Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 49 , Issue 7
Showing 1-50 articles out of 72 articles from the selected issue
  • Gaku Izumi, Makoto Sato, Sakae Shoji, Kanenao Oikawa
    1976 Volume 49 Issue 7 Pages 1727-1731
    Published: 1976
    Released: April 19, 2006
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    In order to highly selectively remove and recover heavy metals, usually harmful, from wastewater, a modified foam-separating method using a fatty compound, i.e. N-monodecanoyl diethylenetriamine, was investigated on real and model wastewater, containing several kinds of metals. This agent forms soluble and foamy complexes with the metals.
  • Katsumi Sakurai, Yasuaki Okamoto, Toshinobu Imanaka, Shiichiro Teranis ...
    1976 Volume 49 Issue 7 Pages 1732-1735
    Published: 1976
    Released: April 19, 2006
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    In the catalytic NO–CO reaction over metal oxide catalysts, the surface states of reduced metal oxides were studied with ESCA, and the correlation of the activities of the reduced metal oxide catalysts for the NO–CO reaction with their surface states was investigated. The surfaces of the catalysts were studied with ESCA after treatments in situ. It was revealed that the surface states of the metal oxides did not always agree with their bulk constituents. For example, it was found that the oxygen in the surface layer of the cobalt oxide after a proper reduction treatment by CO was richer than in its bulk. Moreover, the correlation between the surface states and the activities of those oxides was successfully explained. It was also concluded that, in the NO–CO reaction, the metal states were most active for the cobalt, iron, and nickel oxides, while the Cu+ state was more active than the Gu metal state for the copper oxide.
  • Hiroki Imoto, Nobuatsu Watanabe
    1976 Volume 49 Issue 7 Pages 1736-1739
    Published: 1976
    Released: April 19, 2006
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    The anodic behavior of pyrolytic graphite has been studied by voltammetry and ESCA analysis in the molten KF-2HF system at 100°C, attention being given to the difference in anodic behavior between the edge plane and layer-plane of the pyrolytic graphite. The polarization current obtained by a linear potential sweep experiment decreased rapidly with increasing potential after the onset of the anode effect. When the edge plane was used as a working electrode surface the current density was recovered on the subsequent sweep toward negative potentials, whereas the current density was hardly recovered on the layer-plane surface of the electrode. The difference in polarization behavior was interpreted on the basis of the difference in the rate of decomposition reaction of graphite fluoride, (CF)n, formed on the electrode surface. ESCA spectra of the electrodes polarized at various potentials indicate that (CF)n was formed even at 2.0 V vs. Pt, below the fluorine evolution potential, on the edge plane of the pyrolytic graphite and that its amount did not increase appreciably with increasing potential. On the layer-plane, however, no formation of (CF)n was observed at 2 V vs. Pt, its amount increasing appreciably with potential at the potentials above 3 V vs. Pt.
  • Naoki Furuta, Tokuko Watanabe, Shizuo Fujiwara
    1976 Volume 49 Issue 7 Pages 1740-1747
    Published: 1976
    Released: April 19, 2006
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    ESR results for γ-irradiated K3[Co(CN)6] in powder and single crystal forms are reported. The main paramagnetic species detected at 77 K were diisocyanide [CoII(CN)4(NC)2]4− and pentacyanocobaltate (II) [CoII(CN)5]3−. On annealing, diisocyanide was lost and pentacyanocobaltate was formed. In Part I the reaction mechanism is discussed from the results of the powdered sample and in Part II the noncollinear structure is presented as the plausible molecular form of diisocyanide from the results of the single crystal.
  • Masayuki Nakagaki, Shuji Kitagawa
    1976 Volume 49 Issue 7 Pages 1748-1753
    Published: 1976
    Released: April 19, 2006
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    Reverse diffusion is the migration of solutes in the direction opposite to that expected from the concentration gradient, that is, from a portion with a lower concentration to that with a higher concentration. This type of diffusion of ions in mixed electrolyte solutions was studied theoretically on the basis of nonequilibrium thermodynamics. For a solution containing two kinds of cations and one kind of anion, it has been concluded that the reverse diffusion occurs when the mobilities of the coexisting ions differ largely, because the effect of the diffusion potential is pronounced in such a case. It has also been concluded that the practical diffusion coefficient of an ion varies linearly with the ratio of the concentration gradient of a coexisting ion to that of the diffusing ion when the average concentration ratio of the ions is fixed. Moreover, the range of the concentration-gradient ratio, where the practical diffusion coefficient is negative, has been determined. These theoretical conclusions were tested experimentally for the HCl–CaCl2–H2O ternary system. The results satisfactorily verified that reverse diffusion actually occurred and that the relationship between the diffusion coefficient and the concentration-gradient ratio was linear, as has been expected.
  • Akihiko Yamagishi
    1976 Volume 49 Issue 7 Pages 1754-1757
    Published: 1976
    Released: April 19, 2006
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    Rate constants were obtained with a temperature-jump apparatus for the electron-transfer reaction between 7,7,8,8-tetracyanoquinodimethane anion radical and 2,3-dichloro-5,6-dicyano-p-benzoquinone in acetonitrile/ tetrahydrofuran (MeCN/THF) and in acetonitrile/water (MeCN/H2O) mixtures. In MeCN/THF, the forward rate constant (k) was determined in three kinds of mixed solvents: k=(5±2)×109 M−1s−1 (pure MeCN), (2.2±0.2)×109 M−1s−1 (1: 2 MeCN/THF), and (6±2)×108 M−1s−1 (1: 10 MeCN/THF) at 25±2°C. In MeCN/H2O the forward rate constant increases with the square of the H2O concentration in the range of [H2O]=2–10 M; k=k0[H2O]2 with k0=(1.0±0.2)×106 M−3s−1 at 25±2 °C. The results are discussed in terms of the specific solvation and the ion-pairing of ion radicals.
  • Kohji Tadasa, Naomi Imai, Tetsuo Inaba
    1976 Volume 49 Issue 7 Pages 1758-1761
    Published: 1976
    Released: April 19, 2006
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    The photolysis of CH2O has been studied in the absence and presence of NO from room temperature to 300°C. In the photolysis of CH2O alone, the CO and H2 formation rates increase greatly with temperature. When NO is added, these rates vary and reach constant values with an increase in the amount of NO. These limiting rates are independent of the temperature to within the experimental error, in contrast to the rates observed for CH2O alone. It is suggested that the limiting rate of CO formation corresponds to the sum of the rates of the two primary processes, the molecular and radical reactions, and that that of H2 formation corresponds to the rate of the molecular process. For photolysis totally inhibited by NO, the rates of formation of CO, H2, N2, and N2O were examined and a reaction mechanism is proposed which is consistent with that for the photosensitized reaction between hydrogen and nitric oxide previously studied in this laboratory.
  • Hiroyuki Yamaguchi, Teruki Ikeda, Hiroaki Mametsuka
    1976 Volume 49 Issue 7 Pages 1762-1765
    Published: 1976
    Released: April 19, 2006
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    The dipole moments of the lower two singlet excited states of azulene (I) and 3,5-dimethyl derivative of cyclopenta[ef]heptalene (II) have been determined from the frequency shift of the absorption and emission spectra in various solvents. The direction of the excited-state dipole moments of molecules I and II is opposite to the direction of the ground-state dipole moments. The dipole moments of the two excited states of molecules I and II have been calculated by using the semi-empirical SCF-π-MO CI method. There is a general agreement between the theoretical results and the experimental results. This agreement shows that the polarization effect of the σ-electrons is almost identical in the ground and excited states of both molecules.
  • Muneteru Kozuka, Taro Isobe
    1976 Volume 49 Issue 7 Pages 1766-1771
    Published: 1976
    Released: April 19, 2006
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    A rapid-scan infrared spectrometer capable of scanning the region from 5000 to 650 cm−1 in 200 μs was constructed and successfully applied to study CF3CO radical produced by flash photolysis. Four absorption bands of the radical were detected at 1574, 1338, 1115, and 1024 cm−1 for scanning started 25 μs after the firing of a Xe flash tube. They were tentatively assigned to the CO stretching, CF3 stretching (a species), CF3 stretching (e species), and CC stretching vibrations, respectively.
  • Hiromitu Naono, Kazuko Moori, Tetsuo Morimoto
    1976 Volume 49 Issue 7 Pages 1772-1775
    Published: 1976
    Released: April 19, 2006
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    The amounts of physisorbed and chemisorbed pyridine on silica–alumina in the hexane solution were measured at 30°C, and found to be 1.25 and 0.25 molecules/100 Å2 respectively. The number of strong acid sites determined by Benesi’s method are in good agreement with the chemisorbed molecules, which indicates that the ratio of the number of chemisorbed pyridine molecules to that of the strong acid sites on the surface of silica–alumina is equal. The adsorption calorimetry was carried out on the same system by means of a flow microcalorimeter which permits us to differentiate the heats of physisorption and chemisorption: the results showed that the heats of physisorption and chemisorption of pyridine are 11.3±0.3 and 22±4 kcal/mol respectively.
  • Masaharu Ueno, Hiroshi Kishimoto, Yoshimasa Kyogoku
    1976 Volume 49 Issue 7 Pages 1776-1779
    Published: 1976
    Released: April 19, 2006
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    The dynamic structure of Aerosol OT molecules in micellar state was studied by measurements of 13C-NMR spin-lattice relaxation time (T1) and the effect of a lantanide shift reagent Yb(fod)3 in chloroform at 25 MHz and 40°C. The results were analyzed on the basis of the conformation and segmental motions of Aerosol OT molecules in micellar state, with the following conclusions: Aerosol OT molecules in the micellar state associate with each other by the polar head groups; their hydrocarbon chains are flexible; the mobility of side chain is restricted to a greater extent than that of the main chain; carbonyl carbon-(2′) is located nearer to the polar group than carbon-(2) in steric conformation.
  • Teijiro Tamura, Takuya Hamamura
    1976 Volume 49 Issue 7 Pages 1780-1784
    Published: 1976
    Released: April 19, 2006
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    The chemisorption of nitrogen oxide and nitrogen on a polycrystalline tungsten filament was studied using flash desorption mass spectroscopy. The saturation coverage for nitrogen oxide and nitrogen on tungsten is 8.8×1014 molecules/cm2 and 1.9×1014 molecules/cm2, respectively. These saturation coverages on tungsten are about 1.7 times those on rhenium. The initial sticking probability of nitrogen oxide is very high compared with other gases. It is assumed that the nitrogen oxide adsorption is non-dissociative on tungsten, while the nitrogen is adsorbed dissociatively. When the temperature of the tungsten filament saturated with nitrogen oxide is raised, a small amount of nitrogen oxide molecules desorb at about 475 K, and dissociation occurs at more elevated temperatures. The greater part of the nitrogen desorbs before the temperature reaches 1500 K. No oxygen desorption was detected upon heating the tungsten saturated with nitrogen oxide. It appears that oxygen probably desorbs as tungsten oxide. Three states of nitrogen desorption, designated α, β1, and β2, on tungsten appeared at room temperature. The activation energy of the desorption for the strongly chemisorbed nitrogen of the β1 and β2 states on tungsten are 78 kcal/mol and 80.5 kcal/mol, respectively.
  • Hideyuki Arai, Isao Kanesaka, Yukio Kagawa
    1976 Volume 49 Issue 7 Pages 1785-1787
    Published: 1976
    Released: April 19, 2006
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    The finite element approach was successfully applied to the vibrational Schrödinger equation of diatomic species. An O2 molecule with a harmonic potential and an Ar2 molecule with a Lennard-Jones potential were examined and their eigen values and the associated eigen function were obtained. The calculated eigen values of the O2 molecule agree with those expected. In the case of the Ar2 molecule the calculated eigen values agree with those experimentally obtained when Lennard-Jones parameters are ε=115.1 (cm−1) and σ=3.35 (Å). This verifies the validity of the present approach.
  • Koichi Mizuno, Masanori Ikeda, Toshiaki Imokawa, Jun-ichiro Take, Yuki ...
    1976 Volume 49 Issue 7 Pages 1788-1793
    Published: 1976
    Released: April 19, 2006
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    When pyridine chemisorbed on silica–alumina was evacuated at 350°C, the 1460 cm−1 band due to Lewis-bound pyridine (LPY) remained while the 1540 cm−1 band due to Brønsted-bound pyridine (BPY) completely disappeared. This disappearance of the BPY band was revealed to accompany a loss of the Brønsted acid sites themselves besides their liberation. However, the lost Brønsted acid sites were regenerated by allowing the sample to stand overnight at 110°C. Thus, strong Lewis acid sites of silica–alumina were able to be selectively poisoned by pyridine without any damage to the Brønsted acid sites. By poisoning catalysts in situ by controlled amounts in this way, the nature of the active site was investigated for polymerization of propylene or cis-2-butene at a low temperature of 30 °C. The initial activity declined sharply as the extent of pyridine poisoning of the Lewis acid sites increased. Therefore, it was concluded that strong Lewis acid sites (25–30% of the total Lewis acid content) were active in polymerization over silica–alumina.
  • Norisuke Hata, Isao Ono
    1976 Volume 49 Issue 7 Pages 1794-1798
    Published: 1976
    Released: April 19, 2006
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    The quantum yields for the photochemical isomerization of azanaphthalene N-oxides, such as quinoline N-oxide and isoquinoline N-oxide, into lactam (Process I) or oxazepine (Process II) were determined in benzene (or carbon tetrachloride), in methanol, and in mixtures of the two solvents. Consequently, the reaction was revealed to be closely related to whether or not the N-oxide oxygen atom forms a hydrogen bond with the solvent molecule; that is, a strong hydrogen-bonding interaction between the excited singlet N-oxide and alcohol is essential for Process I, but not for Process II. It was further demonstrated that Process II occurred with the formation of powerful oxidants (probably oxaziridines) from the excited singlet N-oxide, whereas such an oxidizing species was not involved in Process I. The reaction mechanisms of Processes I and II were also discussed on the basis of the present experimental results.
  • Tsuguhiro Kaneda, Jiro Tanaka
    1976 Volume 49 Issue 7 Pages 1799-1804
    Published: 1976
    Released: April 19, 2006
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    The crystal structure of a 1: 1 complex of 9-ethyladenine and indole has been determined by the X-ray method. The crystal system is monoclinic with the space group of P21/c. The cell dimensions are a=15.712(2), b=8.098(1), c=11.838(1)Å, and β=103.90(1)°C. Adenines form walls made of double layer. An overlap of adenines is found between layers. The adenine molecule in the front layer is found to be joined by the hydrogen bond with the molecule in the back layer. An intermolecular hydrogen bond is found between adenine and indole rings. The significance of these observations in the interaction of adenine with tryptophan in biological systems is discussed.
  • Kenji Okuyama, Nobuo Tanaka, Tamaichi Ashida, Masao Kakudo
    1976 Volume 49 Issue 7 Pages 1805-1810
    Published: 1976
    Released: April 19, 2006
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    A detailed conformation study of the polypeptide (Pro–Pro–Gly)10, synthesized as a collagen model, has been done using X-ray diffraction. Several structures having the observed helical parameters (unit height=8.61 Å, unit twist=51.4°) together with standard bond lengths and angles were generated and tested in terms of an existence of intermolecular van der Waals contacts and least squares calculations using 49 equatorial reflections. It was found from these studies that three polypeptide chains make a three-stranded rope of which the helical parameters are similar to but significantly different from those of the collagen models proposed so far. There exist two possible models for (Pro–Pro–GIy)10 according to the type of hydrogen bonding. One is the model having a hydrogen bond so-called ‘standard’ structure type, and the other has a hydrogen bond of collagen 11 type. The two-dimensional electron density map, synthesized with the observed structure factors, agrees well with these models. In the least squares calculations, atomic scattering factors were modified by taking into account of effects of amorphous water between the three-stranded ropes.
  • Ivan Gutman, Tamië Yamaguchi, Haruo Hosoya
    1976 Volume 49 Issue 7 Pages 1811-1816
    Published: 1976
    Released: April 19, 2006
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    The topological factors which cause non-uniform π-electron charge distribution in non-alternant hydrocarbons (NAH′s) are discussed. For estimating and analyzing the net-charge density a novel topological index, topological charge density, QrT, is proposed. It is defined as QrT=Re(FG,r(1)), the real part of FG,r(y)=Δr,r(iy)⁄Δ(iy), where Δ(x) is the secular determinant of graph G and Δr,r(x) is its adjunct with row r and column r struck out. This quantity QrT, corresponding to the Coulson net charge density Qr=1−qr, is related with the topological indices \widetildeZG and \widetildeYG which are defined in terms of the coefficients of the characteristic polynomial of graph G. As all the newly proposed indices can be enumerated graphically, one can easily estimate the net-charge densities of NAH′s.
  • Chikara Amano, Shizuo Fujiwara
    1976 Volume 49 Issue 7 Pages 1817-1819
    Published: 1976
    Released: April 19, 2006
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    It has been shown that univalent nickel complex ions are produced in rigid solutions by electrons released on photo-ionization of N,N,N′,N′-tetramethyl-p-phenylenediamine. These complexes have the same g-values as those obtained by γ-irradiation, suggesting that the univalent nickel complex ions produced on γ-irradiation can be formed as a result of the capture of near-thermal electrons by bivalent nickel complexes. Upon UV-exposure at various sample temperatures between −196 °C and −70 °C, a new chemical species with g⁄⁄ of 2.37 and g of 2.128 has been observed, which appears to be an exchange-coupled dimer of the univalent hexaaqua nickel complex ions.
  • J. Sreekantha Babu, Km. Veena Joshi, A. K. Bhattacharya
    1976 Volume 49 Issue 7 Pages 1820-1823
    Published: 1976
    Released: April 19, 2006
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    A detailed kinetic study of the oxidation of propyl-, isopropyl-, butyl- and isobutylamines by potassium peroxydisulfate in presence of silver ions has been carried out in aqueous medium. The effects of silver ion concentration and various neutral salts have been detected and the variation of the order of reaction with respect to amine had been explained. The activity of Ag+ ion has been correlated with the amine structure and probable rate law and the mechanism has been proposed.
  • Buta Singh, J. K. Vij
    1976 Volume 49 Issue 7 Pages 1824-1828
    Published: 1976
    Released: April 19, 2006
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    The relative permittivity at 1 MHz, the refractive index at the wavelength of sodium D-line and density of the nine alcohols, 1-propanol (A), 2-propanol (B), 1-butanol (C), 2-methyl-1-propanol (D), 1-pentanol (E), 1-hexanol (F), 1-heptanol (G), 3-methyl-2-hexanol (H), 3-methyl-3-hexanol (I), have been measured at 25 °C in benzene in the entire concentration range. The measurements for 1-dodecanol (J) have been made in dilute solutions only. The dipole moments of these molecules in dilute solutions, using Higasi’s equation, and the apparent dipole moment for various solute concentrations, using Kirkwood-Fröhlich equation, have been calculated. The results suggest that at low concentrations the alcohols associate to form weakly polar multimers. At high concentrations and in pure liquids, the isomers in which the hydroxyl group is relatively free, favour the formation of highly polar multimers, whereas the isomers in which the hydroxyl group is sterically blocked by the methyl group, favour the formation of closed or ring dimers having low dipole moment.
  • A. K. Mandal, S. C. Lahiri
    1976 Volume 49 Issue 7 Pages 1829-1831
    Published: 1976
    Released: April 19, 2006
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    The dissociation constants of salicylic acid in water and ethanol-water mixtures (8–87.6 wt % of ethanol), have been determined by the modified conductometric method as suggested by Gelb. The results have been checked independently from the plot Λ C vs. 1/Λ of salicylic acid in mixed solvents. Λ°HCIO4 and Λ°salicylic acid have also been determined.
  • Subrata Chatterjee, Nanda K. Das Gupta
    1976 Volume 49 Issue 7 Pages 1832-1837
    Published: 1976
    Released: April 19, 2006
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    The molecules pentaleno[def]heptalene, cyclohept[fg]acenaphthylene, naphth[cde]azulene and cyclohept[bc]acenaphthylene have been studied using β-variable methods proposed by Dewar et al. and Yamaguchi et al. The predicted results are compared with experimental values and with other theoretical results.
  • A. N. Srivastava, P. R. Talesara
    1976 Volume 49 Issue 7 Pages 1838-1840
    Published: 1976
    Released: April 19, 2006
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    Evidence of donor-acceptor complexes as a result of interaction between thiols and carbon tetrachloride has been obtained from the studies of dipole moment at 30°C. Our polarisation data in other solvents except benzene are new. The results obtained have been discussed in terms of the influence of solvent on dipole moments in the light of general theory of Higasi.
  • Hisaya Oki, Kiyoe Otsuka
    1976 Volume 49 Issue 7 Pages 1841-1844
    Published: 1976
    Released: April 19, 2006
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    A comparison has been made between the synthesis carried out by the isothermal matrix method in solid state and that by the usual method in solution for chromium(III) complexes with glycine and dl-α-amino acids (alanine, aminobutyric acid, norvaline, norleucine, valine, isoleucine and leucine). The effect of the length of the skeletal carbon chain or the presence of the side chain in α-amino acids on the formation of complexes was investigated. The complexes with α-amino acids which have a normal chain were obtained in fac-structure except for norleucine complexes, whereas the complexes with α-amino acids which have a side chain were obtained only in dimertype by the matrix method in solid state. The chromium(III) complexes with dl-α-amino acids were all prepared as tris-type structure, except for α-aminobutyric acid and valine, whereas all the complexes of dimer-type structure were prepared in solution, except for alanine and norleucine.
  • Masatoshi Watabe, Shigeji Kawaai, Sadao Yoshikawa
    1976 Volume 49 Issue 7 Pages 1845-1848
    Published: 1976
    Released: April 19, 2006
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    The isomerization of two of the three possible geometrical isomers for the (D-aspartato)(L-2,4-diaminobutyrato)cobalt(III) complex afforded the residual third isomer which has not here to fore been obtained. The equilibrium mole fractions of these isomers in water in the presence of activated carbon were found for D-cisO5cisN5, D-transO5transN5, D-fac to 0.68, 0.11, 0.21, respectively. As the two ligands coordinated are considered to involve no intermolecular hydrogen bonding or steric hindrance, the relative positions of the six coordinated atoms around a cobalt atom may cause these unequal isomer ratios. These isomerisms are dealt with by means of a network of firstorder reversible reactions and the relative values of the rate constants are determined.
  • Tadashi Tokii, Yoneichiro Muto
    1976 Volume 49 Issue 7 Pages 1849-1854
    Published: 1976
    Released: April 19, 2006
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    Compounds with the stoichiometry of Cu(5-R″-sal·N–R)R′COO (5-R″-sal·N–=·\overset2O·C6H3(\overset5R″)·\overset1CH=N–; R= methyl, phenyl, o-tolyl and p-tolyl; R′=ethyl, monochloromethyl and dichloromethyl; R″=H, CH3 and Cl) have been prepared, and their magnetic and spectral properties have been studied. The magnetic and IR spectral data of the compounds where R=methyl and o-tolyl, R′=dichloromethyl, and R″=H indicate that they have phenolic oxygen-bridged dimer units in their crystals. On the other hand, a carboxylate-bridged binuclear structure is postulated for the other complexes on the basis of magnetic and IR spectral data. It has been observed that, in the latter group of complexes, both the −2J(singlet-triplet separation) and νmax (ligand-field transition energy) values decrease in the order of Cu(Sal·N–R)C2H5COO>Cu(Sal·N–R)ClCH2COO>Cu(Sal·N–R)Cl2CHCOO, where Sal·N–=·\overset2O·C6H4·\overset1CH=N–. The preparation and characterization of the Cu(Sal·N–R)HCOO·DMF compounds (R=p-tolyl and p-chlorophenyl; DMF=N,N-dimethylformamide) are also reported.
  • Masao Kiyama
    1976 Volume 49 Issue 7 Pages 1855-1860
    Published: 1976
    Released: April 19, 2006
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    Suspensions containing either iron(III) hydroxide or hydroxide oxide and barium ions were subjected to autoclaving at various temperatures from 100 to 300 °C, and the properties of the resulting products were studied. A ferromagnetic precipitate, BaO·6Fe2O3, consisting of hexagonal plate-like particles, was obtained by suitable combination of temperature, kind and particle size of iron(III) hydroxide oxide, and concentration of Ba(OH)2. Nonferromagnetic precipitates, BaO·4.5Fe2O3 and BaO·2Fe2O3, were also formed depending on the conditions. The mechanism of their formation is discussed. The magnetic properties of the BaO·6Fe2O3 precipitates are investigated.
  • Mutsuo Yamada
    1976 Volume 49 Issue 7 Pages 1861-1863
    Published: 1976
    Released: April 19, 2006
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    The rate constants for the formation of the diprotonated bimetallic complex of copper(II) with 3,3′-bis[N,N-bis(carboxymethyl)aminomethyl]-o-cresolsulfonphthalein (XO) have been determined by the stoppedflow method. The results are interpreted in terms of the reactions, Cu+LH2\ ightleftharpoonsCuLH2 (Remark: Graphics omitted.) Cu2LH2 and Cu+LH3\ ightleftharpoonsCuLH2+H (Remark: Graphics omitted.) Cu2LH2+H. The over-all rate constants, k1 and k2 for both reactions are determined to be k1=(3.6±0.3)×106M−1s−1 and k2=(8.7±1.3)×103M−1s−1 and 25.0 °C and I=0.1 M.
  • Keiji Yokoho, Keiji Matsumoto, Shun’ichiro Ooi, Hisao Kuroya
    1976 Volume 49 Issue 7 Pages 1864-1866
    Published: 1976
    Released: April 19, 2006
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    X-Ray structure analysis of the title compound has revealed that the asymmetric secondary nitrogen center in the complex cation has the S absolute configuration. The crystals are orthorhombic, with the space group P212121and with Z=4 in a unit cell with dimensions of: a=18.783(6), b=14.138(4), and c=8.473(2)Å. The crystal structure has been determined from three-dimensional diffractometer data and refined by the least-squares method to R of 0.030 for 1971 independent reflections with I>3σ(I). The Pt atom has a square-planar coordination by four N atoms, and the methyl group bonded to the secondary nitrogen is equatorial with respect to the chelate ring. Each complex cation is surrounded octahedrally by six di-μ-(+)-tartrato(4-)-bis(antimonate(III)) anions.
  • Toshiaki Taura, Ushio Sakaguchi, Hayami Yoneda
    1976 Volume 49 Issue 7 Pages 1867-1870
    Published: 1976
    Released: April 19, 2006
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    The rates of amine hydrogen isotopic exchange in the [Co(O)2(N)4]+ complex ions, where (O)2 represents carbonate, oxalate, or malonate ions, and (N)4, tetraammine, bis(ethylenediamine), or bis(trimethylenediamine), were measured in D2O at 35 °C by the PMR technique. It was found that: (1) the rates for trans (to oxygen) amines are faster than those for cis amines; (2) the rates, especially for trans amines, in the carbonato complexes are slower than those in the oxalato and malonato analogs, and (3) the difference between the rates for cis and trans amines is smaller in the bis(diamine) complexes than in the tetraammine complexes. These results are discussed in terms of the influence of the chelate geometry in the complex on the exchange reaction.
  • Yoshimi Ohtani, Masatoshi Fujimoto, Akihiko Yamagishi
    1976 Volume 49 Issue 7 Pages 1871-1873
    Published: 1976
    Released: April 19, 2006
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    The monomer-dimer equilibrium of RhCl(PPh3)3 in benzene has been studied with a stopped-flow apparatus under He gas pressure. The decomposition rate of a dimer, [RhCl(PPh3)2]2, obeys pseudo-first-order kinetics with respect to the concentration of PPh3, whereas the formation rate of a dimer obtained by diluting an equilibrium solution with benzene depends on the equilibrium concentration of a monomer, a dimer and PPh3 in a complexed manner. The kinetic results are consistent with the following mechanism; 2RhCl(PPh3)3\ ightleftarrowsRhCl(PPh3)2+RhCl(PPh3)3+PPh3\ ightleftarrows[RhCl(PPh3)2]2+2PPh3.
  • Isao Yoshida, Hiroshi Kobayashi, Keihei Ueno
    1976 Volume 49 Issue 7 Pages 1874-1878
    Published: 1976
    Released: April 19, 2006
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    The solute distribution profile on a columned charge of length L after m-cycles of the intermittent zone melting with j zones of length l, was computed for a range of distribution coefficient, k. The effects of j, l and k upon the separation efficiencies by this method were investigated in terms of the fractional length, α, which was refined to an required purity level, γ, in a limited number of m, and the fractional ratio, σ, of a solute amount which was concentrated into a limited portion of a fractional column length, β. The intermittent method is superior in respect to the separation efficiencies, α as well as σ, over the usual method, if a columned charge was zone-melted with the same number of zones of the same length at the same zone-travelling speed. Results of theoretical calculation were confirmed on systems of azobenzene in naphthalene and those of some metal acetylacetonates in the beryllium chelate of the same ligand compound.
  • Masafumi Goto, Tadashi Makino, Masahiko Saburi, Sadao Yoshikawa
    1976 Volume 49 Issue 7 Pages 1879-1882
    Published: 1976
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A novel complex, trans (R,S)-[CoCl2((2S,10S)-Me2-2,3,2-tet)]ClO4((2S,10S)-Me2-2,3,2-tet=(2S,10S)-4,8-diazaundecane-2,10-diamine) was prepared from the trans(R,R) isomer in basic methanol. The configuration of the trans(R,S) isomer was determined from the PMR and CD evidences. The equilibrium ratio of the R,S and R,R isomers in basic methanol was estimated to be 7.6±0.3: 1 (ΔG298=1.20±0.03 kcal/mol), the former being in preference to the latter.
  • Haruko Ikeuchi, Yoshimi Fujita, Kyoichi Iwai, Gen P. Satô
    1976 Volume 49 Issue 7 Pages 1883-1887
    Published: 1976
    Released: April 19, 2006
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    The diffusion coefficient and the product of the charge number of electrode reaction n and the concentration of depolarizer c can be determined simultaneously from the time dependence of the diffusion limiting current observed at a spherical electrode of known size. Nearly ideal spherical diffusion was realized by means of a mercury drop electrode hanging from the tip of a fine glass capillary (0.2 mm, outer diameter) which was kept at constant size by adjusting the mercury head. The diffusion coefficients of thallium(I), cadmium(II), bismuth(III), and hexamminecobalt(III) ions in 0.1 mol dm−3 potassium nitrate aqueous solutions were determined at 25 °C. The experimental nc values agreed with the corresponding known values within 3%.
  • Takashi Abe, Shunji Nagase, Hajime Baba
    1976 Volume 49 Issue 7 Pages 1888-1892
    Published: 1976
    Released: April 19, 2006
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    The perfluorocyclic ethers as well as the perfluoroalkanoyl fluorides were obtained by the electrochemical fluorination of primary monohydric alcohols and aldehydes containing 4–8 carbon atoms. The five-membered rather than the six-membered perfluorocyclic ethers were formed as the cyclic products. The over-all yields of the perfluorocyclic ethers and the perfluoroalkanoyl fluorides from the alcohols were in the range of 10–20%, and 3–12% respectively. Those from the aldehydes were poor because of the formation of a considerable amount of tarry by-products. The physical properties of the perfluorocyclic ethers obtained are also described.
  • Manabu Sen\={o}, Shinsaku Shiraishi, Yukio Suzuki, Teruzo Asahara
    1976 Volume 49 Issue 7 Pages 1893-1896
    Published: 1976
    Released: April 19, 2006
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    Solvolytic ring-opening reactions of gem-dichloroaziridines in the presence of sulfuric acid were investigated. The reaction products from 1-aryl-2,2-dichloro-3-phenylaziridines varied with the kind of substituent at 3-position of the aziridine ring. 2,2-Dichloro-1,3-diphenylaziridine gave α-chloro-α-phenylacetanilide, 2,2-dichloro-3-methyl-3-phenyl-1-(m-tolyl)aziridine gave N-(m-tolyl)atropamide and 2,2-dichloro-1,3,3-triphenylaziridine gave 3,3-diphenyloxindole. 1-Benzyl-2,2-dichloro-3,3-diphenylaziridine and 2,2-dichloro-1 -phenethyl-3,3-diphenylaziridine gave 4,4-diphenyl-1,2,3,4-tetrahydroisoquinoline-3-one and 1,1-diphenyl-1,2,3,4,5-pentahydro-3-benzazepine-2-one, respectively. It was found that the substituent on C3-carbon determines the mode of reaction.
  • Syun-ichi Kiyooka, Keiko Takeshima, Hidehumi Yamamoto, Kojiro Suzuki
    1976 Volume 49 Issue 7 Pages 1897-1900
    Published: 1976
    Released: April 19, 2006
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    Optically active α-alanines have been synthesized by the asymmetric hydrogenolysis of the chiral hydrazones which were derived from chiral amines and ethyl pyruvate. Reduction of the C=N group in the hydrazones was carried out using PtO2 catalyst in acetic acid at room temperature, followed by hydrogenolysis of the N–N linkage using the same catalyst in 1 M HCl at 100 °C (autoclave). The synthesis using (S)-bornylamine as a chiral reagent afforded L-alanine with optical purity of 46.5%. By using (S)-1,2-dimethylpropylamine as a simple chiral reagent, L-alanine was also obtained with optical purity of 32.2%. It has become apparent that the synthesis using (S)-alkylamine gave L-alanine, while D-alanine was obtained by using (S)-α-methylbenzylamine.
  • Manabu Sen\={o}, Koji Araki, Shinsaku Shiraishi
    1976 Volume 49 Issue 7 Pages 1901-1905
    Published: 1976
    Released: April 19, 2006
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    The iodination reactions of ketones in the reversed micellar systems of dodecylammonium propionate (DAP) in hexane were studied at 25.0 °C in relation to the enzymatic function of aldolase or enolase. The reaction rate in the DAP reversed micellar system is 106–107 times greater than that in the system without DAP, 100 times greater even in comparison with that in DAP aqueous system at pH 6.8. As in the ammonium ion catalyzed reaction in aqueous media, the reaction in the presence of DAP proceeds via ketimine formation between ammonium groups of DAP and acetone and subsequent enolization of ketimine to enamine, which reacts very rapidly with iodine. The catalytic effect of DAP reversed micellar system in each reaction step was discussed. Further, this reversed micellar system shows a marked selectivity for acetone as compared with higher analogs.
  • Hiroaki Sawai, Takeo Takizawa
    1976 Volume 49 Issue 7 Pages 1906-1908
    Published: 1976
    Released: April 19, 2006
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    Isocyanides reacted with mercury(II) chloride in dry tetrahydrofuran upon heating to afford low molecular weight polymers and oligomers. Isocyanides without bulky groups underwent polymerization catalyzed by mercury(II) chloride. Various heterocyclic oligomers were obtained from the reaction of 2,6-xylyl isocyanide with mercury(II) chloride.
  • Chung-gi Shin, Yoshiaki Sato, Juji Yoshimura
    1976 Volume 49 Issue 7 Pages 1909-1912
    Published: 1976
    Released: April 19, 2006
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    It was found that the halogenation of t-butyl 2-acetylamino-3-bromo-2-alkenoate (3) by NBS or NCS gave t-butyl 2-acetylimino-3,3-dihaloalkanoate (6 and 7). The addition of water or several saturated, unsaturated and polyhydric alcohols to the carbon-nitrogen double bond of 6 or 7 was accomplished to give t-butyl 2-acetylamino-2-alkoxy- and hydroxy-3,3-dihaloalkanoate. Similarly, the treatment of t-butyl 2-bromoacetylamino-2-alkenoate in alcohol gave t-butyl 2-acetylamino-2-alkoxy-3-bromoalkanoate, via the addition of alcohol to the imino intermediate (2). The formation mechanism and the structural assignment are discussed.
  • Kin-ya Akiba, Takayuki Kawamura, Masahide Ochiumi, Naoki Inamoto
    1976 Volume 49 Issue 7 Pages 1913-1916
    Published: 1976
    Released: April 19, 2006
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    3-Substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) were reduced with lithium aluminum hydride to give the corresponding thiazolone azines and bis[o-(N-substituted N-formylamino)phenyl] disulfides as major products. Reactions of 1 with some substituted diazomethanes gave the corresponding unsymmetrical azine N-monoxides (16) or azines (17) depending on the structure of the diazomethane.
  • Hiroyoshi Kamogawa, Shinya Okabe, Masato Nanasawa
    1976 Volume 49 Issue 7 Pages 1917-1919
    Published: 1976
    Released: April 19, 2006
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    Several acetal monomers and a hemiacetal monomer of vinylbenzaldehydes were synthesized from the reaction with some perfume alcohols in the presence of p-toluenesulfonic acid as an acid catalyst. It was found that primary alcohols such as citronellol and geraniol with the exception of cinnamyl alcohol afforded acetal monomers in high yields, secondary alcohols such as borneol and menthol in low yields, with the latter affording only hemiacetal monomer, and linalool, a tertiary alcohol, neither acetal nor hemiacetal monomers. The radical polymerizations of the acetal and hemiacetal monomers synthesized provided soluble polymers which easily release perfume alcohols under mild acidic conditions.
  • Suketaka Ito, Yumo Tanaka, Akikazu Kakehi, Ken-ichi Kondo
    1976 Volume 49 Issue 7 Pages 1920-1923
    Published: 1976
    Released: April 19, 2006
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    2,5-Disubstituted tetrazoles are obtained in good yields by the reaction of phenylsulfonylhydrazones of aromatic aldehydes (and cinnamaldehyde) with arenediazonium salts. From the synthetic viewpoint for tetrazoles, this method may be of high synthetic utility on account of the availability of starting materials, the simplicity of procedure, and higher yields.
  • Takayuki Kawashima, Naoki Inamoto
    1976 Volume 49 Issue 7 Pages 1924-1927
    Published: 1976
    Released: April 19, 2006
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    2,4-Diethoxy-1,3-diphenyl-1,3,2,4-diazadiphosphetidine (1a) reacted with benzil, benzalacetophenone, and α-phenyliminobenzyl phenyl ketone in refluxing o-dichlorobenzene to give 2-ethoxy-3,4,5-triphenyl-Δ4-1,3,2-oxazaphospholine 2-oxide, 2-ethoxy-1,3,5-triphenyl-Δ4-1,2-azaphospholine 2-oxide, and 2-anilino-3,4,5-triphenyl-Δ4-1,3,2-oxazaphospholine 2-oxide, respectively. Under mild conditions, reaction of 1a with benzil gave a Ramirez type 1:2 adduct, which thermally decomposed to give oxazaphospholine derivatives.
  • Hajime Matsushita, Masao Noguchi, Sadao Yoshikawa
    1976 Volume 49 Issue 7 Pages 1928-1930
    Published: 1976
    Released: April 19, 2006
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    Hydrolysis of immonium salts of enamines consisting of optically active amines and racemic α-substituted carbonyl compounds with hydrochloric acid gave the corresponding optically active carbonyl compounds. The NMR spectra showed that the immonium salt is a mixture of two diastereomeric isomers. The mechanism of the optical activation is discussed on the basis of an isotope labeling experiment and the NMR spectra.
  • Shigeo Tanimoto, Ryôzô Taniyasu, Tôru Takahashi, Tak ...
    1976 Volume 49 Issue 7 Pages 1931-1936
    Published: 1976
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The reactions of several gem- and vic-polychloroethanes containing 3–5 Cl atoms with PhONa in dimethyl sulfoxide and with PhSNa in N,N-dimethylformamide were examined. Either the mono-, di-, or tetra-substituted compounds of polychloroethylenes were obtained as the main products, depending on the kinds of substrates as well as on the amounts of the bases. The reaction products from polychloroethylenes with 2–4 Cl atoms were also examined under similar conditions for the sake of comparison. Reasonable reaction paths leading to these products were given.
  • Shosuke Yamamura, Yukimasa Terada
    1976 Volume 49 Issue 7 Pages 1937-1939
    Published: 1976
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Tetrahydroasatone (3) and tetrahydroisoasatone (4) both are pretty unstable to various kinds of acid. Action of 6M·HCl–AcOH on the former converted it to the naphthalene-type compound (5) in high yield, whose structure was determined on the basis of its spectral data. In the case of tetrahydroisoasatone, twofold Wagner-Meerwein rearrangements take place, leading to the formation of the isomer-A (9), further rearrangements of which give rise to the bisnordiadamantane-type isomer-B (10a).
  • Shosuke Yamamura, Yukimasa Terada, Yuh-Pan Chen, Mina Hong, Hong-Yen H ...
    1976 Volume 49 Issue 7 Pages 1940-1948
    Published: 1976
    Released: April 19, 2006
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    Isolation and structures of two novel neolignans, asatone (1) and isoasatone (2), are described. The structure of the latter, established by means of an X-ray crystallographic analysis of its dihydroxy derivative, is in full agreement with its chemical and spectral data. From a biogenetic point of view, furthermore, thermal and photochemical reactions of these neolignans and their derivatives were carried out. In particular,asatone was photochemically converted into isoasatone.
  • Hirochika Sakuragi, Shun-ichi Ishikawa, Toshihiro Nishimura, Masayuki ...
    1976 Volume 49 Issue 7 Pages 1949-1954
    Published: 1976
    Released: April 19, 2006
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    Irradiation of benzophenone O-acetyloxime, O-phenylacetyloxime, O-benzoyloxime, and O-(p-chlorobenzoyl)oxime in benzene, toluene, chlorobenzene, or o-xylene effected aromatic substitution on the solvent molecules by diphenylmethaniminyl radicals to give N-diphenylmethylenearylamines only when benzoxyl or p-chlorobenzoxyl radicals were generated concurrently. A mechanism involving a participation of the sufficiently long-lived acyloxyl radicals is proposed for the iminylation reaction on the basis of the reactivity patterns in this substitution reaction. o-Phenylbenzophenone O-benzoyloxime was also photolyzed in benzene to give 9-phenylphenanthridine, the intramolecular cyclization product of 2-biphenylylphenylmethaniminyl radicals.
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