Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 49 , Issue 9
Showing 1-50 articles out of 75 articles from the selected issue
  • Hisashi Ueda
    1976 Volume 49 Issue 9 Pages 2343-2345
    Published: 1976
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The simulation of the ESR spectra of the perylene cation formed on the surface of silica gel (with MoO3), silica–alumina, and γ-alumina (with MoO3) was studied. These oxides were pretreated in a vacuum of 10−5 Torr and at 300 °C, and were then brought into contact with a purified perylene solution in benzene. The main parameters which determine the shape of spectra were investigated. By comparing the experimental spectra with the simulated ones, it was concluded that unpaired electron-spin densities on the carbon atoms of the perylene cation are identical to those of the perylene cation in the H2SO4 solution. However, the number of γ-protons which have spin-nuclear interactions with the unpaired electron is three or less. It was found that a considerable part of the line-width is caused by g-unisotropies. If the perylene cation is bound more strongly on the surface, more g-unisotropy is observed and the half-width becomes wider. When the perylene cation is prepared in the air, O2 and H2O molecules coordinate to the perylene cation formed. It was found that the complex cations thus formed have different g-unisotropies and that the ESR spectrum of this cation mixture is structureless, smooth, and a continuous curve.
  • Tsunetake Fujiyama, Masao Kakimoto
    1976 Volume 49 Issue 9 Pages 2346-2350
    Published: 1976
    Released: April 19, 2006
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    The Raman intensities of some fundamental lines of 1,2-dichloroethane and 1,2-dibromoethane and related molecules with internal rotation axes were observed at various temperatures. The observed relative intensities were corrected for some systematic errors expected in the intensity measurement. The importance of a local-field effect was emphasized. The van’t Hoff plot of the observed intensity ratios of the trans and gauche isomers showed the existence of strong intermolecular interactions in the liquid phase. The intermolecular interaction energy in the liquid phase was theoretically estimated from both the macroscopic and microscopic points of view. The usefulness of a dipole-dipole interaction model was emphasized.
  • Katsuomi Takehira, Toshio Ishikawa
    1976 Volume 49 Issue 9 Pages 2351-2357
    Published: 1976
    Released: April 19, 2006
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    The catalytic activities of various binary oxides containing vanadium for the liquid-phase oxidation of cyclohexene have been studied, in comparison with those of one component oxides and soluble metal acetylacetonates. The reaction was carried out at 60 °C in benzene solvent. The distribution of reaction products suggests the occurrence of autoxidation and epoxidation when vanadium system catalysts are used. Among the binary catalysts, V–Cr and V–Mo systems showed relatively high specific activities, especially high activity being obtained by the former systems calcined at a low temperature. It seems that cyclohexene oxide is formed mainly by two successive catalytic processes, i.e., the formation of cyclohexenyl hydroperoxide by autoxidation and the selective oxidation of cyclohexene with the hydroperoxide. The machanism of epoxidation was confirmed by the reaction of cyclohexene with t-butyl hydroperoxide in the presence of V–Cr catalyst.
  • Jiro Tanaka, Masashi Tanaka, Takashi Kawai, Teruhiro Takabe, Osamu Mak ...
    1976 Volume 49 Issue 9 Pages 2358-2373
    Published: 1976
    Released: April 19, 2006
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    Electronic spectra of several TCNQ, complexes have been measured with single crystals by the transmission method. The assignment of electronic transitions are presented based on the electronic structure of the crystals. The molecular viewpoint is stressed in a theoretical treatment. The spectra are interpreted in terms of the charge transfer between TCNQ species and the local transitions of TCNQ and the donor molecules. It is shown that the electronic structure of the crystal may be deduced from the spectral analysis. The magnetic and electric properties of several conducting TCNQ complexes are discussed by this model with the wavefunctions determined by a theoretical calculation and the analysis of the spectral results.
  • Tetsuo Morimoto, Hiromitu Naono, Kuniji N\={o}so, Yasumasa Shigetomi
    1976 Volume 49 Issue 9 Pages 2374-2376
    Published: 1976
    Released: April 19, 2006
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    The applicability of flow micro-calorimetry to the measurement of ion exchange heat was investigated by use of H-form resin of Dowex 50W×4 having a low degree of cross-linking. It was found that: accurate measurement of ion exchange heat can be performed by means of flow micro-calorimetry; the data obtained include additional heat effects such as heats of invasion and dilution; the effects can be exactly analyzed experimentally and eliminated for calibrating the data of pure ion exchange heat. The ion exchange heat thus obtained for the H-form resin and alkali metal ions was found to agree with the results obtained by means of heat of immersion measurements.
  • Takashi Okada, Shigeru Nagase, Kizashi Yamaguchi, Takayuki Fueno
    1976 Volume 49 Issue 9 Pages 2377-2378
    Published: 1976
    Released: April 19, 2006
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    A procedure is described which enables to trace the variations of electronic configuration of molecular systems undergoing structural deformation. The mapping operator proposed by Trindle is used to derive a reference set of molecular orbitals which is suitable to the analysis of the wave functions for deformed molecules. The method has been applied to the twisting of ethylene as well as the electrocyclic reactions of butadiene. The results corroborate Bader’s symmetry requirement for the electronic excitations accompanying nuclear displacements.
  • Kazuhiro Endo, Shigeru Yamauchi, Kazuo Fueki, Takashi Mukaibo
    1976 Volume 49 Issue 9 Pages 2379-2383
    Published: 1976
    Released: April 19, 2006
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    In order to contribute to the study of the thermodynamics of point defects in ionic crystals, the nonstoichiometry, δ, of Pr1−yGdyO1.5+δ (y=0, 0.1, 0.2, and 0.4) with a wide nonstoichiometric composition range was measured as a function of the oxygen partial pressure. Assuming that excess oxygen ions preferentially occupy Z-sites of the bixbyite structure and that the Pr3+ and Pr4+ ions are distributed on cationic sites at random, the equilibrium constant, K, was calculated for
    2Pr^4++O_z^2-=2Pr^3++V_z+\frac12O_2
    It was found that lnK changes with δ in the relation;
    lnK=A+Bδ+Cδ^2
    The parabolic dependence of lnK on δ is interpreted in terms of the changes in the energy of the defect formation and in the interaction energy between defects with the volume.
  • Koichi Honda, Akira Yabe, Hideaki Tanaka
    1976 Volume 49 Issue 9 Pages 2384-2390
    Published: 1976
    Released: April 19, 2006
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    The photocleavage reaction of naphthalene perp-fused cyclobutanes (I–IV) in rigid media is found to proceed from one (or several) of the upper triplet states. Nearly planar cyclobutanes (I–III), which were photocleaved in fluid solutions to yield acenaphthylene and 1,2-ethylenedicarboxylic acid derivatives, afford 1,8-naphthalenediacrylic acid derivatives in addition to the above products by irradiation in rigid media. Twisted cyclobutane (IV), which is considerably stable to irradiation in fluid solutions, was also photocleaved in rigid media to give dimethyl 1,8-naphthalenediacrylate. An NMR study shows that the formation of these diacrylic acid derivatives from I–IV in rigid media is considerably stereospecific. The yield ratio of diacrylic acid derivatives to acenaphthylene formed in the photolysis of I–III is independent of the viscosity of the solvents, i.e., of the matrix rigidity, but depends on other properties of the rigid solvents. A concerted mechanism is proposed for the photocleavage reaction of I–IV in rigid media in order to explain the photochemistry different from that in fluid solutions.
  • Mitsunori Tsuda, Hidekazu Touhara, Koichiro Nakanishi, Nobuatsu Watana ...
    1976 Volume 49 Issue 9 Pages 2391-2396
    Published: 1976
    Released: April 19, 2006
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    CNDO/2 calculations were carried out for the hydrogen bonded complexes between hydrogen fluoride (HF) and a series of organic compounds having a carbonyl group as a proton acceptor. Infrared spectral measurements were also made to obtain the frequency shifts of H–F stretching vibration, ΔνHF, for the same complexes in dilute carbon tetrachloride solution. Optimum geometry was obtained on the assumption of planar complex. For all the carbonyl compounds used, the interatomic angles, ∠C–O···H, were 120°–123° for the most stable conformation. The changes in the distance between H atom and F atom, ΔRHF, were in good correlation with ΔνHF obtained from IR spectra. Calculated hydrogen bond energies were also in good correlation with ΔνHF, though their absolute values were somewhat larger than those derived from experimental observations. This indicates that the CNDO/2 calculations give relatively correct enthalpy values for the hydrogen bond complexes of a given donor with a series of molecules having a common acceptor group. Other correlations of ΔνHF with properties expected to change with the hydrogen bond formation were also confirmed. These include the energies of each bond obtained by the partitioning of the total energy and the force constant of H–F bond. The electron population on the oxygen atom and other atoms participating in the hydrogen bond formation, the charge transfer, ionization potentials and dipole moment enhancements were also calculated and discussed in terms of the measure of hydrogen bond strength.
  • Katsutoshi Ohkubo, Toshiaki Yoshida, Katsumi Tomiyoshi
    1976 Volume 49 Issue 9 Pages 2397-2402
    Published: 1976
    Released: April 19, 2006
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    INDO-SCF calculations were performed on several protonated compounds, HCHOH+ CH3CHOH+, (CH3)2COH+, HCO2H2+, CH3CO2H2+, and CH3OH2+, and also on the corresponding parent molecules in order to investigate their conformations and electronic structures. Geometric optimization resulted in reasonable conformations as compared with the previous ab initio calculations and in sufficient magnitudes of the energy differences between the rotational isomers in comparison with the NMR observations. The change in the electronic structures of the parent molecules due to protonation is also discussed by paying attention to the polarization caused by electron delocalization, hybridization at the proton-bound oxygen atom, the protonation energy, and the ionization potentials.
  • Kohji Tadasa, Naomi Imai, Tetsuo Inaba, Yutaka Kubokawa
    1976 Volume 49 Issue 9 Pages 2403-2406
    Published: 1976
    Released: April 19, 2006
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    The effect of NO addition on the thermal decomposition of CH3OCH3 has been studied at 500 °C. The rate of pyrolysis decreases markedly when the amount of NO is small, but increases linearly with increase in amount. Acceleration of pyrolysis was studied. Major reaction products are CH4, CH2O, CO, H2O, and N2, the minor ones being H2, N2O, and C2H6. The quantities of all the products were determined under different conditions except CH2O and H2O. It was found that the rate of formation is nearly of first order with respect to both NO and CH3OCH3. A reaction scheme is proposed. It is suggested that the rate of decomposition is nearly equal to that of the second order reaction NO+CH3OCH3→HNO+CH3OCH2.
  • Kentaro Murano, Yusuke Kamura, Hiroo Inokuchi
    1976 Volume 49 Issue 9 Pages 2407-2409
    Published: 1976
    Released: April 19, 2006
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    The methyl viologen film evaporated at about 250 °C has a violet color, and its electronic absorption spectrum resembles that of the enzymatically reduced methyl viologen. The evaporated film becomes colorless upon the introduction of air. By means of the photoemission spectroscopical method, a very low ionization potential, 3.6 eV, was obtained for the evaporated methyl viologen film. The character of the evaporated methyl viologen is a free-radical one, and its specific resistivity is very low as compared with other organic radicals.
  • Kenji Kubota, Kenji Kubo, Kazuyoshi Ogino
    1976 Volume 49 Issue 9 Pages 2410-2418
    Published: 1976
    Released: April 19, 2006
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    A new light-scattering optical cell was designed in order to perform light-scattering measurements at various temperatures and under pressures up to 400 kg/cm2. The second virial coefficients and the radii of gyration were determined at high polymer dilutions for polydimethylsiloxane in cyclohexyl bromide at 27.0, 36.5, 47.2, and 56.2 °C, in benzene and toluene at 27.0 °C, and in chlorobenzene at 30.0 °C. The method employed to determine the dimensions of the polymer is described. By a series of measurements of polydimethylsiloxane solutions, it is shown that the second virial coefficients, the radii of gyration, and the fundamental thermodynamic properties of the solutions depend on the pressure. The correlation between values of A2 and ⟨S21⁄2 shows that pressure influences these quantities through its effect on the polymer-solvent interaction parameter, χ or z. The values of the relative partial molar excess volume were calculated directly from the data. The obtained data were compared with the excluded volume theories and the corresponding state theories; the agreement was fair.
  • Isao Takayanagi, Koichi Kobayashi, Keiko Hachisuka, Tsunetaka Sasaki
    1976 Volume 49 Issue 9 Pages 2419-2423
    Published: 1976
    Released: April 19, 2006
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    The removals of MnO4 and Fe3+ ions from an aqueous solution by the combined use of silicate ions(SiO32−) and a cationic surfactant, hexadecyltrimethylammonium chloride (HTAC), were studied by means of ion flotation techniques. The effect of variables such as pH, the surfactant concentration, and the order of addition of the reagents on the floatability of the ions were studied. More than 98 and 97% of the MnO4 and Fe3+ ions, respectively, could be floated under the optimum conditions. The optimum composition of SiO32− and HTAC was found to be about 0.9 in mole fraction of SiO32− for both systems. It was also found that the order of the addition of the reagents markedly affects the floatability. Further, a schematic model of flotation was proposed, taking account of the compositions of the sublate. MnO4 and Fe3+ ion flotations differed from each other in that MnO4 ions combine with SiO32− ions through the double layer of HTAC molecules, which are subsequently coagulated and floated by HTAC, while Fe3+ ions or polynuclear Fe3+ ions combine directly with SiO32− ions, which are subsequently coagulated and floated by HTAC.
  • Yukio Kubota, Yoshio Eguchi, Kazumasa Hashimoto, Masaaki Wakita, Yumi ...
    1976 Volume 49 Issue 9 Pages 2424-2426
    Published: 1976
    Released: April 19, 2006
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    The strong binding of acridine dyes with DNA was studied by means of equilibrium dialysis. Ten acridine derivatives were used to elucidate the effect of the dye structure on the nature of strong binding. In the strong binding, up to one dye molecule per 4–6 nucleotides was bound with the change of free energy in 5–9 kcal mol−1. The introduction of bulky groups to the 10 or 3,6-positions of the acridine ring led to a marked decrease in both the association constant and the maximum number of binding sites per DNA phosphate. These findings suggest that, when a dye molecule is intercalated, the dye is located in such a way that the bulky groups attached to the acridine ring produce some steric hindrance to the binding.
  • Yonezo Maeda, Yoshimasa Takashima, Yuzo Nishida
    1976 Volume 49 Issue 9 Pages 2427-2432
    Published: 1976
    Released: April 19, 2006
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    Iron complexes with the Schiff bases of quinolinecarbaldehyde and pyridinecarbaldehyde were prepared. Mössbauer spectra and magnetic susceptibilities of the compounds, Fe(pipa)2(NCS)2, Fe(pa)2(NCS)2, Fe(pot)2(NCS)2·1/2CHCl3, Fe(ppt)2(NCS)2, Fe(ppca)2(NCS)2, and Fe(ppa)2(NCS)2 were studied in the temperature range between 298 and 27 K. It was found that these complexes showed an incomplete 5T2-1A1 transition in the solid. The compound Fe(poca)2(NCS)2 also showed a similar phenomenon. The observations of the behavior of the various complexes indicated that the magnetic changeover from spin-paired to spin-free would be closely associated with a modification of the crystal lattice. The FeL′Cl2(L′: the Schiff bases of quinolinecarbaldehyde) were found to have distorted tetrahedral structures.
  • Katsumi Yamamoto, Kousaburo Ohashi
    1976 Volume 49 Issue 9 Pages 2433-2436
    Published: 1976
    Released: April 19, 2006
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    The rate of the reaction between chromium(III) ion and ethylenediamine-N,N,N′,N′-tetraacetate was found to be accelerated upon the addition of a large excess of hydrogen peroxide. Under such a condition the rate of CrIII(edta)(H2O) formation shows a first-order dependence on the concentrations of hydrogen peroxide and chromium(III) ions, but is independent of the concentration of EDTA. The rate of CrIII(edta)(H2O) formation catalyzed by the hydrogen peroxide increases with an increase in the pH and decreases with an increase in the acetate ion concentration. The kinetic study suggested that the initiation of the reaction takes place as follows: Cr(III)+H2O2→Cr(IV)+OH·+OH The reaction mechanism of the hydrogen-peroxide catalysis is discussed in terms of the formation of the chromium(IV)– and /or the chronium(V)–EDTA complex in the course of the reaction. It was found that monohydroxochromium(III) is much more reactive than the chromium(III) ion toward hydrogen peroxide.
  • Souichi Nakano, Jukichi Honboh, Noriake Urabe
    1976 Volume 49 Issue 9 Pages 2437-2439
    Published: 1976
    Released: April 19, 2006
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    A radiochemical neutron activation procedure has been designed for the determination of mercury in soils. After the irradiation of 100 mg of soil it was decomposed with a hydrofluoric and perchloric acid mixture in a platinum crucible, and the mercury was separated radiochemically by solvent extraction from sulfuric acid·potassium iodide media into toluene, followed by precipitation as a sulfide. The radioactivity of 197Hg was measured by using a Ge(Li) detector. The chemical yield, as determined by atomic absorption spectrophotometry, was high enough, and the precision was satisfactory. The detection limit is estimated to be 1–2 ppb [(1–2)×10−10 g] by this method. The above procedure was applied to the determination of mercury in soils sampled in the Kumamoto and Minamata districts and in between.
  • Kousaburo Ohashi, Morito Matsuzawa, Eichi Hamano, Katsumi Yamamoto
    1976 Volume 49 Issue 9 Pages 2440-2444
    Published: 1976
    Released: April 19, 2006
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    The kinetics of the oxidation of CoII–EDTA and CoII(bpy)32+ by the peroxodisulfate ion (S2O82−) in acidic media have been studied spectrophotometrically; EDTA and bpy represent ethylenediamine-N,N,N′,N′-tetraacetic acid and 2,2′-bipyridine respectively. The stoichiometry of the reactions of CoII–EDTA with the peroxodisulfate ion was 2CoII–EDTA+S2O82−=2CoII(edta)+2SO42−. The rate for the oxidation of CoII–EDTA by the peroxodisulfate ion is independent of the concentration of CoII–EDTA, but first-order dependent with respect to the peroxodisulfate-ion concentration. The rate law is d[CoII(edta)]/dt=2k[S2O82−]. The rate-determining step must be the decomposition of S2O82− into 2SO4\ ewdot. The first-order rate constant, the activation enthalpy, and the activation entropy are 5.5×10−8 s−1, 24 kcal mol−1, and −12 eu respectively at pH 3.60, 25 °C, and I=0.50 (NaClO4). Two moles of CoII(bpy)32+ are oxidized by one mole of the peroxodisulfate ion. For the oxidation of CoII(bpy)32+, the following reaction path and rate law were proposed:
    & Co^II(bpy)_3^2++S_3O_8^2-\oversetk_e\ ightleftarrows[Co^II(bpy)_3^2+·S_2O_8^2-]\xrightarrowkCo^II(bpy)_3^3++SO_4^2-+SO_4^\ ewdot
    & Co^II(bpy)_3^2++SO_4^\ ewdot\xrightarrowfastCo^III(bpy)_3^3++SO_4^2-
    & \fracd[Co^II(bpy)_3^3+]dt=\left{\frac2k·K_e1+K_e[S_2O_8^2-]\ ight}[S_2O_8^2-][Co^II(bpy)_3^3+]_T
    At pH 3.60, 25 °C, and I=0.50 (Na2SO4), the rate constant, k, and the equilibrium constant, Ke, are 0.53 s−1 and 5.6 M−1 respectively. The difference in the rate law and mechanism between CoII–EDTA and CoII–(bpy)32+ may come from the difference in charge on the cobalt(II) complexes.
  • Kashiro Kuroda, Kouzou Yoshitani, Kazufumi Kunigita, Yukiko Kamiiba, K ...
    1976 Volume 49 Issue 9 Pages 2445-2450
    Published: 1976
    Released: April 19, 2006
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    In six kinds of mixed ligand acetylacetonatocobalt(III) complexes ((NH3)4-, (en)2-, α-trien-, β-trien-, fac(N)-i-dtma-, and mer(N)-i-dtma-complexes), the methine hydrogen of the coordinated acetylacetonate ion has been substituted with chlorine, bromine, and iodine, and in five of them excepting the mer(N)-i-dtma complex, it has been substituted with a nitro group. The halogenated and the nitrated complexes were isolated and identified by means of electronic absorption spectra and NMR spectra. The effects of the substitutions on the properties and the characteristics of the substitution reactions are described and discussed.
  • Sadayuki Himeno
    1976 Volume 49 Issue 9 Pages 2451-2455
    Published: 1976
    Released: April 19, 2006
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    The normal pulse polarogram of Fe(II) showed a double-wave behavior in an unbuffered solution containing iodate. The results of pulse polarographic and cyclic voltammetric studies indicate that colloidal Fe(OH)2 formed by the reaction between aqua-Fe(II) and OH arising from the iodate reduction is responsible for the second wave. A catalytic wave was observed in the presence of chlorate in Tast polarography. The catalytic wave which appears to be a polarographic maximum, has an abnormal form, in which the current increases at every second or third drop because of the depletion of colloidal Fe(OH)2 around the electrode. The catalytic current is due to the reaction of chlorate with colloidal Fe(OH)2 formed in the vicinity of the electrode.
  • Yoshinobu Shiokawa, Akiko Sato, Shin Suzuki
    1976 Volume 49 Issue 9 Pages 2456-2460
    Published: 1976
    Released: April 19, 2006
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    The hydrolytic behavior of zirconium(IV) and niobium(V) in a hydrochloric acid solution was studied using light scattering measurements. It is found that the species of zirconium(IV) have a degree of polymerization of 3 and a charge per monomer unit of 1.5 in a 1.5 M hydrochloric acid solution with [Cl]=1.7 M. Also, it was found that for a chloride ion concentration of 11 M, the species of niobium(V) are monomeric in 8–11 M hydrochloric acid and colloidal below 8 M. The effect of standing time of the hydrochloric acid solution of niobium(V) was also investigated.
  • Hideyoshi Morita, Shigeru Shimomura, Shinichi Kawaguchi
    1976 Volume 49 Issue 9 Pages 2461-2464
    Published: 1976
    Released: April 19, 2006
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    Bis(3-hydroxy-2-methyl-4-pyronato) complexes of cobalt(II), nickel(II), copper(II), and zinc(II) have been prepared: CoL2(OH2)2, NiL2(OH2)2, CuL2, and [ZnL2(OH2)2]·1/2H2O. The 2,2′-bipyridine-(bpy) and 1,10-phenanthroline(phen) adducts of these complexes were also synthesized: CoL2(bpy), CoL2(phen), NiL2(bpy), ZnL2(bpy), and ZnL2(phen). Based on the magnetic, spectral, and thermogravimetric data, the structures of these complexes are proposed: all of the cobalt(II), nickel(II), and zinc(II) complexes are octahedral, and CuL2 is square planar. The NMR spectra of the zinc(II) complexes are discussed.
  • Mutsuo Kodama, Eiichi Kimura
    1976 Volume 49 Issue 9 Pages 2465-2468
    Published: 1976
    Released: April 19, 2006
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    logK, ΔH and ΔS values were polarographically determined for the interaction in aqueous solution of Pb2+ and Tl+ ions with a cyclic polyether, 1,4,7,10,13,16-hexaoxacyclooctadecane(18-crown-6), and a linear polyether, tetraethylene glycol dimethyl ether (tetraglyme). The stability constant of a 1:1 Pb2+ complex with the macrocyclic ligand is four figures higher than that with the linear ligand. This macrocyclic effect is explained in terms of entropy.
  • Mitsunori Tanaka, Michiyo Kitaoka, Hisashi Okawa, Sigeo Kida
    1976 Volume 49 Issue 9 Pages 2469-2473
    Published: 1976
    Released: April 19, 2006
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    Copper(II) and nickel(II) complexes of the 3-formylsalicylic acid-diamine Schiff bases, H4fsaen, H4fsapn, H4fsatn, H4fsaph, and H4fsach, where en, pn, tn, ph, and ch denote ethylenediamine, propylenediamine, trimethylenediamine, o-phenylenediamine, and 1,2-cyclohexanediamine respectively, have been obtained and characterized. Binuclear copper(II) complexes, Cu2(fsaen)·2H2O, Cu2(fsapn)·2H2O, Cu2(fsatn)·2H2O, Cu2(fsaph)·H2O, and Cu2(fsach)·2H2O, show a strong antiferromagnetic spin-exchange interaction between metal ions, −2J values being more than 555 cm−1. It was revealed that Ni2(fsaen)·3H2O, Ni2(fsapn)·3H2O, Ni2(fsaph)·5H2O, and Ni2(fsach)·3H2O are novel binuclear complexes composed of one paramagnetic and one diamagnetic nickel(II) ions. On the other hand, Ni2(fsatn)·5H2O is a binuclear complex of paramagnetic nickel(II) ions. Its magnetism obeys the Curie-Weiss law in the range from liquid nitrogen temperature to room temperature with the Weiss constant of −40 K.
  • Makoto Watanabe, Shoji Sato, Hajime Saito
    1976 Volume 49 Issue 9 Pages 2474-2478
    Published: 1976
    Released: April 19, 2006
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    The hydrolysis of sodium pyro-, tripoly-, trimeta-, and tetrametaphosphates was run in water, aqueous ethanol, aqueous glycerol, aqueous acetonitrile, aqueous dimethyl sulfoxide, and aqueous tetrahydrofuran at various pH values and temperatures. The initial concentration of the phosphates was 0.025 mol/l. The hydrolysis of the poly- and metaphosphates followed first-order kinetics with respect to the concentration of the phosphate, under all conditions studied. The hydrolysis of sodium pyro- and tripolyphosphates was an acid-catalyzed reaction and that of sodium trimeta- and tetrametaphosphates was an acid- and base-catalyzed reaction. In acidic solutions, the rate of hydrolysis of the poly- and metaphosphates in water was slower than that in any aqueous organic solution. It is concluded that the nucleophilicity of the water molecule in the aqueous organic solutions may increase on account of the interaction of the water molecule with the organic molecules. The hydrolysis of sodium pyro-, tripoly-, trimeta-, and tetrametaphosphates in acidic solutions is considered to be of the SN2 type, because the overall-reaction rate is highly dependent on the nucleophilicity of the water molecule. The solvent effect on the rate of hydrolysis of sodium tripolyphosphate in basic solutions was the same as that in acidic solutions and hence the mechanism of the hydrolysis of sodium tripolyphosphate in basic solutions may be the same as that in acidic solutions. The rate of hydrolysis of sodium trimeta- and tetrametaphosphates in a basic water solvent was much faster than that in basic aqueous ethanol and basic aqueous dimethyl sulfoxide and was largely slower than that in basic aqueous glycerol. Consequently, the mechanism of the hydrolysis of sodium trimeta- and tetrametaphosphates in basic solutions seems to differ from that in acidic solutions. The acceleration of the rate of hydrolysis of the metaphosphates by the organic molecules depends significantly upon the activation energy. The activation energy of the hydrolysis of sodium pyro-, tripoly-, trimeta-, and tetrametaphosphates was 17–34 kcal/mol in the pH range of 1.0–12.2 and increased with an increase in the pH value of the phosphate solution in water and aqueous ethyl alcohol solventss.
  • Kingo Mizuno, Giroku Miyatani
    1976 Volume 49 Issue 9 Pages 2479-2480
    Published: 1976
    Released: April 19, 2006
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    The absorbance of the water soluble red complex of palladium(II) and 4-(2-pyridylazo)resorcinol (PAR) was measured at 513 nm. Coned hydrochloric acid and tin(II) chloride were added to an aliquot of the red solution, and both the palladium complex and the excess of PAR were decolorized by the reduction of the azo radical of PAR. The absorbance of the platinum complex with tin(II) chloride was measured at 403 nm.
  • Shigenobu Funahashi, Motoharu Tanaka
    1976 Volume 49 Issue 9 Pages 2481-2484
    Published: 1976
    Released: April 19, 2006
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    The substitution reactions of some Ni(II)–L complexes (L: ethylenediamine-N,N′-diacetate, edda2−·, nitrilo-triacetate, nta3−·, iminodiacetate, ida2−) with 4-(2-pyridylazo)resorcinol (H2par) have been studied spectrophoto-metrically at I=0.10. Rate constant k (mol dm−3, s) at 25°C, activation enthalpy ΔH\ eweq/kJ mol−1 and activation entropy ΔS\ eweq/J K−1 mol−1 are respectively: 1.7×103, 58.5 and 12.5 for k[Ni2+][Hpar]; 4.0×102, 51.8 and −22 for k[Ni(nta)][Hpar]; 1.0×103, 41.8 and −46 for k[(par)Ni(edda)][Hpar]; 2.7×10−4, 109 and 30 for k[(par)Ni(edda)2−]; 5.1×103, 88 and 17 for k[(par)Ni(Hedda)]; 1.7×103, 122 and 226 for k[Ni(ida)][Hpar]. In terms of activation parameters some discussions are made on the effect of coordinated ligands on the lability of leaving ligands and pre-equilibrium involving partial dissociation of leaving ligands.
  • Keiichi Ito, Hitoshi Oba, Minoru Sekiya
    1976 Volume 49 Issue 9 Pages 2485-2490
    Published: 1976
    Released: April 19, 2006
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    The Leuckart-Wallach reaction paths were investigated by means of catalytic reduction in the Leuckart-Wallach reaction system and on the basis of analogous formic acid reductions. It was determined that, in the early stage of the Leuckart-Wallach reaction, ammonia, amine and also formamide undergo addition reactions to carbonyl compounds. The addition of formamide catalyzed by formic acid plays a significant role only for the more reactive substrates such as benzaldehyde. The behaviors of plausible intermediates for the formic acid reduction are discussed on the basis of the data of similar formic acid reductions.
  • Tomoya Kitazume, Toru Otaka, Ryutaro Takei, Nobuo Ishikawa
    1976 Volume 49 Issue 9 Pages 2491-2494
    Published: 1976
    Released: April 19, 2006
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    4-Alkoxy-2,2-bis(trifluoromethyl)thietanes, 3 (R=Me and Et), were prepared by the reactions of 2,2,4,4-tetrakis(trifluoromethyl)-1,-dithietane with alkyl vinyl ethers in a KF–DMF system. A bimolecular condensation product, bis[4,4-bis(trifluoromethyl)thietan-2-yl]ether, 5, was obtained by the treatment of 3 with concentrated sulfuric acid. On the other hand, when treated with sulfur in DMF in the presence of diethylamine, 3 gave 5-alkoxy-3,3-bis(trifluoromethyl)-1,2-dithiolanes, 8, in rather good yields. Several reactions of these thietanes and 1,2-dithiolanes, including those with butyllithium, were examined.
  • Akira Yabe, Koichi Honda
    1976 Volume 49 Issue 9 Pages 2495-2499
    Published: 1976
    Released: April 19, 2006
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    The direct, triplet-sensitized, and low-temperature photolyses of 2,2′-diazidobiphenyl have been studied. The direct irradiation afforded 4-azidocarbazole, and the triplet sensitization resulted in the predominant formation of the azo dimer, accompanied by a low yield of benzo[c]cinnoline. The photolysis in a rigid matrix at 77 K afforded benzo[c]cinnoline quantitatively. The mechanism for its preferential formation in low-temperature matrix photolysis is discussed, and we propose a biphotonic process involving a dinitrene via a mononitrene.
  • Nanao Watanabe, Sakae Uemura, Masaya Okano
    1976 Volume 49 Issue 9 Pages 2500-2502
    Published: 1976
    Released: April 19, 2006
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    The reaction of primary and secondary alkyl iodides and bromides with Hg(OAc)2 and HgCl2 in tetrahydrofuran (THF) affords the THF-incorporated compounds (1), RO(CH2)4X [X=OAc and Cl, respectively], in good yields. When HgBr2 and aqueous or alcoholic Hg(ClO4)2 were used as mercury(II) salts, the yields of 1(X=Br, OH, and OR′) were low. Similar treatment with HgI2 gave scarcely any 1. A reaction scheme which involves O-alkyltetrahydrofuranium ion as the intermediate is proposed for the formation of 1.
  • Fumio Toda, Eishiro Todo
    1976 Volume 49 Issue 9 Pages 2503-2505
    Published: 1976
    Released: April 19, 2006
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    The photolysis of the title methylenecyclobutenone (1) and 2-bromomethylenecyclobutanone (9) in MeOH afforded 4,4-diphenyl-3-(2,2-diphenylvinyl)-2-buten-4-olide (5) and 3,3,5-triphenyl-1,3-dihydronaphtho[1,2-c]-furan-2-one (11) respectively. The photolysis of 1 and 9 in benzene, however, afforded 4,4-diphenyl-3-(diphenylvinylidene)-4-butanolide (2), and bromo-derivative of 5 (8) and 11 respectively. The thermolysis of 1 and 9 in o-xylene afforded 2 and 2-bromo derivative of 5(10) respectively. The mechanisms of these reactions were discussed. The solvent effect on the photolysis of 1 and 9 was also discussed.
  • Juji Yoshimura, Masaharu Iwakawa, Yoshio Ogura
    1976 Volume 49 Issue 9 Pages 2506-2510
    Published: 1976
    Released: April 19, 2006
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    As the attempted substitution of methyl 4-deoxy-2,3-di-O-mesyl-6-O-trityl-α-D-xylo-hexopyranoside with sodium azide gave the unsaturated compound: methyl 2,3,4-trideoxy-6-O-trityl-α-D-glycero-hex-2-enopyranoside (4), benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-mannopyranoside was used as the starting material, which was converted into benzyl 2-acetamido-2-deoxy-3-O-mesyl-6-O-trityl-α-D-mannopyranoside (10). For the deoxygenation of C-4 position, chlorination of 10 with sulfuryl chloride gave unexpectedly benzyl 3′-O-mesyl-6′-O-trityl-α-D-talopyranosid [2′,3′,4′; 4,5,6]-2-methyl-4,5-dihydro-6H-oxazine, due to the anchimeric effect of the C2-axial acetamido group. However, previous change of the conformation of 10 by the substitution of C3-mesyl group with azido group gave successfully the corresponding chloro derivative (13). Reduction of 13 with tributyltin hydride gave the corresponding 3,4-epimino derivative (14), due to participation of initially hydrogenated azido group, but, catalytic hydrogenation of 14 gave the title compound as the main product.
  • Juji Yoshimura, Hiroaki Ando, Tadahide Sato, Shigeru Tsuchida, Hironob ...
    1976 Volume 49 Issue 9 Pages 2511-2514
    Published: 1976
    Released: April 19, 2006
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    Synthesis and properties of amido-bonded disaccharides containing hexosaminuronic acids are described. The amino group of D-gluco- and D-mannosamine derivatives was acylated with D-gluco- and D-mannosaminuronic acid derivatives by the dicyclohexylcarbodiimide method, and the protecting groups of a few products were removed. Some of them showed the additive patterns of components in their PMR spectra.
  • Fumio Toda, Yutaka Takahara
    1976 Volume 49 Issue 9 Pages 2515-2517
    Published: 1976
    Released: April 19, 2006
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    The title compound (15) which has two cyclobutadienes fused to a benzene ring, was synthesized by heating dl- (7), meso-3,8-di-t-butyl-1,5,6,10-tetraphenyldeca-3,4,6,7-tetraene-1,9-diyne (8), or E,Z,-3,4-bis (1-t-butyl-3-phenyl-2-propynylidene)-1,2-diphenyl-1-cyclobutene (12).
  • Nobuyuki Muramoto, Tameichi Ochiai, Masayuki Yoshida, Osamu Simamura
    1976 Volume 49 Issue 9 Pages 2518-2521
    Published: 1976
    Released: April 19, 2006
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    Decomposition of phenylpropioloyl peroxide and t-butyl phenylperoxypropiolate in cumene, toluene, and cyclohexane was investigated. Product analysis and kinetic study together with the findings that radicals separately generated caused the decomposition of these peroxides demonstrate of a new type of induced decomposition involving radical attack on the triple bond of these peroxides and subsequent β-scission.
  • Tameichi Ochiai, Yoshitsugu Usuda, Masayuki Yoshida, Osamu Simamura
    1976 Volume 49 Issue 9 Pages 2522-2525
    Published: 1976
    Released: April 19, 2006
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    Phenyl and benzyl radicals were found to induce decomposition of cinnamoyl peroxide or t-butylperoxycinnamate to give stilbene and 1,3-diphenylpropene, respectively. Similarly, t-butoxyl radicals caused t-butyl 2,3-diphenylperoxypropionate to decompose affording stilbene. A mechanism is proposed which involves a radical atttack on a substrate peroxide producing a radical carrying an odd electron on the carbon atom β to the carboxyl group and its subsequent collapse to final products by way of β-scission.
  • Tameichi Ochiai, Masayuki Yoshida, Osamu Simamura
    1976 Volume 49 Issue 9 Pages 2525-2528
    Published: 1976
    Released: April 19, 2006
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    Decomposition of t-butyl erythro- and threo-2,3-diphenylperoxybutyrate was examined in solution at 60 °C; there was no indication of induced decomposition taking place as is the case with t-butyl 2,3-diphenylperoxypropionate. Various hydrocarbons resulting from the reaction of the 1,2-diphenylpropyl radical in a variety of ways were identified in the product, and t-butyl 1,2-diphenylpropyl ether was found to be formed as cage recombination product in the threo/erythro isomeric ratio which depended on the stereochemistry of the starting peroxybutyrate.
  • Hisanobu Ogoshi, Ei-ichi Watanabe, Norihisa Koketsu, Zen-ichi Yoshida
    1976 Volume 49 Issue 9 Pages 2529-2536
    Published: 1976
    Released: April 19, 2006
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    The syntheses of alkylcobalt(III)octaethylporphyrins(OEP) via nucleophilic attack of the Co(I) complex to unsaturated compounds are reported. Olefins with an electron-withdrawing group and acetylenes react with Co(I)(OEP), whereas olefins with an electron-donating group such as propylene and cyclohexene are unreactive. A novel ring cleavage of cyclopropyl methy ketone initiated by Co(I)(OEP) affords alkylCo(III)(OEP). The reduction of cobalt(II) N-methyloctaethylporphyrin acetate results in intramolecular methyl migration from nitrogen to the central cobalt atom. Five-coordination has been established for the organocobalt(III)(OEP) complexes on the basis of their analytical, infrared and NMR data. Some anomalous behavior of the proton signals of the α-carbon atom in their NMR spectra has been discussed in terms of quadrupolar relaxation and electronegativity of the cobalt ion.
  • Klaus Albert, Karl-Michael Dangel, Anton Rieker, Hiizu Iwamura, Yuzo I ...
    1976 Volume 49 Issue 9 Pages 2537-2546
    Published: 1976
    Released: April 19, 2006
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    Thermolysis of asymmetric triazenes Ar–N=N–NH–R 1 produces anilines Ar–NH2 2, hydrocarbons R–H 3, and N-alkylated anilines Ar–NH–R 4 as the main reaction products. 1H- and 13C-CIDNP experiments show polarization of nuclei in Ar–NH2, Ar–NH–R, R–H and some additional products (especially ring alkylated anilines). These observations are in agreement with the formation of an intermediate radical pair [Ar–NH··R] which must have been formed via homolysis of the tautomeric form ArNH–N=N–R 1′. Temperature-dependent 13C-NMR spectra show a rapid equilibrium between 1 and 1′ at room temperature and above, the tautomeric form 1 being predominant. From the CIDNP spectra the signs of the 1H and 13C hyperfine couplings of aminyl radicals Ar–NH and alkyl radicals R. have been determined.
  • Toyoki Kunitake, Yoshio Okahata, Reiko Ando, Sumio Hirotsu
    1976 Volume 49 Issue 9 Pages 2547-2552
    Published: 1976
    Released: April 19, 2006
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    Salicylohydroxamic acid(SHA), N-methylsalicylohydroxamic acid(MSHA), and N-methylphthalohydroxamic acid(MPHA) were prepared and their acylation reactions with p-nitrophenyl acetate were studied in aqueous ethanol at 30 °C. Both the acidity and nucleophilicity of the hydroxamic acid group were affected by the functional ortho-substituents(–OH, –COOH). In particular, the undissociated hydroxamic acid group in the MPHA monoanion possessed nucleophilic reactivity. This was brought forth by the general base assistance of the adjacent carboxylate group, as confirmed by the presence of the solvent isotope effect of kHkD=2.5. Only the hydroxamate anion acted as the nucleophile in all other cases.
  • Sanshiro Komiya, Akio Yamamoto
    1976 Volume 49 Issue 9 Pages 2553-2559
    Published: 1976
    Released: April 19, 2006
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    Dihydridotetrakis(triphenylphosphine)ruthenium(II), RuH2(PPh3)4, reacts with olefins (ethylene, propylene, styrene and butadiene) to give olefin-coordinated complexes of the type, Ru(olefin)(PPh3)3 and equimolar amounts of their hydrogenation products per mol of the dihydride complex. The olefin coordinated with ruthenium can be exchanged with other olefins. Olefin-coordinated complexes easily react with molecular hydrogen to afford tetrahydridotris(triphenylphosphine)ruthenium, RuH4(PPh3)3, releasing alkane at room temperature. Under hydrogen atmosphere, catalytic hydrogenation of the olefins smoothly takes place with RuH2(PPh3)4. (Ethylene) tris(triphenylphosphine) ruthenium (0) reacts with methyl iodide to give propylene and a trace of bu adiere along with methane, ethylene, and small amounts of ethane and butenes. The formation of propylene suggests that oxidative addition involving cleavage of the C–H bond of ethylene to ruthenium giving a hydridovinyl complex may be taking place. Reactions of Ru(C2H4)(PPh3)3 with methyl-d3 iodide and ethyl iodide, and of Ru(C3H6)(PPh3)3 with methyl iodide were examined to test the generality of this type of reaction. The reaction of Ru(C2H4)(PPh3)3 with CD3I released CD4 and CD2H2 together with CD3H suggesting the involvement of α-hydrogen abstraction.
  • Takaaki Sonoda, Shinjiro Kobayashi, Hiroshi Taniguchi
    1976 Volume 49 Issue 9 Pages 2560-2566
    Published: 1976
    Released: April 19, 2006
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    The reactions of 1-aryl-2,2-bis(o-methoxyphenyl)vinyl halides (4)–(7) in 80% aqueous ethanol (80% EtOH), acetic acid (AcOH), or 70% aqueous N,N-dimethylformamide gave benzofurans (8)–(10), respectively. The kinetic results i.e., 1) first-order reaction rates, 2) large α-substituent effect (ρ=−4.12 against σ+), 3) large leaving group effect (kBtkCl=85 in 80% EtOH and 28 in AcOH) and 4) the solvent effect (m=0.53), are consistent with the formation of the intermediate vinyl cations (3) which are captured exclusively by the β-o-methoxyl group. In the reaction of vinyl bromide (7), the formation of 7–9% of benzofuran (11) results from the β-o-methoxyphenyl migration in the vinyl cation (17) followed by cyclization. The exclusive intramolecular cyclization of the vinyl cations is discussed in terms of the proximity effect of the β-o-methoxyl group.
  • Kensuke Shima, Tadatoshi Kubota, Hiroshi Sakurai
    1976 Volume 49 Issue 9 Pages 2567-2571
    Published: 1976
    Released: April 19, 2006
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    The photocycloaddition of propanal to 1,3-cyclohexadiene leads to oxetanes, as well as to the dimers of 1,3-cyclohexadiene. A mechanism of oxetane formation is proposed in which singlet excited propanal attacks a ground-state 1,3-cyclohexadiene to give a singlet complex with a charge-transfer character. The complex either decays to the ground-state reactants or reacts to give oxetanes. Quantum yield measurements and kinetic analysis show a rate constant of 4×109 M−1 s−1 for singlet complex formation from propanal and 1,3-cyclohexadiene in benzene. The quenching data of propanal fluorescence support such a mechanism.
  • Noboru Torimoto, Tadao Shingaki, Toshikazu Nagai
    1976 Volume 49 Issue 9 Pages 2572-2578
    Published: 1976
    Released: April 19, 2006
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    Ethoxycarbonyl nitrene, generated by the photolysis of ethyl azidoformate (I), were inserted preferentially into the α C–H bonds of cyclic ethers. The α C–H bonds of cyclic ethers were much more reactive than the corresponding C–H bonds of hydrocarbons for the insertion of the nitrene. In addition, the reactions in cyclic ethers with an alkyl group at the α-position gave unsaturated alkoxyurethanes via a cleavage of the ring C–O bond. It was found that the nitrene insertion into the α C–H bonds of cis- and trans-2,5-dimethyltetrahydrofurans proceeded non-stereospecifically, while the insertion into the C–H bonds of hydrocarbons proceeded stereospecifically. The formation of the alkoxyurethanes can be explained by a mechanism in which an O–N ylide is included as an intermediate of the nitrene reaction; the non-stereospecific insertion of the nitrene give support to this mechanism.
  • Shuzo Akiyama, Tateo Nomoto, Masahiko Iyoda, Masazumi Nakagawa
    1976 Volume 49 Issue 9 Pages 2579-2581
    Published: 1976
    Released: April 19, 2006
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    1,6,12,17-Tetraphenyl-2,4,13,15-tetrakisdehydro[22]annulene has been synthesized. The sparlingly soluble tetrakisdehydro[22]annulene was found to be conformationally stable and strongly diatropic.
  • Sakae Uemura, Akio Toshimitsu, Masaya Okano
    1976 Volume 49 Issue 9 Pages 2582-2584
    Published: 1976
    Released: April 19, 2006
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    Arylthallium(III) compounds react smoothly with various metal nitrites such as NaNO2, KNO2, and AgNO2in trifluoroacetic acid to give nitroarenes in good yields. It has been clarified that the reaction proceeds through substitution of thallium moiety by nitroso group at the (ipso) position where thallium was attached previously to aromatic ring to give nitrosoarenes, followed by their oxidation to nitroarenes.
  • Seiichiro Ogawa, Hitoshi Fujimori, Tetsuo Suami
    1976 Volume 49 Issue 9 Pages 2585-2586
    Published: 1976
    Released: April 19, 2006
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    The title compound has been prepared as an intermediate for the chemical synthesis of glycosides of 2,6-diamino sugar.
  • Shigeaki Muto, Yoshio Kamiya
    1976 Volume 49 Issue 9 Pages 2587-2589
    Published: 1976
    Released: April 19, 2006
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    The reaction of carboxylic acids with dioxygen complexes MO2(PPh3)2(M=Pt, Pd) at low temperature gives rise to the selective formation of H2O2 and the corresponding dicarboxylato complexes characterized by their physical properties. It is suggested that the reaction can be influenced by either the capability of reactant for coordination to metal center or the stability of resulting metal complex. An equimolar addition of CH2ClCOOH to the dioxygen complexes in the presence of triphenylmethyl bromide at ca. −70 °C gives triphenylmethyl hydroperoxide and the corresponding monocarboxylato complexes in good yields, indicating that the reaction of organic acids with MO2(PPh3)2 proceeds by stepwise mechanism.
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