Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 1
Showing 1-50 articles out of 57 articles from the selected issue
  • Seizo Misumi, Toshiyuki Isobe, Kuniyoshi Sugiyama
    1974 Volume 47 Issue 1 Pages 1-3
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The single crystal ESR spectra of some five-coordinate adducts of copper(II)-doped zinc(II) β-diketonate complexes [Cu/Zn(acac)2H2O], [Cu/Zn(acac)2γ-pic], [Cu/Zn(bzac)2MeOH], and [Cu/Zn(bzac)2py] (acac=acetylacetone anion, bzac=benzoylacetone anion, py=pyridine, γ-pic=γ-picoline, MeOH=methanol) were measured at room temperature. The principal values of the g tensor and A tensor of 63Cu were calculated. The single crystal g-values of all the adducts suggested a dx2y2 ground state for the approximately square-based pyramidal structure, and were found to be consistent with crystallographic data. In the single crystals of [Cu/Zn(acac)2H2O] and [Cu/Zn(bzac)2py], two magnetic centers were determined, this being the first time for them to have been found by ESR study.
  • Keiichiro Hatano, Norio Shimamoto, Takashi Katsu, Yuzaburo Fujita
    1974 Volume 47 Issue 1 Pages 4-8
    Published: 1974
    Released: March 27, 2006
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    The photochemical decomposition of methylamines adsorbed on the surface of the porous Vycor glass was studied at 77 K by the ESR method, and the ESR spectra of the methylamino radicals, CH3NH, CH3ND, CD3NH, CD3ND, CH2DNH, and CH2DND, were observed as primary radicals from variously-deuterated methylamines upon irradiation with the light of a low-pressure mercury lamp. This result shows that the primary process is preferentially a rupture of the N–H or N–D bond of methylamine. These spectra were characterized by an apparent quenching of the N-hyperfine splitting resulting from large hyperfine anisotropy, and by nearly isotropic proton hyperfine splittings in both methyl and amino groups. The hyperfine splitting constants of the N, H, and D nuclei of each radical were determined, and consequently a D-substitution effect on the β-proton hf splitting in the methyl group was found. The characteristics of the ESR spectra were discussed in relation to the adsorbed state of the methylamino radical on the porous Vycor glass surface.
  • Shigeo Koizumi, Yoshio Matsunaga
    1974 Volume 47 Issue 1 Pages 9-13
    Published: 1974
    Released: March 27, 2006
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    The phase relations in the phenanthrene/anthracene–picric acid system have been determined by calorimetry and X-ray diffraction. Four series of solid solutions occur in this system: the terminal solid solutions P and A, which are based on the parent picrate lattices, and the I and II solutions, which are based on the incongruentlymelting ternary compounds. A eutectic is observed at about 47 mol% anthracene and at 124 °C. Enantiotropic transitions appear at about 76, 103, and 120 °C in the I solid solution and at about 80, 103, and 120 °C in the II solid solution. The Gibbs energy of formation from the solid component compounds has been estimated as −2.04, −1.67, −1.21, and −0.68 kcal/mol for the stable forms at the room temperature of the phenanthrene picrate, the I solid solution (at 34.58 mol% anthracene), the II solid solution (at 58.96 mol%), and the anthracene picrate respectively. The two transitions in the phenanthrene picrate have been shown to be easily detectable by recording the electrical resistivity as a function of the temperature.
  • Kazuo Shimokoshi
    1974 Volume 47 Issue 1 Pages 14-17
    Published: 1974
    Released: March 27, 2006
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    The electron spin resonance spectra have been measured for the radical formed by the photolysis of methylene iodide adsorbed on silica gel. The spectra were anisotropic and were attributed to the radical of the ≡Si–O–CH2form by an analysis of the hyperfine splittings due to two protons, taking into consideration the photochemical processes on the silica gel surface. From a line-shape analysis of the observed spectrum, the following anisotropic hyperfine interaction parameters for the protons and g-value have been obtained:
    A_//=28.5±0.5G, A_⊥=18.8 ±0.5G, g=2.0030±0.0005.
    It has been concluded from the analysis of the spectra that the hyperfine structure observed with axially-symmetric tensors is a result of the fast internal rotation of the methylene group of the radical.
  • Yoji Tokuma, Shigetaka Koda, Toshio Miyoshi, Yukiyoshi Morimoto
    1974 Volume 47 Issue 1 Pages 18-23
    Published: 1974
    Released: March 27, 2006
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    The molecular structure of a new antibiotic, Bicyclomycin (C12H18O7N2), has been elucidated by X-ray diffraction analysis. Bicyclomycin crystallizes from aqueous solution in two forms, an orthorhombic and a monoclinic systems. The crystal data for the former are a=11.72, b=12.72, c=8.80 Å and the space group P212121, while those for the latter are a=10.27, b=10.91, c=6.67 Å, β=101.4°, and the space group P21 The crystal structure of the former was solved by the direct method and refined by least-squares method to a final R factor of 0.07 for 1623 reflections. The established structure is
    (Remark: Graphics omitted.)
    The diketopiperazine ring is folded into a boat form. The conformations of the side chain are all gauche or nearly so. All the oxygen and nitrogen atoms participate in two intramolecular and four intermolecular hydrogen bonds.
  • Sanyo Hamai, Hiroshi Kokubun
    1974 Volume 47 Issue 1 Pages 24-27
    Published: 1974
    Released: March 27, 2006
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    Rotaional depolarization of 1-anthrol fluorescence was studied in liquid paraffin. The molecular volume of 1-anthrol becomes large when it forms a hydrogen bonded complex. The molecular volume of the complex depends on the concentration of acceptor as well as the kind of acceptor. The molecular volume obtained by extrapolation to nil acceptor concentration increases with increasing size of acceptor molecule and is appreciably larger for amines than for ethers. The emitting species in the case of amines is 1-anthrolate ion pair whose strong dipolar nature may cause further interaction with excess amine molecules. It is probable that more than one molecule of amine participate in the rotating unit, leading to a large molecular volume. The rotational relaxation time was evaluated and found to depend on acceptor concentration. Two competitive effects occur by the increase in acceptor concentration, one shortening the relaxation time because of reduction of viscosity, and the other lengthening it because of molecular volume enlargement.
  • Masaru Shiotani, Claude Chachaty
    1974 Volume 47 Issue 1 Pages 28-30
    Published: 1974
    Released: March 27, 2006
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    Experiments were carried out in order to elucidate the formation mechanism of C2H5 · radicals formed by the UV irradiation (250<λ<350 nm) of CH3\dotCHOH radicals. The kinetics of the formation of the C2H5· radical was examined by means of ESR in neutral, acidic, and alkaline ethanol glasses at 77 K. The initial rate of the formation of C2H5· was nearly independent of the concentration of added acid (H2SO4), but it decreased sharply with that of added NaOH. Moreover, the limiting yield of C2H5· decreased with the concentrations of both the acid and the base. Our experimental results suggest that the C2H5· radicals are formed by this reaction:
    C_2H_5OH_2^++e^-→C_2H_5·+H_2O
    The C2H5OH2+ ion and the electron result from the photoionization of CH3\dotCHOH radicals according to these reactions:
    & CH_3\dotCHOH\xrightarrowhv(CH_3CHOH)^++e^-
    & (CH_3CHOH)^++C_2H_5OH→CH_3CHO+C_2H_5OH_2^+
  • Hideo Yamazaki, Koichi Oka, Masabumi Sato, Shoji Shida
    1974 Volume 47 Issue 1 Pages 31-33
    Published: 1974
    Released: March 27, 2006
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    The radiophoto-luminescence (RPL) from γ-irradiated hydrocarbon glasses, i.e., 3-methylhexane, methylcyclohexane, and ethylcyclohexane, containing small amounts of various aromatics (1,3,5-trimethylbenzene, biphenyl, naphthalene, and 1,4-diazine) is investigated at 77 K by infrared-light irradiation. The spectra of the R PL consist of the fluorescence and phosphorescence of the guest aromatic molecule, and the ratio of the phosphorescence to the fluorescence intensity is larger than that in the photoexcitation, indicating the existence of another path to the triplet state. The RPL is quenched by the addition of N2O, but it is not much affected by that of NH3. A possible mechanism for the RPL is considered, and its analysis is given.
  • Akira Igawa, Hideo Fukutome
    1974 Volume 47 Issue 1 Pages 34-39
    Published: 1974
    Released: March 27, 2006
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    Effects of the excess charges at the donor and acceptor atoms on the properties of the hydrogen bond were studied in a simple three-center four-electron model for a hydrogen bond system using CNDO/2 type molecular orbital calculation. It was shown that three types of hydrogen bonds, normal, proton transferred and abnormal, are possible according to the value of the excess charges. The dependence of the hydrogen bond distance, proton equilibrium distance, frequency of proton stretching vibration and hydrogen bond energy on the excess charges were calculated for the normal type hydrogen bond. The correlations between these quantities obtained by changing the amounts of the excess charges are in good agreement with the experimental results, suggesting that the excess charges at the donor and acceptor atoms primarily determine the correlation. The potential of proton movement at the equilibrium hydrogen bond distance is shown not to have double minima for any value of the excess charges, indicating that the excess charges are not essential for producing a double well potential.
  • Masao Hashimoto, Taro Isobe
    1974 Volume 47 Issue 1 Pages 40-44
    Published: 1974
    Released: March 27, 2006
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    The assumption of pairwise additivity of the intermolecular forces was examined within a CNDO/2-Clementi approximation. It was found that the deviation from the pairwise additivity, defined as the difference between the three-body interaction and the sum of the two-body interaction energies in the system of three neighboring molecules in a crystal, was small enough to be neglected as compared with the lattice energy. The CNDO/2 -Glementi method, in which the overlap integrals are calculated by using the Clementi AO’s, was found to be more useful than the usual CNDO/2 method, in which the overlap integrals are calculated by means of Slater AO’s. The discrepancy in the calculated interaction energies from the experimental ones in the form of the heat of sublimation was found to be quite large for CO. This discrepancy becomes small, though, if the centers of the molecules are displaced away from the origin and along the nonintersecting threefold axes of the unit cell; the crystal structure belongs not to the Pa3 space group, but to the P213 space group. From a comparison of the CNDO/2-Clementi results and the results of the exp-6 potential superimposed on the quadrupole-quadrupole interaction potential, it was found that the former is superior to the latter in anticipating the conformation of the (CO2)2 dimer.
  • Yashige Kotake, Keiji Kuwata
    1974 Volume 47 Issue 1 Pages 45-49
    Published: 1974
    Released: March 27, 2006
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    The ENDOR intensities of several semiquinone anion radicals were measured at various temperatures. The optimum temperature for the ENDOR intensity of protons in a radical was interpreted on the basis of their characteristic ways of relaxation. The electron nuclear dipolar (END) mechanism could be applied very well in most cases. However, in the case of protons whose END terms are very small this interaction might not explain the optimum temperature. Possible substitute mechanisms were discussed.
  • Tooru Yoshida, Shigemasa sawada
    1974 Volume 47 Issue 1 Pages 50-53
    Published: 1974
    Released: March 27, 2006
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    The binding energies of N(1s) in ethylenediaminetetraacetic acid (EDTA) and its related compounds were measured by means of a photoelectron spectrometer, and the molecular structures of EDTA were discussed. Two kinds of peaks were observed in the N(1s) spectra of EDTA and its related compounds, with binding energies of about 401 and 399 eV. In EDTA-4H, the heights of the two peaks were almost equal, while in its sodium salts the peak height with the higher binding energy decreased as the number of carboxylate groups in the molecule increased. In EDTA-4Na, only a single peak with a low binding energy was observed. In EDTP-4H and GEDTA-4H, the spectra showed two peaks with different heights. The binding energy values of the main peaks of simple amino acids, such as glycine and alanine, were about 401 eV. From the above results, it can be deduced that there are two kinds of N atoms, =N+H– and =N– types, in an EDTA molecule.
  • Masayuki Katsumoto, Kazuo Fueki, Takashi Mukaibo
    1974 Volume 47 Issue 1 Pages 54-56
    Published: 1974
    Released: March 27, 2006
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    In order to elucidate the mechanism of the redox reaction at the gas-solid interface, the isotopic exchange between H2S and D2 on Ag and Ag2S has been studied in the temperature range from 410 to 521°C. The transfer of isotopic species between “hydrogen sulfide” 1) and “hydrogen” 1) was found to proceed by means of the reaction:
    “H_2S”^1)\oversetk_i\undersetk_i’\ ightleftarrows“H_2”^1)+S(ad)
    on both surfaces. From the analysis of the kinetic data, the redox reaction rate constants, ki and ki′, were determined as a function of the sulfur activity. It was found that ki is inversely proportional to the sulfur activity, whereas ki′ is independent of it. The mechanism of the reaction on the surfaces of Ag and Ag2S is discussed.
  • Takasuke Matsuo, Masaharu Oguni, Hiroshi Suga, S\^{y}uzô Seki, J ...
    1974 Volume 47 Issue 1 Pages 57-66
    Published: 1974
    Released: March 27, 2006
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    The heat capacity of SnCl2·2H2O and SnCl2·2D2O crystals, substances with layer structure, was measured from 13 to 300 K. Anomalies due to ordering of the hydrogen (deuterium) position were observed at TC(H2O)=217.94 K and at Tc(D2O)=234.47±0.05 K. The total entropy change of the transition was estimated to be 4.6 J K−1 mol−1 for both compounds. An exact calculation of the high temperature entropy based on the two-dimensional lattice model gave 3.13 J K−1 mol−1. The critical indices α± of the divergent heat capacity anomalies are as follows: α+(H2O)=0.53, αH2O)=0.48, α+(D2O)=0.57, α(D2O)=0.54. Another heat capacity anomaly was found at 140–160 K where the heat capacity values depended on the thermal history of the specimen. The enthalpy relaxation observed at the temperature region was analysed by use of the first-order rate equation, giving the activation enthalpies ΔHa(H2O)=49.9 kJ mol−1 and ΔHa(D2O)=49.8 kJ mol−1. The concept of long-range-ordered glassy state was introduced for description of the non-equilibrium state of the present substances below 140 K. A general consideration of the relation between molecular relaxation and phase change in terms of the Deborah number is presented.
  • Mitsuo Kitano, Kozo Kuchitsu
    1974 Volume 47 Issue 1 Pages 67-72
    Published: 1974
    Released: March 27, 2006
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    The structure of formamide HCONH2 has been determined by gas electron diffraction. The rotational constants determined in previous microwave studies have also been used for determining the hydrogen parameters. From a joint least-squares analysis of the diffraction intensity and the rotational constants, where the out-of-plane vibrations are treated as finite-amplitude motions in the corrections for vibrational effects, the following rg bond distances and rz angles have been derived: C–N=1.368±0.003 Å, C=O=1.212±0.003 Å, ∠N–C=O=125.0±0.4°, N–H(average)=1.027±0.006Å, C–H=1.125±0.012 Å, ∠C–N–H(cis to C=O)=118.7±1.0°C, and ∠C–N–H (trans to C=O)=119.7±1.0°, where the uncertainties represent estimated limits of experimental error. The C–N bond is about 0.07 Å longer, whereas the C=O bond is about 0.04 Å shorter, in the free molecule than in the crystal studied by X-ray diffraction. The C–N and C=O bonds are about 0.01 Å or more shorter, and the N–C=O angle is about 3°C larger than the corresponding parameters in acetamide and N-methylacetamide.
  • Keietsu Tamagake, Masamichi Tsuboi
    1974 Volume 47 Issue 1 Pages 73-77
    Published: 1974
    Released: March 27, 2006
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    Infrared absorption spectra of methyl-d-amine and methyl-d-amine-d2 have been observed in their gaseous states. For each of seven vibrations of the former and seven vibrations of the latter, two Q-branch peaks are observed assignable to trans and gauche forms of the molecule. In the microwave absorption spectrum of methyl-d-amine 60 lines assignable to the trans form (whose rotational constants are A=86085, B=20546, and C=20475 MHz) and 140 lines assignable to the gauche form (A=86512, B=21243, and C=19911 MHz) are found. Every trans line shows an inversion doubling which is considered to reach an observable amount only through a trans-gauche mixing of the vibration-rotation wavefunctions. This trans-gauche mixing should in turn depend upon the energy difference ΔETG between the ground vibration-rotation levels of the trans and gauche forms. On the basis of the observed amount of the inversion splitting, ΔETG has been determined to be 6.7±0.4 cm−1. The ΔETG value has then been refined by observing an accidental degeneracy of the trans and gauche energy levels, so that ΔETG=7.06±0.03 cm−1.
  • Katsunosuke Machida, Bak-Kwang Kim, Yutaka Saito, Kyoko Igarashi, Toyo ...
    1974 Volume 47 Issue 1 Pages 78-83
    Published: 1974
    Released: March 27, 2006
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    Resonance Raman spectra between 1800 and 1000 cm−1 of methyl orange and a few other p-aminoazobenzene-type acid-base indicators have been investigated at various pH, and a marked spectral change has been observed on the transformation between the acid and the base forms of these indicators. The characteristic Raman frequencies have been assigned by referring to the spectra of related compounds and the deuteration effects. The spectra of the acid form are well elucidated on the basis of the quinoid-type structure.
  • Yoshinori Koga, Hiroaki Takahashi, Keniti Higasi
    1974 Volume 47 Issue 1 Pages 84-87
    Published: 1974
    Released: March 27, 2006
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    Dielectric constants and losses at the microwave frequency of 96.52 GHz have been measured at 25°C for methyl, ethyl, n-butyl, isobutyl, s-butyl, t-butyl, n-amyl, isoamyl, n-hexyl, and n-octyl acetates in benzene solutions. Static dielectric constants, refractive indices and densities have also been measured. The effective mean relaxation times of normal alkyl acetates increase with increasing chain length of the alkyl radical, eventually approaching a steady value. The distribution parameters α of all these molecules seem to have appreciable values which may be due to various segment orientations by internal rotation.
  • Kozo Inuzuka, Ralph S. Becker
    1974 Volume 47 Issue 1 Pages 88-91
    Published: 1974
    Released: March 27, 2006
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    The lower n* and π,π* excited state energies of four tomj-polyenecarbaldehydes, acrolein, 2,4-pentadienal, 2,4,6-heptatrienal, and 2,4,6,8-nonatetraenal, were calculated within the framework of the conventional P-P-P SGF-MO-CI method and then discussed. Also, the oscillator strength for the π,π* transition was obtained in terms of the dipole length and the dipole velocity.
  • Tetsuo Morimoto, Kunimitsu Morishige
    1974 Volume 47 Issue 1 Pages 92-94
    Published: 1974
    Released: March 27, 2006
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    The adsorption of carbon dioxide has been measured at 25°C on zinc oxide surfaces with different amounts of preadsorbed carbon dioxide. As a result, it has been found that carbon dioxide molecules are chemisorbed more weakly to zinc oxide surfaces than water; the desorbability of carbon dioxide is almost complete upon evacuation at temperatures higher than 300 °C, whereas upon evacuation at 25°C 80% of the carbon dioxide remains on the surface. Also, the adsorption isotherms of carbon dioxide have been obtained at 25°C on differentlyhydroxylated surfaces of zinc oxide. On such surfaces, the adsorption amount of carbon dioxide decreases linearly with an increase in the amount of surface hydroxyl groups. This suggests that most of the carbon dioxide is adsorbed strongly on the vacant sites formed by dehydroxylation, and not on the surface hydroxyl groups.
  • Minoru Toyoda, Teiichiro Ogawa, Nobuhiko Ishibashi
    1974 Volume 47 Issue 1 Pages 95-98
    Published: 1974
    Released: March 27, 2006
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    The emission spectra in the 200–600 nm region produced by the controlled electron impact method were investigated in the vapor phase on hydrogen sulfide, carbon disulfide, methanethiol, and ethanethiol at low pressures. The photoemissions were observed and assigned for an excited parent molecule, molecular ions, and fragments, such as CS2, CS2+, H2S+, H, CH, CS, and HS+. The intensities of the photoemission of most of the species were found to increase linearly with both the electron beam current and the gas pressure, and these species were concluded to be produced in some one-electron unimolecular processes.
  • Yoichi Iida
    1974 Volume 47 Issue 1 Pages 99-103
    Published: 1974
    Released: March 27, 2006
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    The infrared spectra (400–4000 cm−1) of neutral 2,5-dibromo-3,6-dichloro-1,4-benzoquinone and its anion radical were measured in order to observe the appreciable frequency differences between their corresponding bands. The vibrational assignments were made and the simple Urey-Bradley force fields were determined for both the neutral 2,5-dibromo-3,6-dichloro-1,4-benzoquinone and its anion radical. The differences in the molecular and electronic structures between these two molecules were investigated on the basis of these experimental and theoretical results. The half-occupied molecular orbital of the anion radical was found to belong to the bg irreducible representation.
  • Isamu Kawasuji, Shin Suzuki
    1974 Volume 47 Issue 1 Pages 104-108
    Published: 1974
    Released: March 27, 2006
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    Cr(II) has been used for reducing protactinium in microquantities to the tetravalent state and for protecting it from re-oxidation. However, the effect of Cr(II) on the extraction behavior of Pa(IV) has not been taken into account by all of the previous investigators. On the basis of the above facts, the influence of Cr(II) on the extraction of Pa(IV) was studied by using such extractants as BPHA, TTA, and TOA. In every case, the distribution ratio of Pa(IV) decreased with an increase in the concentration of Cr(II) in the aqueous phase. One of the most reliable explanations for the phenomena is the possibility that a multi-nuclear complex between Pa(IV) and Cr(II) or Cr(III) is formed. However, the effect of Cr(II) on the absorption spectra of Pa(IV) could not be found, and many more experiments will be necessary to explain the effect of Cr(II) on the extraction behavior of Pa(IV).
  • Yoshihiro Sasaki, Tsunenobu Shigematsu
    1974 Volume 47 Issue 1 Pages 109-111
    Published: 1974
    Released: March 27, 2006
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    Bis[2-(2-pyridyl)imidazole]iron(II) complexes, Fe(PI)2X2 (X=C1, Br, NCS, N3, and CN), were prepared and characterized on the basis of their infrared and Mössbauer spectra and their magnetic data. In Fe(PI)2(NCS)2 the NCS groups are N-bonded and are in a cis position. Fe(PI)2(CN)2H2O also has a cis configuration about the CN ligands. Except for Fe(PI)2(CN)2H2O, the magnetic moments of the complexes lie in the 4.94–5.27 B.M. range. Fe(PI)2(CN)2H2O is a diamagnetic compound.
  • Akira Yokoyama, Hiroji Aiba, Hisashi Tanaka
    1974 Volume 47 Issue 1 Pages 112-117
    Published: 1974
    Released: March 27, 2006
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    Glycyl-L-histidine, L-histidylglycine, glycylglycyl-L-histidine, glycyl-L-histidylglycine, and L-histidylglycylglycine were synthesized by the carbobenzoxy azide procedure. The acid dissociation constants of these peptides and their related compounds were determined from the potentiometric titration curves of 0.01 M solutions at 21°C. The dissociation of one ionization group is greatly influenced by the charge on the other groups. The formation constants of metal complexes of L-histidylglycine, L-histidylglycylglycine, and L-3-benzylhistidine were calculated by the least-squares method from the titration curves of the solution containing the ligand (0.01 M) and metal in the molar ratio 2: 1, assuming the formation of 1: 1 and 2: 1 normal complexes (ML+ and ML2), and the results were compared with those of L-histidine-metal complexes. For any metal ion, the order of formation constants was found to be histidine≈3-benzylhistidine>histidylglycine>histidylglycylglycine, in agreement with that of the basicity of amino and imidazole groups. In these metal complexes, metal ion is considered to bind through amino, imidazole, and carboxyl or carbonyl groups of histidine residue.
  • Takejiro Takamatsu
    1974 Volume 47 Issue 1 Pages 118-126
    Published: 1974
    Released: March 27, 2006
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    Tris(1,10-phenanthroline)Ru(II) was extracted into various organic solvents with several anions, such as the perchlorate ion, the iodide ion, or the thiocyanate ion. The association constants of ion-pairs were successfully determined by analysis of the extraction curves in the solvents with low polarities. It was found that the ion-pairs were extracted mainly as the associated form and that only the first-step dissociation could slightly occur (<10−7) in such solvents; furthermore, the degree of association was considerable even in water. Therefore, the distribution ratio of the complex cation must be governed by both the hydration energy of the counter anion and the solubility parameter of the extraction solvent rather than its dielectric property. An abnormal decrease in the distribution ratio was observed when the tetraphenylborate ion was used as the counter anion. This phenomenon can be explained clearly in terms of the hydrotropism which was often encountered in the solution of an electrolyte with a large ion.
  • Seizo Misumi, Makoto Aihara, Setsuko Kinoshita
    1974 Volume 47 Issue 1 Pages 127-130
    Published: 1974
    Released: March 27, 2006
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    The formation of thiocyanate complexes of cadmium (II), copper(II), cobalt(II), and iron(II) has been studied in acetonitrile by polarographic, conductometric, and spectrophotometric methods. The values of overall stability constants were found to be; logβ4=19.7 for [Cd(SCN)4]2−, logβ2=7.6 for [Cu(SCN)2] and logβ4=15.5 for [Co(NCS)4]2−. The reaction between copper(II) species and mercury metal was investigated and the electrode reaction was estimated. Kinetic current for cobalt(II)-thiocyanate complex was observed and the rate constant for the dissociation of the complex was obtained. The rate constant of reduction in the iron(II)-thiocyanate system was determined to be 1.9×10−3 cm/s by cyclic voltammetry.
  • Akira Nagasawa, Kazuo Saito
    1974 Volume 47 Issue 1 Pages 131-135
    Published: 1974
    Released: March 27, 2006
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    The tris(acetylacetonato)germanium(IV) has been resolved by the crystallization of its hydrogen-R,R-di-benzoyltartrate in a mixture of acetonitrile, ethanol, and water. The racemization kinetics of perchlorate of the Δ-enantiomer has been studied in 1,1,2,2-tetrachloroethane (TCE), nitromethane, acetonitrile (AN), and N,N-dimethylformamide, the activation enthalpies (ΔH\ eweq/kacl· mol−1) and the activation entropies (ΔS\ eweq/cal· K −1 mol−1) being 27.9, 26.6, 24.3, and 23.3, and +3.7, −1.1, −4.4, and −5.0, respectively. The ligand isotopic exchange is much slower than the racemization under similar conditions. Consideration of acid (in TCE) and base (in AN) catalysis, influence of ionic strength and solvent effect suggests an intra-molecular mechanism via an intermediate in which one of the ligands is in unidentate state.
  • Hiroji Aiba, Akira Yokoyama, Hisashi Tanaka
    1974 Volume 47 Issue 1 Pages 136-142
    Published: 1974
    Released: March 27, 2006
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    Equilibrium constants were determined in the complex formations of L-histidylgylcine (HG) and L-histidylglycylglycine (HGG) with copper(II) ion in aqueous solution by potentiometric titration, and the structures of the complexes were discussed based on the observations in the titration and infrared and electronic absorption spectra. In the acid region, a cationic chelate, in which copper(II) binds to nitrogen atoms of amino and imidazole groups, is formed. In the neutral region, deprotonation of the peptide amide group occurs to form a dimer, in which four coordination positions of copper(II) are occupied by nitrogen atoms of deprotonated amide and amino groups and an oxygen atom of carboxyl or carbonyl group in one molecule and a nitrogen atom of imidazole group of another molecule. In HGG–Cu(II) system, the dimer is decomposed in the alkaline region with further deprotonation of the second peptide amide group to form an anionic chelate as in the case of the glycylglycylglycine–Cu(II) complex.
  • Sakae Uemura, Akira Onoe, Masaya Okano
    1974 Volume 47 Issue 1 Pages 143-146
    Published: 1974
    Released: March 27, 2006
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    By the reaction of olefins with equimolar mixtures of SbCl5 and Br2 or LiBr, and of SbCl3 and Br2, in carbon tetrachloride, various bromochloroalkanes were obtained in good yields. The mixtures of certain metal chlorides of the Lewis acid type (e.g., FeCl3, SnCl4, and TiCl4) and Br2 could also be used as chlorobrominating agents, but these mixtures were found to be inferior to the SbCl5–Br2 mixture in product selectivities.
  • Sakae Uemura, Akira Onoe, Masaya Okano
    1974 Volume 47 Issue 1 Pages 147-150
    Published: 1974
    Released: March 27, 2006
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    Equimolar mixtures of SbCl5 and Br2 or I2 were found to be elegant reagents for the halogenation of certain aromatic substrates. In carbon tetrachloride, halogenobenzenes afforded the corresponding bromo- and iododerivatives with high para-selectivities (more than 95%) in good yields. The bromination of aromatic compounds with deactivating groups, such as ethyl benzoate and nitrobenzene, was simply achieved in 1,2-dichloroethane. Based on competitive halogenation data, the attack of BrCl or ICl (both formed in situ) on aromatics has been suggested.
  • Yasuhiko Seto, Kazuhira Torii, K\={o}ichi Bori, Kenichiro Inabata, Shi ...
    1974 Volume 47 Issue 1 Pages 151-155
    Published: 1974
    Released: March 27, 2006
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    In order to obtain an optically-active β-(2-thiazolyl)-β-alanine, N-acyl-L-aspartic α-thionamide-β-methyl ester was condensed with diethyl bromoacetal, but the amino acid thus obtained showed no perceptible optical activity. The racemic amino acid, however, could be resolved into its antipodes by treating its phthalyl derivative with brucine. Thus, the (+)-amino acid, a constituent of bottromycin, was isolated in a pure state; it was determined to belong to the L-series by examining its optical behavior. This amino acid was proved to racemize easily under the conditions of the acid hydrolysis of bottromycin.
  • Takao Hara, Yasukazu Ohkatsu, Tetsuo Osa
    1974 Volume 47 Issue 1 Pages 156-159
    Published: 1974
    Released: March 27, 2006
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    The kinetics of the liquid-phase autoxidation of acrolein were studied using di-t-butyl diperoxyoxalate as an initiator. The ratios of the rate constants for the propagation vs the termination steps (k3k6−1⁄2 and k2k4−1⁄2) in the autoxidation mechanism were determined from the empirical rate equation thus obtained. The lower reactivity of acrolein was explained by comparing the ratios with those of saturated aldehydes.
  • Masajiro Kawana, Sakae Emoto
    1974 Volume 47 Issue 1 Pages 160-165
    Published: 1974
    Released: March 27, 2006
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    The styrene-2% divinylbenzene copolymer containing 1,2-O-cyclohexylidene-5-O-trityl-α-D- or -L-xylofuranose (D- or L-3a) was prepared. Asymmetric Grignard additions to benzoylformate (3b) and pyruvate (3c) were carried out using these polymers as chiral ester-components. Enantiomers of α-hydroxy acids, such as atrolactic acid (4) and 2-hydroxy-2-phenyl-2-(p-tolyl)acetic acid (5), were obtained in relatively good synthetic and optical yields, depending on the use of either D- or L-3a. The optical yields of 4 for the polymer were higher than those for a low-molecular-weight compound, 1,2-O-cyclohexylidene-5-O-trityl-α-D-xylofuranose (8a). It was shown that the polymer could be used repeatedly.
  • Shigeru Oae, Osamu Yamada, Tetsuya Maeda
    1974 Volume 47 Issue 1 Pages 166-169
    Published: 1974
    Released: March 27, 2006
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    When N,N-dimethylaniline was allowed to react with p-toluenesulfnic acid, unusual demethylation products, i.e., p-(N,N-dimethylamino)benzyl p-tolyl sulfone and p-(N-methylamino)benzyl p-toly sulfone were obtained. N-p-Toluenesulfonylmethyl-N-methylaniline was proposed to be a discrete intermediate, which undergoes intermolecular rearrangement in the presence of acid eventually to afford the above products. Similar results were obtained for the reaction of N-methylaniline with p-toluenesulfinic acid.
  • Noboru Yamazaki, Fukuji Higashi
    1974 Volume 47 Issue 1 Pages 170-173
    Published: 1974
    Released: March 27, 2006
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    The oxidation of phosphorous acid and its esters with an equimolar amount of mercurous chloride and half an equimolar amount of mercuric chloride was carried out in tertiary amines. On the treatment of the oxidation mixture with carboxylic acids, amines, and alcohols, followed by aminolysis, alcoholysis, or acidolysis, the corresponding carboxylic amides and esters were obtained in good yields, together with a nearly quantitative yield of metallic mercury. The yield was affected by the tertiary amines, the alkyl groups in the dialkyl phosphites, and the steric effect of the carboxylic acids. The reaction was proposed to proceed through the activation of carboxylic acids, amines, and alcohols via the N-phosphonium salts prepared by the oxidation. The electron-transfer processes involved in the oxidation were discussed on the basis of the yield of the amides obtained. These procedures were successfully extended to the preparation of peptides and active esters of amino acids, using diphenyl phosphite in pyridine.
  • Yoshiro Ogata, Kazuo Nate, Mitsuji Yamashita
    1974 Volume 47 Issue 1 Pages 174-178
    Published: 1974
    Released: March 27, 2006
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    Autoxidation of 2-substituted anthranols to the corresponding anthraquinones in alkaline buffered aqueous dioxane (2:1 in vol) has been studied kinetically at 35 °C by means of the manometric method. The relative rate constants for the autoxidation of anthranyl oxide ions have been evaluated, in which dissociation of anthrones is taken into account. Application of substituent effect on the one-electron transfer to the oxide ion to the Hammett equation gives an average ρ-value of −1.5, which was little influenced by pH of the solution.
  • Shigeru Oae, Masaru Moriyama, Tatsuo Numata, Norio Kunieda
    1974 Volume 47 Issue 1 Pages 179-182
    Published: 1974
    Released: March 27, 2006
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    Mechanistic investigations of the concurrent oxygen exchange and racemization reactions of 18O-labeled and optically active n-butyl methyl sulfoxide in sulfuric acid of various concentrations have been carried out. The kinetic data were analyzed in the light of kex/krac values, activation parameters, correlations between the rates and acidity functions, etc. The results seem to suggest that the reaction proceeds through an A-1-like route to afford a cation radical (–\overset+·S–) or a dication (–\overset++S–) intermediate, followed by a fast nucleophilic attack of water to give the starting sulfoxide.
  • Akira Kasahara, Taeko Izumi, Toru Takeda, Hayao Imamura
    1974 Volume 47 Issue 1 Pages 183-185
    Published: 1974
    Released: March 27, 2006
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    In the presence of lithium chloropalladite, 2-vinylpyridine reacted with phenylmercuric chloride to give di-μ-chloro-bis[2-phenyl-2-(α-pyridyl)ethyl]dipalladium (II). Similar complexes were obtained from p-toy-, p-anisyl-, or m-nitrophenylmercuric chloride. The σ-bonded structures of these complexes have been confirmed by a study of their absorption and of the NMR spectra.
  • Shunzo Fukatsu, Aiko Sawa, Sumio Umezawa
    1974 Volume 47 Issue 1 Pages 186-188
    Published: 1974
    Released: March 27, 2006
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    Condensation of 5-nitrofurfuryl iodide with uracil in dimethylformamide in the presence of lithium hydride gave 1-(5′-nitrofurfuryl)uracil. When the iodide was treated with adenine, 3-substituted adenine was mainly obtained, whereas the analogous reaction of benzamidopurine gave 9-substituted adenine. These compounds showed antitumor and broad antibacterial activity. Furfuryl derivatives were also described.
  • Yoshio Otsuji, Shigeo Wake, Eiichi Maeda, Eiji Imoto
    1974 Volume 47 Issue 1 Pages 189-192
    Published: 1974
    Released: March 27, 2006
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    Irradiation of 2,2-diethoxy-2,3-dihydrophenalene-1,3-dione (6) with a pyrex-filtered high-pressure Hg arc lamp afforded acetaldehyde, 2-ethoxy-3-hydroxyphenalene-1-one (7) and bis-2-(2-ethoxy-l,3-dioxo-2,3-dihydro) phenalenyl (8). Mechanistic studies revealed that the first step of this photoreaction was a homolytic fission of the C–OC2H5 bond to 2-(2-ethoxy-1,3-dioxo-2,3-dihydro)phenalenyl radical (9) and ethoxyl radical. This homolytic fission occurred mostly from the triplet and in part from the singlet excited state of 6. Dimerization of 9 gave 8 and the disproportionation between 9 and ethoxyl radical gave acetaldehyde and 7. The photochemical behaviors of a variety of triketone derivatives were discussed.
  • Hiizu Iwamura, Michiko Tsuchimoto, Shigeo Nishimura
    1974 Volume 47 Issue 1 Pages 193-196
    Published: 1974
    Released: March 27, 2006
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    When N-isopropylideneanilines are dissolved in methanol-d4, three types of reactions, exchange of protons in isopropylidene moiety, formation of carbinolamine ethers, and liberation of anilines with formation of acetone dimethyl acetal take place as revealed by NMR spectra of the solutions. The H–D exchange reaction is favored by electron-releasing ring substituents and yet is considerably slower than the rates of the E–Z isomerization of the corresponding imines. The carbinolamine ethers are formed when the substituents are strongly electronegative. Formation of acetone dimethyl acetal occurs additionally with imines carrying halogen atoms as the ring substituents. The competitive reaction mechanism is proposed.
  • Mitsuaki Narita, Masayasu Akiyama
    1974 Volume 47 Issue 1 Pages 197-201
    Published: 1974
    Released: March 27, 2006
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    N-Vinylbenzyl-L-amino acids were synthesized by the reaction of L-amino acids with formylstyrenes and the subsequent reduction of the condensation products with sodium borohydride. The procedure was performed without protection of the various functional groups of amino acids and racemization was not accompanied by the above process. The method is useful for the synthesis of optically active vinyl monomers containing various amino acids with their intact functionality. As a representative L-amino acid, a variety of N-vinylbenzyl-L-leucine derivatives such as N-methyl-L-leucine, L-leucine ethyl ester, L-leucinol and N-formyl-L-leucine ethyl ester were prepared by means of chemical transformation. These optically active monomers of leucine derivatives were polymerized to optically active polymers.
  • Ken Inouye, Atsushi Sasaki, Nobuo Yoshida
    1974 Volume 47 Issue 1 Pages 202-203
    Published: 1974
    Released: March 27, 2006
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    A synthesis is described of TACK, the chloromethyl ketone derivative of Nα-tosyl-L-arginine, in which a crystalline intermediate NG-nitro-TACK is found to be converted into TACK with hydrogen fluoride without appreciable impairment of the chloromethyl ketone moiety.
  • Yoshio Baba
    1974 Volume 47 Issue 1 Pages 204-209
    Published: 1974
    Released: March 27, 2006
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    The photolysis of crude naphtha in the presence of an oxidizing reagent was studied with a view to accomplishing the desulfurization of crude naphtha. The irradiation of crude naphtha consisting of 0.15% sulfur by means of a 200-W high-pressure mercury-vapor lamp, with the aeration of air or oxygen at the flow rates of 5–15 ml/min at 0 °C, resulted in an 80–90% photolysis of the principal mercaptans and sulfides in the crude naphtha within 20 min. The major photo-oxidation products were water-soluble oxygenated sulfur compounds; thus, this process resulted in 67.8% desulfurization when the irradiated naphtha was washed with water. The effects on the photolysis of the molecular weights and the structures of sulfur compounds were also examined with 11 mercaptans and 3 sulfides.
  • Yasuzo Suzuki, Takashi Tamaki, Masaki Hasegawa
    1974 Volume 47 Issue 1 Pages 210-214
    Published: 1974
    Released: March 27, 2006
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    The solution photopolymerization of 2,5-distyrylpyrazine (DSP) and its related compounds with the general formula of Ar–CH=CH–Ar′–CH=CH–Ar, where Ar and Ar′ represent aryl and arylene groups respectively, have been investigated. All diolefines were converted in good yields into amorphous oligomers with cyclobutane in the main chain on the exclusive excitation of the monomer molecules, while, in the crystalline state, only DSP and 1,4-bis[β-pyridyl-(2)-vinyl] benzene are known to yield highly crystalline oligomers under the same light. All the oligomers were found to be photodepolymerized to the original monomers in the solution on the excitation of the terminal groups of these oligomers. In consequence, a photoreverse scheme has been demonstrated between the diolefinic monomer and the oligomer, depending on the excitation wavelength. Poly-DSP was photodepolymerized into the monomer in tifluoroacetic acid solution, while amorphous poly-DSP in film was readily photooxidized in the air under sunlight. From the photochemical behavior of DSP, oligo-DSP, and poly-DSP, it was found that chemically the same substance, oligo-DSP, behaved in three ways, photopolymerization, photodepolymerization and no photoreaction, according to the physical state. Such a matrix effect is discussed from the point of view of topochemical reaction.
  • Yoshikazu Isowa, Muneki Ohmori, Hideaki Kurita
    1974 Volume 47 Issue 1 Pages 215-220
    Published: 1974
    Released: March 27, 2006
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    Two different sequence hexapeptides for the synthesis of ferrichrome were prepared using Nδ-tosyl-Nδ-benzyloxy-L-ornithine by means of N-hydroxysuccinimide plus N,N-dicyclohexylcarbodiimide or Woodward reagent K method. The linear hexapeptides (XII·HCl and XIX·HCl) were cyclized by excess N,N-dicyclohexylcarbodiimide to give cyclo-triglycyltri-Nδ-tosyl-Nδ-benzyloxy-L-ornithyl (XX). Detosylation, acetylation and successive reductive debenzylation of XX afforded deferri-ferrichrome (XXIV). Addition of ferric iron to XXIV gave ferrichrome, which had the same crystalline form, superimposable infrared and well-agreeing visible spectra and the same value in optical rotation compared with the data in the literature of natural product.
  • Hideo Takiguchi, Nobuo Izumiya
    1974 Volume 47 Issue 1 Pages 221-225
    Published: 1974
    Released: March 27, 2006
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    Structural isomers of gramicidin S and [2,2′-lysine]-gramicidin S, namely iso-gramicidin S and iso-[2,2′-lysine]-gramicidin S, were prepared to investigate the influence of the ring size for antibacterial activity and conformation of natural gramicidin S. Each isomer involves two peptide bonds between carboxyl group of valine residue and ω-amino group of ornithine or lysine residue. Two isomers showed no antibacterial activity toward several microorganisms. In the experiment of optical rotatory dispersion, two isomers showed similar shaped curves as gramicidin S in a solvent of ethanol. In 6 M urea, the trough of two isomers was moved significantly, whereas that of gramicidin S remained constant.
  • Kunio Kogami, Ju Kumanotani
    1974 Volume 47 Issue 1 Pages 226-233
    Published: 1974
    Released: March 27, 2006
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    The mechanism of the allylic rearrangement of linalyl acetate in the medium of acetic acid, propionic acid, or acetic acid containing dioxane or sulfuric acid has been investigated. The nature of the carbonium-ion pairs generated from linalyl acetate in low-dielectric-constant solvents or in strong acids, and the behavior of the active intermediate in the transition state were postulated from the kinetic data as well as from the physicochemical properties and distributions of the products.
  • Kiyoshi Otsuka, Tominaga Keii
    1974 Volume 47 Issue 1 Pages 234-235
    Published: 1974
    Released: March 27, 2006
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    The corrected activities, rates divided by square of spin magnatic moment of a metal ion, in ortho-parahydrogen conversion on first series transition metal oxides at 77°C were shown to give a very similar activity pattern to that obtain in hydrogen-deuterium equilibrtation.
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