry of the alkylation with 1 is elucidated by the mechanism involving a neighboring phenyl π-assisted cation; benzene attacks only the β-carbon of 1 from the side on which the previously attached chloride anion is located. The result of the reaction with 2 can be explained by a process involving the 1,2-shift of phenyl group in the ionization step of 2, followed by the formation of the same intermediate as in the reaction with 1. The mechanism of the overall reaction is discussed.
  • Masajiro Kawana, Tetsuo Koresawa, Hiroyoshi Kuzuhara
    1983 Volume 56 Issue 4 Pages 1095-1100
    Published: 1983
    Released: June 27, 2006
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    The reactions of methyl 5-O-benzyl-2-O- and -3-O-tosyl-β-D-ribofuranosides with methylmagnesium iodide gave, in one-step, 2-deoxy-3-C- and 3-deoxy-2-C-methyl branched-chain sugars, respectively. These sugars were anomerized with Grignard reagents; the thermodynamically more stable anomers were converted preferentially into the respective less stable anomers.
  • Kenji Ogino, Katsuhiko Shindo, Tooru Minami, Waichiro Tagaki, Toshio E ...
    1983 Volume 56 Issue 4 Pages 1101-1106
    Published: 1983
    Released: June 27, 2006
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    Rate constants for hydrolysis of p-nitrophenyl picolinate at 25 °C in the pH range 6.5–8.5 were measured in the absence and presence of divalent metal ions (Ni(II), Zn(II), Co(II), Ca, Mg) and substituted imidazoles or pyridines as ligands having alcoholic hydroxyl groups in their side chains. In the presence of either metal ion or ligand, the rate is slow and the pseudo-first-order rate constant (kobsd) increases linearly in a first-order manner with respect to the concentration of metal ion or ligand until it gives the second-order rate constant, kM or kL, respectively. In the presence of both a metal ion (Ni(II) or Zn(II)) and a ligand, rate increase is remarkable for some ligands and the increase in kobsd values constructs saturation curves with respect to increase in either metal ion or ligand concentration. The saturation curves were analyzed based upon rate equations formulated by assuming the formation of 1 : 1 complex of metal ion and ligands as the catalyst, leading to evaluation of the association constant K for complexes and the second-order rate constant kc for the reaction of complex with substrate. Values of kobsd, kc, and K are dependent greatly upon the structure of ligands and pH. The ligands complexed with Zn(II) ion appear to be simple but highly active models of hydrolytic metalloenzymes.
  • Toyonori Takebayashi, Nobuharu Iwasawa, Teruaki Mukaiyama
    1983 Volume 56 Issue 4 Pages 1107-1112
    Published: 1983
    Released: June 27, 2006
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    An efficient method for the acceleration of the intramolecular Diels-Alder reaction was established utilizing the internal interaction—the internal hydrogen bonding and the internal coordination of a magnesium salt. The intramolecular Diels-Alder reaction between nitrofuran derivatives and various acrylic acid derivatives give good yields of the cycloadducts when internal hydrogen bonding is present. When cyclic α,β-unsaturated amides are employed as dienophile, the corresponding cycloadducts are obtained in high yield utilizing internal coordination of a magnesium salt.
  • Riichiro Nakajima, Masaji Kinosada, Takashi Tamura, Tadashi Hara
    1983 Volume 56 Issue 4 Pages 1113-1115
    Published: 1983
    Released: June 27, 2006
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    The function of palladium chloride in the reaction of an arylhydrazine with a haloarene was found to differ from those of other metal salts; palladium chloride was reduced with arylhydrazine, and the palladium metal produced was again oxidized with haloarene to give palladium halide. Thus the reductive coupling of haloarene occurred in the presence of a catalytic amount of palladium chloride. Addition of mercury(II) chloride promoted this reaction. The reaction of o-, m-, and p-bromotoluene with the corresponding tolylhydrazine gave the corresponding bitolyl in 99, 112, and 115% yield, respectively, based on the haloarene.
  • Ken Otagiri, Ichizo Miyake, Norio Ishibashi, Hiroshi Fukui, Hidenori K ...
    1983 Volume 56 Issue 4 Pages 1116-1119
    Published: 1983
    Released: June 27, 2006
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    In order to investigate the relationship between bitterness and chemical structure of BPIa, eleven kinds of fragments and analogs of BPIa were synthesized. des–Gly2–BPIa and des-Pro4-BPIa exhibited extremely bitter taste. However, the pentapeptide (Arg–Gly–Pro–Pro–Phe) of BPIa possessed weak bitterness. The bitterness exhibition of BPIa probably derived from the spatial structure of its molecule.
  • Reiji Takeda, Yoshimoto Ohta, Yoshio Hirose
    1983 Volume 56 Issue 4 Pages 1120-1124
    Published: 1983
    Released: June 27, 2006
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    Two new sesquiterpene lactones, (+)-β-frullanolide and (+)-brothenolide, have been isolated from the liverwort Frullania brotheri STEPH. One of them, (+)-brothenolide, has an allergenic property. The absolute structures of these lactones have been established by spectroscopic analysis and chemical transformation.
  • Reiji Takeda, Hideo Naoki, Takashi Iwashita, Kosei Mizukawa, Yoshio Hi ...
    1983 Volume 56 Issue 4 Pages 1125-1132
    Published: 1983
    Released: June 27, 2006
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    Four sesquiterpenoids, striatene, striatol, β-monocyclonerolidol and ptychanolide, were isolated from the liverwort Ptychanthus striatus (LEHM. et. LINDENB.)NEES. Their structures have been established by spectroscopic analysis and chemical transformation. Three of them, striatene, striatol and β-monocyclonerolidol, are interesting in terms of the evolution of the liverwort from the algae.
  • Yasuhiko Sawaki, Hiroshi Inoue, Yoshiro Ogata
    1983 Volume 56 Issue 4 Pages 1133-1138
    Published: 1983
    Released: June 27, 2006
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    4-Phenyl-3-butyn-2-one (1a) was effectively cleaved by alkaline hydrogen peroxide to afford benzoic and acetic acids. The rate ratio for the addition of HOO and HO to 1a resulted in kHOO/kHO=1400, which is comparable to that of benzylideneacetone. The major reaction of the cleavage proceeds via benzoylacetone. As a minor pathway, α-keto oxirene intermediate is formed and rearranges only to α-benzoylpropionate in a different way from the corresponding diketo carbene. α-Keto esters are found to be converted by HOO to α-alkoxy ketones via a novel oxidative substitution of ester group. Methyl phenylpropiolate is oxidized by HOO similarly as 1a. The mechanism is discussed on the basis of oxirene intermediate inconvertible to keto carbene.
  • Yoshiyasu Fukuyama, Iwao Miura, Masamitsu Ochi
    1983 Volume 56 Issue 4 Pages 1139-1142
    Published: 1983
    Released: June 27, 2006
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    Two new bitter limonoids, ohchinolal (1) and ohchinin (2), have been isolated from the fruit of Melia azedarach L. var. japonica Makino, and their structures have been established as 1 and 2 by spectroscopic and chemical methods. The complete assignments of the 1H and 13C NMR data are described.
  • Akira Kasahara, Taeko Izumi, Iwao Shimizu, Tadashi Oikawa, Hiroshi Ume ...
    1983 Volume 56 Issue 4 Pages 1143-1148
    Published: 1983
    Released: June 27, 2006
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    Several ferrocenophanes, in which the two cyclopentadienyl rings are linked by acetylenic and olefinic bonds and aromatic rings, have been synthesized via the titanium-induced reductive coupling of the corresponding formyl compounds. The structures of these ferrocenophane compounds were determined by means of their IR and NMR spectra. The transannular π-electronic interactions between the two chromophores were examined on the basis of the electronic spectra.
  • Toshiaki Miyake, Tsutomu Tsuchiya, Toshiyuki Nishi, Sumio Umezawa
    1983 Volume 56 Issue 4 Pages 1149-1154
    Published: 1983
    Released: June 27, 2006
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    5,4′-Dideoxy-5,4′-diepichlorokanamycin A has been synthesized from 1,3,6′,3″-tetrakis(N-benzyloxycarbonyl)-4″,6″-O-cyclohexylidenekanamycin A by treatment with sulfuryl chloride, followed by deblocking. Similar treatment of 2′,3′,4′,2″-tetra-O-acetyl-1,3,6′,3″-tetrakis(N-benzyloxycarbonyl)-4″,6″-O-cyclohexylidenekanamycin A gave 5-deoxy-5-epichlorokanamycin A. 5,4′-Dideoxykanamycin A and 5-deoxykanamycin A were synthesized from the corresponding 5,4′-diepichloro and 5-epichloro derivatives by reductive dechlorination with sodium metal in liquid ammonia or tributylstannane. The structures of these derivatives were confirmed by the 1H- and 13C-NMR spectroscopy.
  • Masao Tanihara, Tae Hiza, Yukio Imanishi, Toshinobu Higashimura
    1983 Volume 56 Issue 4 Pages 1155-1160
    Published: 1983
    Released: June 27, 2006
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    Cyclic dipeptides having aliphatic side chains, cyclo(L-Val)2, cyclo(L-Val–D-Val), cyclo(L-Leu)2, and cyclo(L-Leu–D-Leu) were synthesized and their conformation in solution was investigated by circular dichroism (CD) and proton nuclear magnetic resonance (1H NMR) spectroscopy. 1H NMR spectra in (CD3)2SO of cyclo(L-Val–D-Val) and cyclo(L-Leu–D-Leu) indicated that the diketopiperazine ring of these trans cyclic dipeptides takes a planar or a chair conformation and the molecules take a center-symmetric conformation. 1H NMR spectra in (CD3)2SO and CD spectra in CH3OH and H2O of cyclo(L-Val)2 and cyclo(L-Leu)2 indicated that the conformation of these cis cyclic dipeptides is planar-axial and flagpole-boat-type respectively. It is suggested that cis cyclic dipeptides having aliphatic side chains take such conformations in polar solvents because of the stabilization by attractive forces between aliphatic side chains.
  • Tatsushi Toyokuni, Seiichiro Ogawa, Tetsuo Suami
    1983 Volume 56 Issue 4 Pages 1161-1170
    Published: 1983
    Released: June 27, 2006
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    The first synthesis has been achieved of the racemates of valienamine and its related, branched-chain unsaturated aminocyclitols. Two synthetic routes for valienamine were developed, one of which is stereoselective and highly efficient. The key transformation is a stereospecific SN2′ attack (apofacial) by an azide ion on the allyl chloride, prepared by regioselective epoxidation of the conjugated diene followed by treatment with hydrochloric acid. Some information is described which is furnished from 13C NMR spectra for the new branched-chain unsaturated aminocyclitols and cyclitols.
  • Shinkiti Koto, Naohiko Morishima, Toyosaku Yoshida, Masaharu Uchino, S ...
    1983 Volume 56 Issue 4 Pages 1171-1175
    Published: 1983
    Released: June 27, 2006
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    The ditritylation of methyl and benzyl α-D-gluco-, -manno-, and -galactopyranosides with trityl chloride in pyridine at 70 °C proceeds in a regioselective manner to give the 2,6-ditrityl ethers of the glucosides, the 3,6-ones of the mannosides, and both 2,6- and 3,6-ones of the galactosides. The rearrangement of the trityl group from O-3 to O-2 of the mannosides at 100 °C causes the selective formation of the 2,6-ditrityl ethers. From the 2,6- and the 3,6-ditrityl ethers, the 3,4- and 2,4-dibenzyl ethers of the hexopyranosides are prepared.
  • Hiroki Kondo, Shingo Uno, Fumio Moriuchi, Junzo Sunamoto, Susumu Ogush ...
    1983 Volume 56 Issue 4 Pages 1176-1180
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    A biotin-containing pentapeptide Boc–Glu–Ala–Met–Bct–Met (1) that corresponds to the coenzyme binding site of E. coli acetyl–CoA carboxylase has been prepared. Peptide 1 as well as free biotin served as a substrate for the carboxylation reaction catalyzed by the biotin carboxylase subunit dimer of E. coli acetyl–CoA carboxylase. The Michaelis constant, Km, and the maximum velocity, Vmax, for 1 were 18 mM and 2.8 μM min−1 (1 M=1 mol dm−3), respectively. The corresponding values for biotin were 214 mM and 28 μM min−1. Thus, the overall reactivity (VmaxKm) of peptide 1 exceeded that of biotin by 20%.
  • Masato Kodaka, Toru Shimizu, Masahiro Hatano
    1983 Volume 56 Issue 4 Pages 1181-1186
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Proton NMR spectra of a cyclic peptide, cyclo-(S-acetarnidoinethyl-L-cysteinyl)-D-leucyl-L-histidyl-(S-acetamidomethyl-L-cysteinyl)-D-leucyl-L-histidyl, were measured and analyzed in order to investigate its conformation and its interaction with Cu(II). A linear peptide, [N-(t-butoxycarbonyl)-S-acetamidomethyl-L-cysteinyl]-D-leucyl-L-histidyl-(S-acetamidomethyl-L-cysteinyl)-D-leucyl-L-histidine methyl ester, was also investigated for comparison. It was strongly suggested that the cyclic hexapeptide forms transannular hydrogen bonds between the cysteine residue peptide bonds and thus two β-turns exist in the D-leucyl-L-histidyl sequences. This finding is particularly noteworthy because the present cyclic peptide has no prolines which are frequently seen in β-turn structures of proteins, naturally occurring peptides or synthetic peptides and because the cyclic peptide we studied is composed of amino acids all bearing the large side chains which seemed likely to prevent β-turn formation due to their steric hindrance. The interactions of the cyclic peptide and the linear peptide with Cu(II) were also studied by observing 1H NMR spectral changes on addition of CuCl2. It was suggested that the imidazolyl groups in the peptides are directly coordinated to Cu(II).
  • Masaaki Ueki, Kozo Shinozaki
    1983 Volume 56 Issue 4 Pages 1187-1191
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The use of the dimethylphosphinothioyl (Mpt) group for the protection of the thiol function in the cysteine side-chain was studied. N,S-Bis(Mpt)-L-cysteine was obtained directly by means of a Schotten-Baumann-type reaction of Mpt–Cl with L-cysteine. The S–Mpt group was stable under acidic conditions, except for HBr in acetic acid, and it could be removed by treatment with AgNO3 or Hg(OAc)2 in an aqueous medium. Glutathione was synthesized by utilizing the new S-protecting group.
  • Hiroto Kidokoro, Yuko Saito, Masaru Sato, Seiji Ebine, Sadao Sato, Tad ...
    1983 Volume 56 Issue 4 Pages 1192-1195
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    3-Substituted 2-bromobiphenylenes were brominated to give benzocyclooctene or 7(8H)-benzocyclooctenone derivatives, but not biphenyl derivatives. The structure of 5,8,10-tribromo-7(8H)-benzocyclooctenone was determined by X-ray diffraction analysis.
  • Masao Okubo, Masatoshi Yoshida, Kotomi Horinouchi, Hiroshi Nishida, Yo ...
    1983 Volume 56 Issue 4 Pages 1196-1202
    Published: 1983
    Released: June 27, 2006
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    The reactions of aryliminodimagnesium reagents (ArN(MgBr)2) with benzylideneacetophenones, quinones, and benzils were examined. Among the product-distributions in the reactions with the enones and the α-diketones, some examples in which p-MeO-substituted substrates gave higher yields of condensation products were obtained. The results are in contrast with the product-distributions in the reaction of ArMgBr with Ar1COAr2 and that of ArN(MgBr)2 with Ar1NO2: p-Cl-Substituted substrates are advantageous for the formation of addition and/or condensation products. These reactions of the two organomagnesium reagents were classified into “coordination controlled” and “electron-transfer controlled” ones on the basis of the combination of electron-donating ability of reagents with the electron-accepting ability of substrates. The classification was illustrated also on the basis of the relative difference of the energy levels of HOMO’s and LUMO’s of the reactants.
  • Tatsuo Oida, Shigeo Tanimoto, Hideyuki Ikehira, Masaya Okano
    1983 Volume 56 Issue 4 Pages 1203-1205
    Published: 1983
    Released: June 27, 2006
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    The cycloaddition of N,N-diethyl-1,3-butadienylamine with some diarylnitrilimines was investigated. 1,3-diaryl-4-vinylpyrazoles, (1,3-diaryl-2-pyrazolin-5-yl)acetaldehydes, 1,3-diaryl-4-(1,3-diaryl-2-pyrazolin-5-yl)pyrazoles, and 1,3-diarylpyrazoles were obtained.
  • Takehiro Abe
    1983 Volume 56 Issue 4 Pages 1206-1213
    Published: 1983
    Released: June 27, 2006
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    The reaction of 3,5-dinitrobenzonitrile in a methanolic solution containing a low sodium-methoxide concentration has been reinvestigated. The final product has been found to be methoxy(3,5-dinitrophenyl)methanimine, which is produced by a catalytic reaction. The reaction mechanism has been presented for the formation of the Meisenheimer complexes and the final product in the reaction system. The rate and thermodynamic stabilities for their formation have been discussed on the basis of the LUMO coefficients of 3,5-dinitrobenzonitrile and from the relative potential energies of their formation respectively, considering also the solvent effects.
  • Kenji Uneyama, Nobu Hasegawa, Hiroyuki Kawafuchi, Sigeru Torii
    1983 Volume 56 Issue 4 Pages 1214-1218
    Published: 1983
    Released: June 27, 2006
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    3-Chloro-2-chloromethyl-4-(4-chlorophenoxy)-1-butene (1) was prepared in 72% yield by electrooxidative double ene-type chlorination of 1-(4-chlorophenoxy)-3-methyl-2-butene. The electrolysis was conducted at room temperature in a two layer solvent system of dichloromethane and water in the presence of acids (HCl, H2SO4, H3PO4, etc). Either 3-chloro-2-methyl-4-(4-chlorophenoxy)-1-butene or 1 was selectively prepared, respectively after 4 or 10 F/mol of electricity were passed using platinum foils as electrodes in an undivided cell. The similar electrolysis of the related 3-methyl-2-butenyl derivatives 2b and 2c provided the ene-type products, 3-chloro-2-methyl-4-benzyloxy-1-butene and 4-chloro-1-ethynyl-1,5-dimethyl-5-hexenyl acetate, respectively. In contrast, 3-methyl-2-butenyl derivatives 2df and 3-methyl-2-butenoic acid afforded a variety of products such as chlorohydrin, vinyl chloride, and sulfoxide other than ene-type products, suggesting that the functional group of R in 2 affects the reaction course. The elongation at 2-chloromethyl group and the subsequent dechlorophenoxylation convert 1 into 2-(phenylsulfonylmethyl)-1,3-butadiene and 2-(phenylthiomethyl)-1,3-butadiene.
  • Akikazu Kakehi, Suketaka Ito, Tsuyoshi Ohizumi, Masayoshi Ito
    1983 Volume 56 Issue 4 Pages 1219-1222
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Alkaline treatment of 2-(aroylmethoxy)-3-(2,2-dicyanovinyl)indolizine derivatives, readily available from the step-by-step reactions of 1-(ethoxycarbonylmethyl)-2-picolinium salts with a base, (ethoxymethylene)malononitrile followed by some phenacyl bromides in ethanol, afforded smoothly the title compounds, 2-aroylfuro[2,3-b]indolizine derivatives, in good yields. These furoindolizines could be also obtained directly from the pyridinium salts without the isolation of intermediate 3-vinylindolizines. Formation mechanisms and some physical properties of these furoindolizines are also discussed.
  • Takahiro Wada, Fumiko Kimura, Ryoichi Yamamoto
    1983 Volume 56 Issue 4 Pages 1223-1226
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    With a view of developing latent heat storage materials, mixtures of pseudo-binary system, CH3CO2Na·3H2O–CO(NH2)2 (sodium acetate trihydrate–urea) were subjected to differentital scanning calorimetry, and the partial phase diagram for ternary system CH3CO2Na–CO(NH2)2–H2O at ambient pressure was constructed. The eutectic mixture, containing 0.6 mass fraction of CH3CO2Na·3H2O and 0.4 mass fraction of CO(NH2)2, melts congruently at 31.5 °C with a heat of fusion of 226 J/g, which is larger than the heat of fusion of CaCl2·6H2O, 180 Jg. Thus, mixtures of system CH3CO2Na·3H2O–CO(NH2)2 are promising for solar energy storage.
  • H. A. El-Sherief, A. E. Abdel-Rahman, G. M. El-Naggar, A. M. Mahmoud
    1983 Volume 56 Issue 4 Pages 1227-1230
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    2-Hydrazino-3-phenyl-4(3H)-quinazolinone (1) underwent ring closure with aliphatic acid, aldehydes, and carbon disulfide to 1-alkyl-, 1-aryl-, and 1-mercapto-4-phenyl-1,2,4-triazolo[4,3-a]quinazolin-5(4H)-ones (7) for instance. The 1-alkylthio-3-phenyl-1,2,4-triazolo[4,3-a]quinazolin-5(4H)-ones were readily obtained from 7 and alkyl halides. Reaction of 1 with ethyl acetoacetate gave the corresponding hydrazone which was readily converted into 2-(3-methyl-5-oxo-2-pyrazolin-1-yl)-3-phenyl-4(3H)-quinazolinone.
  • Isao Sanemasa, Toyohisa Kobayashi, Toshio Deguchi, Hideo Nagai
    1983 Volume 56 Issue 4 Pages 1231-1232
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The equilibrium constants, Kd, of mercury(I) disproportionation have been measured by passing air containing mercury(0) vapor through mercury(I) solutions. At 15, 20, 25, 30, and 35 °C, the values of Kd were 1.3, 2.9, 5.2, 8.8, and 11×10−9 mol dm−3 respectively at μ=0.1 (NaClO4).
  • Mikio Hoshino, Shiro Konishi, Masao Nakajima, Masashi Imamura
    1983 Volume 56 Issue 4 Pages 1233-1234
    Published: 1983
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    ESR spectra of γ-irradiated glassy solutions of cobalt(II) chelates of N,N′-bis(1-methyl-3-oxobutylidene)ethylenediamine (acacen) having two NH3 in the axial positions at 77 K show the formation of a metastable cobalt(II) complex in which two NH3 are forced to be confined in the axial positions.
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