Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 52 , Issue 11
Showing 1-50 articles out of 80 articles from the selected issue
  • Fumio Kawaizumi, Hiroyasu Nomura, Makoto Ohno, Yutaka Miyahara
    1979 Volume 52 Issue 11 Pages 3135-3138
    Published: 1979
    Released: April 19, 2006
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    Using the pulse method, the ultrasonic absorption was measured for binary mixtures of water and N,N-dimethylformamide (DMF) at 5.5 and 57 MHz in the temperature range of 5–45 °C. At lower temperatures α⁄f2 as a function of the concentration produces a plateau up to x (x is the mole percent of DMF in solution)=1.5, a minimum point at x=6, and a maximum point at x=25. An increase in the temperature causes these characteristic features of α⁄f2 to disappear. At 45 °C the values of α⁄f2 increase monotonically. No relaxation process is observed in the frequency range of this work. The general features of the concentration dependence of α⁄f2 resemble those of the urea–water system in a water-rich region and those of the dioxane–water system in a DMF-rich region. The mechanism of the plateau can be explained by the cooperative nature of the formation and breaking of water clusters. The maximum of α⁄f2 is ascribed to the complex formation between DMF and water molecules, while the minimum of α⁄f2 arises from the competition between the breaking-down of the water structure and the complex formation in solution. The maximum behavior in the ultrasonic absorption can be interpreted in terms of a kinetic model, DMF+mH2O\ ightleftharpoonsDMF·(H2O)m. m is determined to be 3, and the following values have been obtained for the model mentioned above: ΔVm\simeq1 cm3/mol, Km=10±2.
  • Nobuo Yoshida
    1979 Volume 52 Issue 11 Pages 3139-3143
    Published: 1979
    Released: April 19, 2006
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    In a bi-ionic system in which a liquid membrane is interposed between aqueous solutions containing different counterions, the solution composition is often not maintained uniform right up to the membrane–solution interface owing to the presence of diffusion layers adjacent to the interface. Taking the effect of the diffusion layers into account, an expression is derived for the bi-ionic potential across a membrane having completely dissociated ion-exchange sites and counterions. The expression contains as an empirical parameter the ratio between the thicknesses of the diffusion layers at the solution and membrane sides of the interface. The expression is found to agree with experimental data, with the parameter given a single value.
  • Sadao Takagi
    1979 Volume 52 Issue 11 Pages 3144-3148
    Published: 1979
    Released: April 19, 2006
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    Details are described for the apparatus and procedures for the accurate measurement of vapor–liquid equilibria by use of small amounts of samples. The new recirculation still described is a modification of the Brown’s still (Aust. J. Sci. Res., A, 5, 530 (1952)) and its total amount of operating charge is ca. 53 cm3, of which each 7 cm3 is in the vapor- and liquid-sample traps and ca. 23 cm3 is in the boiler. A method of determining an optimum value of the heating current of the boiler is described. Partial condensation of the vapor and entrainment of the liquid phase into the vapor were eliminated. Some results obtained for the system hexane+chlorobenzene at 338.15 K agreed with the thermodynamically consistent values of Brown, showing the reliability of this still operating with the samples having relative volatilities up to 13. The construction of a thermostatted sample vessel without vapor space for a Pulfrich refractometer is also illustrated which is suitable for small quantity of volatile or hygroscopic solution.
  • Koichi Mano, Takefumi Matsukura, Akira Fujino
    1979 Volume 52 Issue 11 Pages 3149-3151
    Published: 1979
    Released: April 19, 2006
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    35Cl-NQR of two chlorocarbons and six oxochlorocarbons, all having a small ring, were measured in the temperature range 77–300 K. The NQR line groups for the allylic and vinylic chlorine atoms appear separately in the five-membered ring compounds, whereas they are concentrated in a rather narrow region near 38 MHz in the four-membered ones. Perchlorocyclopropene possesses at least three crystal modifications at 77 K, the most stable one of which has only two lines in the temperature range examined. The line assignments, and the hyperconjugative effect in some of them, are discussed with reference to the CNDO/2 MO calculation data.
  • Keiichi Moriya, Takasuke Matsuo, Hiroshi Suga, Syûzô Seki
    1979 Volume 52 Issue 11 Pages 3152-3162
    Published: 1979
    Released: April 19, 2006
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    The heat capacities of (NH4)3[AlF6] were measured between 11 and 300 K with an adiabatic calorimeter. Two anomalies were found at (193.0±0.3) K and (220.79±0.05) K. The enthalpy and entropy of the phase transitions are (790±150) J mol−1 and (4.2±0.8) J K−1 mol−1 for the former, and (4030±150) J mol−1 and (18.5±0.7) J K−1 mol−1 for the latter, respectively. The total anomalous entropy, (22.7±1.5) J K−1 mol−1, is in agreement with R In 16=23.05 J K−1 mol−1 predicted by a model involving orientational disorder of the hexafluoroaluminate(III) and the ammonium ions. Discontinuities in fluorine T1 and T at 221 K by pulse NMR measurement also support this model. The potential barrier height of the hindered rotation of the NH4+ ion was estimated to be 7 kJ mol−1 from the heat capacity data. The intermediate phase undercooled and coexisted with the low temperature phase in a limited range of temperature. The upper phase transition is of the first order but the anomalous heat capacity follows the Landau theory of the phase transitions of the second kind. The high symmetry of the crystal structure of the present crystal at room temperatures in comparison with that of the alkali cryolites was discussed in terms of the hydrogen bonding, molecular disorder and packing consideration.
  • Yukio Matsuoka, Kiwamu Yamaoka
    1979 Volume 52 Issue 11 Pages 3163-3170
    Published: 1979
    Released: April 19, 2006
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    The linear dichroic absorption spectra of the protonated and quaternized acridine dyes were measured in the UV and visible regions by the stretched film technique. The dyes examined were acridine, 10-methylacridine, Proflavine, Trypaflavine, Acridine Yellow, 10-Methylacridine Yellow, Acridine Orange, and 10-Methylacridine Orange, all of which belong to the C2v point symmetry group. Poly (vinyl alcohol) was used as a film matrix. The absorption spectrum of each dye was resolved into the long-axis and short-axis polarized components. Two orthogonally-polarized electronic transitions (the 1La and 1Lb bands) of 3,6-disubstituted acridine dyes were reduced to overlap in the visible region of the spectra. The orientation factors Ky and Kz of each dye were evaluated at a constant degree of stretching and were related to the geometry of the dye molecule.
  • Katumitu Hayakawa, Mitsuo Kanda, Iwao Satake
    1979 Volume 52 Issue 11 Pages 3171-3175
    Published: 1979
    Released: April 19, 2006
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    Spectrophotometric measurements were undertaken at 360 nm in order to estimate the formation constant of triiodide ion in micellar solution of dodecyltrimethylammonium chloride. The absorption spectra of the solutions suggested that both iodine molecule and triiodide ion are solubilized in a hydrophilic surface region of the surfactant micelle. The apparent formation constant of triiodide ion, Ka, was found to be much larger in micellar solution than in water. It was also shown that the value of Ka decreases regularly with increasing surfactant concentration. A tentative estimation based on a lamellar micelle model led to the intrinsic formation constant of triiodide ion of 650 mol−1 dm3 or less at 30 °C, which is comparable with that in water. The thermodynamic consideration revealed that the formation reaction of triiodide ion from iodine and iodide ion in micellar solution is accompanied by an anomalous entropy decrease.
  • Shiro Suzuki, Takashi Nakamura, Tamotsu Kondo
    1979 Volume 52 Issue 11 Pages 3176-3179
    Published: 1979
    Released: April 19, 2006
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    Partially sulfonated poly(1,4-piperazinediylterephthaloyl)(SPP) microcapsules were found to undergo disintegration by the action of dodecylpyridinium ions when the surfactant cation concentration exceeded a certain value which was dependent on pH of the medium. At their lower concentrations, dodecylpyridinium ions interacted with negatively charged SPP microcapsules to produce aggregation of the latter. A polyelectrolyte-type viscosity behavior was observed with the complex formed between SPP and dodecylpyridinium ions in the disintegration process of the microcapsules. Crosslinking of the terminal amino groups of SPP microcapsules prevented disintegration from taking place.
  • Kyuya Yakushi, Masaaki Iguchi, Haruo Kuroda
    1979 Volume 52 Issue 11 Pages 3180-3191
    Published: 1979
    Released: April 19, 2006
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    Polarized absorption and reflection spectra were observed on the single crystals of the solventfree and solvent containing modifications of benzidine (BD)–7,7,8,8-tetracyano-p-quinodimethane (TCNQ) molecular complex, by using the microspectrophotometers of transmission and reflection types. The absorption spectra obtained by the dispersion analyses of the reflection spectra agreed fairly well with those directly observed by the transmission method. The spectra showed that the BD–TCNQ, complex has non-ionic ground state in all modifications although the intermolecular interaction is considerably strong and is appreciably affected by the inclusion of solvent molecules. In all modifications, the second charge transfer band was confirmed to be polarized in the direction almost perpendicular to the direction of the donor-acceptor stack, while the first charge transfer band is polarized in the direction of the donor-acceptor stack as it is usually found for a typical charge transfer complex. This anomaly of the polarization direction of the second charge-transfer band was concluded to be due to a strong mixing between the charge-transfer excitation and the local excitation associated with TCNQ.
  • Kaizaburo Saito, Tsutomu Yamaguchi, Kozo Tanabe, Toshimasa Ogura, Misa ...
    1979 Volume 52 Issue 11 Pages 3192-3197
    Published: 1979
    Released: April 19, 2006
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    The metathesis of 1,5-cyclooctadiene (COD) was investigated over supported rhenium oxide catalysts in terms of carrier effects, acid properties of the catalysts, product distributions, and the reversibility of the reaction. Only alumina plays an effective role as a support. The reaction of COD over rhenium oxide–alumina catalyst yields oligomers, C8n, sesqui-oligomers, C8n+4, and polymers. The important results are as follows: 1) The product distribution in terms of the carbon number of the products shows a decay curve with maxima around C12, C16, and C20. 2) The reaction of oligomers gives COD and some products similar to those of COD. 3) The reactivity of 1,5,9-cyclododecatriene (CDT) was low compared with COD, 1,5,9,13-cyclohexadecatetraene (CHT), and 1,5,9,13,17-cycloeicosapentaene (CEP). 4) A reaction of a mixture of macrocyclic polyenes and polymers gave appreciable amounts of CDT, CHT, and CEP, whereas no COD was obtained. On the basis of the results, we conclude that the products, oligomers, sesqui-oligomers, and polymers, are formed independently from the active intermediary polymers which are formed from COD.
  • Shin-ichi Ishiguro, Hitoshi Ohtaki
    1979 Volume 52 Issue 11 Pages 3198-3203
    Published: 1979
    Released: April 19, 2006
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    The hydrolytic reactions of beryllium(II) ions were calorimetrically studied at 25 °C in aqueous solution and dioxane–water mixtures, both containing 3.0 mol dm−3 (Li)ClO4 as a constant ionic medium. On the basis of the formation constants previously determined, the enthalpy and entropy changes for the reaction, qBe2++pH2O=Beq(OH)p(2qp)++pH+, were estimated for the Be2OH3+ and Be3(OH)33+ complexes in aqueous solution and 0.1 mole fraction dioxane–water mixture and for Be2OH3+, Be3(OH)33+, and Be2(OH)22+ complexes in 0.2 mole fraction dioxane–water mixture. The enthalpy and entropy changes of formation of the Beq(OH)p(2qp)+ complex obtained in solutions of various mole fractions of dioxane were as follows: 2Be2++H2O=Be2OH3++H+; ΔH12 (mole fraction: 0.0)=18.6±0.2 kJ mol−1, TΔS12(mole fraction: 0.0)=1.3±0.2 kJ mol−1, ΔH12(0.1)=15.2±0.2 kJ mol−1, TΔS12(0.1)=−3.4±0.2 kJ mol−1, ΔH12(0.2)=8.4±0.4 kJ mol−1, TΔS12(0.2)=−12.4±0.4 kJ mol−1, 3Be2++3H2O=Be3(OH)33++3H+; ΔH33(0.0)=61.7±0.2 kJ mol−1, TΔS33(0.0)=12.2±0.2 kJ mol−1, ΔH33(0.1)=59.4±0.2 kJ mol−1, TΔS33(0.1)=10.0±0.2 kJ mol−1, ΔH33(0.2)=59.0±0.4 kJ mol−1, TΔS33-(0.2)=9.1±0.4 kJ mol−1, 2Be2++2H2O=Be2(OH)22++2H+; ΔH22(0.2)=42.3±0.4 kJ mol−1, TΔS22(0.2)=1.3±0.4 kJ mol−1. The enthalpy and entropy changes of the reaction, H2O=H++OH, in the solutions of the same compositions were also determined as ΔHw(0.0)=56.6±0.1 kJ mol−1, TΔSw(0.0)=−22.6±0.1 kJ mol−1, ΔHw(0.1)=58.1±0.1 kJ mol−1, TΔSw(0.1)=−25.3±0.1 kJ mol−1, ΔHw(0.2)=61.2±0.1 kJ mol−1, TΔSw(0.2)=−26.6±0.1 kJ mol−1. These results were discussed in connection with interactions between the hydroxo complexes and the solvent molecules and with those between solvent molecules in the mixed solvents.
  • Kinya Iijima, Shuzo Shibata
    1979 Volume 52 Issue 11 Pages 3204-3207
    Published: 1979
    Released: April 19, 2006
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    The molecular structure of trimethylphosphine-boron trichloride (CH3)3P·BCl3 has been determined from gas electron-diffraction data. The structure parameters and uncertainties are rg(P–B)=1.941(16) Å, rg(B–Cl)=1.851(7) Å, rg(C–P)=1.800(4) Å, rg(C–H)=1.099(5) Å, rg(Cl…Cl)=3.022(5) Å, and rg(C…C)=2.936(10) Å. The potential barrier about the P–B axis is 3.8±0.7 kcal mol−1 in the gas phase. The data show that the molecular structure in the gas phase is nearly equal to that in the solid phase.
  • Kazuo Yasukouchi, Isao Taniguchi, Hiroko Yamaguchi, Katsuji Miyaguchi, ...
    1979 Volume 52 Issue 11 Pages 3208-3212
    Published: 1979
    Released: April 19, 2006
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    Anodic oxidation of 2-aminofluorene in acetonitrile solutions at a Pt electrode was investigated by using electrochemical techniques and by preparative-scale electrolyses. The cyclic voltammogram of 2-aminofluorene exhibited two anodic waves, which had peak potentials at 0.45 V (Ia) and 1.15 V (IIa) vs. Ag/0.01 M AgClO4. Wave IIa was due to oxidation of protonated 2-aminofluorene. In the voltammogram of repetitive sweeps, another redox couple (IIIa/IIIc) was observed at 0.13 V for IIIa and 0.06 V for IIIc, respectively. This indicates that at wave Ia, a species which is more easily oxidized than 2-aminofluorene was produced by follow-up chemical steps. By controlled-potential electrolysis at 0.5 V of a 2-aminofluorene solution containing pyridine as a prpton acceptor, a dark green product, 3-(2-fluorenylimino)-2,3-dihydro-2-fluorenimine (5) (or 1-(2-fluorenylimino)-1,2-dihydro-1-fluorenimine (5′)), precipitated as the main product in more than 70% yield. The oxidation pathway of 2-aminofluorene (Eqs. 1—4) has been proposed on the bases of the following results: (i) The apparent n-value was 1.95, (ii) two protons/molecule of 2-aminofluorene were released in the follow-up chemical steps, and (iii) the peak potential for oxidation of 2′-amino-2,3′-difluorenylamine (3) (or 2-amino-1,2′-difluorenylamine (3′)) was in good agreement with that of wave IIIa, and the anodic oxidation of 3 (or 3′) gave the same product as that obtained by oxidation of 2-aminofluorene.
  • Takao Itoh, Hiroaki Baba
    1979 Volume 52 Issue 11 Pages 3213-3216
    Published: 1979
    Released: April 19, 2006
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    The emission spectra of 1,4-naphthoquinone (NQ) and 2-methyl-1,4-naphthoquinone (MNQ) vapors have been investigated at various temperatures in the presence of added foreign gases (≈100 Torr). The results indicate that in both NQ, and MNQ, the emission consists of T1(n, π*)→S0 phosphorescence and weak E-type delayed fluorescence, S1(n, π*)→S0, the latter lying at higher frequencies. This new interpretation of the vaporphase emission spectra of the naphthoquinones, which is substantially different from the interpretations given by previous authors, is based on and consistent with the following observations: (1) When the temperature is raised, the ratio of the fluorescence intensity to the phosphorescence intensity increases; (2) the S1–T2 energy separations, 1365±60 and 1500±200 cm−1 for NQ, and MNQ, respectively, determined from the temperature dependence of the emission intensities agree with the corresponding values obtained from spectral data; (3) the emission lifetimes obtained by monitoring the fluorescence and phosphorescence are identical.
  • Tooru Inoue, Akira Fujishima, Kenichi Honda
    1979 Volume 52 Issue 11 Pages 3217-3220
    Published: 1979
    Released: April 19, 2006
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    The study of the photoanodic reaction at the ZnO electrode in an electrolyte solution containing redox agents was carried out by means of the rotating ring-disk electrode technique. The competition reactions between the photocorrosion of ZnO and the oxidation of reducing agents were discussed focusing on the potentials of the electroactive species at the semiconductor-solution interface. The ZnO photoelectrode was stabilized in the course of the oxidation of a strong reducing agent dissolved in a solution.
  • Shizuo Fujiwara, Bernd M. Rode
    1979 Volume 52 Issue 11 Pages 3221-3222
    Published: 1979
    Released: April 19, 2006
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    Quantum chemical calculation has been made for the sizes of the hydration shells of the metal ions as well as for the binding energies of water molecules in the hydration shells. The results of the both calculations give the basis of the size of the molecular space. Although the experimental value of the molecular space, (20±5A)3, does not exactly agree with the calculated value, we assume that the quantum chemically obtained hydration sphere refers to the molecular space.
  • Chikatoshi Utsunomiya, Tsunetoshi Kobayashi, Saburo Nagakura
    1979 Volume 52 Issue 11 Pages 3223-3225
    Published: 1979
    Released: April 19, 2006
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    The photoelectron spectra of typical hydrogen-bonded complexes, CF3COOH–(C2H5)2NCH3, CF3COOH–(n-C3H7)3N, CF3CF2COOH–(C2H5)2NCH3, and CF3CF2COOH–(n-C3H7)3N were observed in the gas phase. It was found that the nonbonding orbital of the proton acceptor is stabilized significantly by hydrogen-bond formation while the three higher occupied orbitals of the proton donor are destabilized. The large orbital energy changes due to hydrogen-bond formation strongly support the charge-transfer model for the hydrogen bond.
  • Takayuki Ebata, Masahiro Kawasaki, Kin-ichi Obi, Ikuzo Tanaka
    1979 Volume 52 Issue 11 Pages 3226-3228
    Published: 1979
    Released: April 19, 2006
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    The vibrational distribution of the CS(X) fragment has been studied by the UV flash photolysis and kinetic spectroscopic technique. The CS fragment was generated by the flash photolysis of CS2 at ≈200 nm. The vibrational distribution is well represented by a sum of two modified Poisson distributions with different mean values. This distribution is explained by assuming the following two photodissociation processes of CS2; one is a predissociation through a triplet state and the other is a direct photodissociation.
    (Remark: Graphics omitted.)
  • Takehiko Chiba
    1979 Volume 52 Issue 11 Pages 3229-3235
    Published: 1979
    Released: April 19, 2006
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    Proton magnetic relaxation times T1, T, and T1D were measured on a single crystal of α-form oxalic acid dihydrate in two modes: temperature dependence at one or two specific crystal orientations, and angular dependence at several temperatures. Results were compared with the calculation based on an isolated three proton system for the assumed modes of motions. The temperature dependence of T1 and that of T and T1D in the low temperature range are reasonably accounted for by the 180°-flip of the water molecule. The activation energy for the motion of 43.6 kJ mol−1 is obtained. T and T1D above about 35 °C decreased as the temperature was raised. The comparison of the observed results in this temperature range with the calculated ones suggests that there is exchange motion among the three spins. An activation energy for this motion of 80.8 kj mol−1 is obtained. This three spin exchange motion may be considered as a combination of a jump of carboxyl proton to a higher potential trough corresponding to the ionic configuration and the three-fold reorientation of the hydronium ion thus formed.
  • Tadaaki Kakutani, Mitsugi Senda
    1979 Volume 52 Issue 11 Pages 3236-3241
    Published: 1979
    Released: April 19, 2006
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    Theoretical equations are presented of the a.c. polarization and of the a.c. polarography and voltammetry for the surface redox reaction (Oad+ne\ ightleftharpoonsRad) in which charge transfer reaction takes place exclusively between the adsorbed reactants Oad and Rad, and both reactants are adsorbed so strongly that the amount of O or R brought to or removed from the electrode surface can be neglected. The interaction between adsorbed molecules is assumed to be expressed by Frumkin’s a-parameters. Also the effect of the double layer impedance is taken into account. Some simplified cases are discussed in detail.
  • Shinichi Yamabe, Tsutomu Minato, Hiroshi Fujimoto, Kenichi Fukui
    1979 Volume 52 Issue 11 Pages 3242-3248
    Published: 1979
    Released: April 19, 2006
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    A molecular orbital (MO) approach to a radical-radical reacting system is proposed within the isolated molecule approximation. The interaction energy, ΔW, is defined as the sum of four components, Coulomb, exchange, charge transfer and polarization energies. The four terms are calculated in the recombination of two methyl radicals. The origin of the deformation of methyl radical (D3h→C3v) and the rotational barrier (staggered→eclipsed) in the course of the recombination was found to be the exchange energy caused by the interaction of both doubly occupied MO’s. The difference-density map shows the characteristic role of exchange and charge transfer interactions for charge redistribution.
  • Hiroyasu Nomura, Shinobu Koda, Yutaka Miyahara
    1979 Volume 52 Issue 11 Pages 3249-3252
    Published: 1979
    Released: April 19, 2006
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    The temperature dependences of reorientational and vibrational relaxation times of benzene and benzene-d6 in the solid and liquid phases were measured by means of Raman line shape analysis. The temperature dependence of the reorientational relaxation times was in very good agreement with that published previously. The vibrational relaxation times of benzene changed drastically at the solid to liquid phase transition point both in C6H6 and C6D6. We consider that this effect is due to the non-radiative energy transfer and the pure dephasing process by molecular collisions in the liquid state.
  • Toyohisa Nakamura, Shiro Haruyama
    1979 Volume 52 Issue 11 Pages 3253-3257
    Published: 1979
    Released: April 19, 2006
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    The formation of a potential-dependent surface layer on VO2 electrode has been investigated from the change in conductance of a thin VO2 film electrode by galvanostatic polarization. The VO2 electrode dissolved as vanadate with 100% current efficiency by anodic polarization. At potentials negative to the immersion potential, the VO2 electrode functioned as an insoluble electrode with the formation of the potential-dependent surface layers of the vanadium oxides by lower valence. The change in composition of the surface layers was traced by resistmetry and coulometry, and illustrated against the amount of electric charge passed, taking V7O13, V6O11, V5O9, V4O7, V3O5, and V2O3 as the possible oxides. The composition at vanadium oxides of outer-most layer was plotted against the electrode potential. The plot shows a multi-step figure as in the equilibrium partial pressures of oxygen on vanadium oxides at high temperatures, suggesting a model in which the composition of the outer-most layer of the oxide responds to the electrode potential applied.
  • Yasunobu Inoue, Seiji Hacho, Eizo Miyazaki, Iwao Yasumori
    1979 Volume 52 Issue 11 Pages 3258-3264
    Published: 1979
    Released: April 19, 2006
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    Catalysis by platinum supported on polyamide-6 was examined for the H2-D2 equilibration reaction at 0 °C in the pressure range of 5–20 Torr (1 Torr=133.3 Pa). Three kinds of polyamides with different molecular weights were prepared as support; the concentration of platinum varied from 0.5 to 2.7 wt%. With preadsorption of hydrogen at 0 °C, the rate of the reaction was found to increase up to 10 times as high as the original level. The rate km (HD molecule s−1Pt atom−1) showed a maximum, depending on surface area of the polyamides used, in the range 0.8–1.0 wt% of Pt content and its dependence on total pressure is represented by km=K1P⁄(1+K2√‾P)2 irrespective of Pt content. No significant isotope effect was observed at 0 °C. It was found that a linear relationship exists between the enhancement of km and the amount of hydrogen preadsorbed, indicating an important role of the preadsorbed hydrogen in activation of the catalysts. In contrast to km, the turn-over frequency kt (HD molecule s−1 site−1) was nearly independent of Pt concentration. The exchange reaction is explained in terms of the Bonhoeffer-Farkas mechanism. XPS spectra provided the evidence for the presence of Pt(II) complexes on the surface. The structure of active sites is discussed.
  • Hiroyuki Shinohara, Akira Imamura
    1979 Volume 52 Issue 11 Pages 3265-3270
    Published: 1979
    Released: April 19, 2006
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    The electrophilicity of the H atom in hydrogen abstraction reactions was studied by the CNDO/2 method. The origin of the electrophilicity of the H atom was well understood using the stabilization energy due to the delocalization of electrons (SEDE) between the radical and substrate; this energy was calculated along the reaction path. The electrophilic energy (SEDE from the substrate to the radical) governs the relative reactivities of substrates, CH4<CH3CH3<CH3CH2CH3<(CH3)3CH which correspond to the order of the increase in the electron density. The electrophilic energy is also important in hydrogen abstraction by the H atom from aliphatic alcohols. In the case of the Cl2 radical, the nucleophilic energy (SEDE from the radical to the substrate) determines the relative reactivities of substrates, CH3OH<C2H5OH<i-C3H7OH. The polarity of a free radical is tentatively clarified by using its ionization potential.
  • Kazuhiro Niisawa, Ko Taki
    1979 Volume 52 Issue 11 Pages 3271-3276
    Published: 1979
    Released: April 19, 2006
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    The sulfur atoms produced by the nuclear transformation of 35Cl(n,p)35S were allowed to react with gaseous ethane in the presence or in the absence of radical scavengers. The products were hydrogen sulfide, methanethiol, ethanethiol, dimethyl sulfide, and other sulfur-containing compounds. The yield of the C–H insertion product (ethanethiol) increased upon the addition of a small amount of the scavenger and then decreased with an increase in the amount of the scavenger to give a constant value, but the yield of the C–C insertion product (dimethyl sulfide) did not vary. The increase in the ethanethiol yield at low concentrations of the scavenger may be ascribed to a protective effect by the scavenger. By the addition of ethanethiol before thermal-neutron irradiation, the yield of ethanethiol was increased, but that of dimethyl sulfide was not increased, therefore the primary yield of ethanethiol could be determined. The spin state of the reactive sulfur atoms in the thermalinsertion reaction was also estimated to be the 3P state upon the addition of COS and C2H4.
  • Osamu Yamaguchi, Muneaki Kamata, Kiyoshi Shimizu
    1979 Volume 52 Issue 11 Pages 3277-3279
    Published: 1979
    Released: April 19, 2006
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    Wollastonite(β-CaSiO3) was formed directly from the mixed powder prepared by simultaneous hydrolysis of calcium and silicon alkoxides. Crystallization isotherms were described by the Avrami equation ln(1−α)=−ktn with n=3 and the activation energy was determined as 284.5 kJ/mol. The kinetics of transformation of β- into α-CaSiO3 was best interpreted by the contracting cube equation 1−(1−α)1⁄3=kt. The value of the activation energy was 983.2 kj/mol.
  • Yoichi Kitamura
    1979 Volume 52 Issue 11 Pages 3280-3283
    Published: 1979
    Released: April 19, 2006
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    The pressure effects on the base hydrolysis reaction rates of α-, β-[Co(edda)(NH3)2]+ and α-[Co(edda)(NO2)2] in a carbonate buffer were measured up to 1500 kg/cm2 (1 kg/cm2=98.0665 kPa). The activation volumes at normal pressure were found to be 16.6, 22.3, and 11.9cm3/mol respectively. These values are consistent with those expected from the SN1 CB mechanism, where the conjugate bases dissociate via the Id mechanism.
  • Kazuko Y. Matsumoto
    1979 Volume 52 Issue 11 Pages 3284-3291
    Published: 1979
    Released: April 19, 2006
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    The crystal and molecular structures of polymolybdo complexes of methylarsonate and dimethylarsinate have been determined by the X-ray diffraction technique. The crystal of (CN3H6)2[CH3AsMo6O21(H2O)6]·6H2O is trigonal, with the space group R3 and the cell dimensions of a=9.653(6) Å, α=87.01(15)°, and Z=l. The anion is an assemblage of six MoO6 octahedra and a tetrahedral CH3AsO3 group. The six MoO6 octahedra constitute a ring with alternate edge- and corner-sharing, and the tetrahedral CH3AsO3 group joins the anion, with its three oxygen atoms shared with the ring. Each molybdenum atom has two terminal oxygen atoms in the cis position and is coordinated by one water molecule. (CN3H6)2[(CH3)2AsMo4O14(OH)]·H2O crystallizes in the space group P21/c of the monoclinic system, with the cell dimensions of a=8.530(5), b=8.532(4), c=30.121(15) Å, β=95.50(16)°, and Z=4. The Mo4O14(OH) moiety in the [(CH3)2AsMo4O14(OH)]2− anion is formed with two face- and two edge-sharings of MoO6 octahedra into an almost flat rectangle. The oxygen atom located at the center of the anion and bonded to all the four molybdenum atoms is protonated and is, in fact, a hydroxyl group.
  • Akimasa Yajima, Ryoko Matsuzaki, Yuzo Saeki
    1979 Volume 52 Issue 11 Pages 3292-3295
    Published: 1979
    Released: April 19, 2006
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    The thermogravimetry and differential thermal analysis of VClO in an argon stream were carried out. The products obtained by heating VClO in an argon stream at various temperatures were examined by chemical analysis and X-ray analysis. Also, the reaction between VClO and oxygen was examined in the same manner. When VClO is heated in an argon stream, it decomposes above about 400 °C to form V2O3 and VCl3, 3VClO(s)→V2O3(s)+VCl3(s). Subsequently, the resulting VCl3 disproportionates to form VCl2 and VCl4, 2VCl3(s)→VCl2(s)+VCl4(g). VClO reacts with oxygen above about 120 °C to form V2O5 and VCl3O, 6VClO(s)+3O2(g)→2V2O5(s)+2VCl3O(g); this reaction is accompanied by the 4VClO(s)+3O2(g)→2V2O5(s)+2Cl2(g) reaction.
  • Seiichi Kanda, Kenichi Yamashita, Kuwako Ohkawa
    1979 Volume 52 Issue 11 Pages 3296-3301
    Published: 1979
    Released: April 19, 2006
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    In a family of catena-μ-N,N′-disubstituted dithiooxamidocopper(II) complexes which have been assumed as two-dimensional coordination polymers, one complex with HOC2H4- substituents is an electronic conductor as well as others, and also a protonic conductor uniquely. The latter property was proved both by spectroscopic detection of the hydrogen molecules evolved from d.c. electrolysis of pressed pellets of the powder specimen and by observation of the anomalous increase (three orders of magnitude) of the electric conductivity as an effect of 103 Pa of H2O or D2O vapor on the dehydrated specimen in an evacuated conductivity cell. A novel conduction mechanism was suggested for such a solid system with both conjugated double bonds and extended hydrogen bonds.
  • Masao Sekizaki, Shunji Utsuno
    1979 Volume 52 Issue 11 Pages 3302-3306
    Published: 1979
    Released: April 19, 2006
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    The crystal structure of ethylenediaminebis[2-(aminomethyl)pyridine]cobalt(III) hexacyanocobaltate(III) dihydrate, [Co(H2NCH2CH2NH2)(C5H4NCH2NH2)2][Co(CN)6]·2H2O, has been determined by the X-ray diffraction method and subsequently refined by a block-diagonal least-squares method to give R=0.050 for 5238 non-zero reflections. The crystals are triclinic with a space group P\bar1; a=9.034(2), b=17.267(2), c=8.395(2) Å, α=87.1(3), β=96.2(3), γ=104.6(3)°, and Z=2. The crystal is ionic, comprising the [Co(H2NCH2CH2NH2)(C5H4NCH2NH2)2]3+ cation and the [Co(CN)6]3− anion. The complex cation is a slightly distorted octahedron with three five-membered chelate rings in a lel conformation. The two pyridine nitrogen atoms occupy trans positions. Thus, the cation has an approximate twofold axis of rotation. The anion is also a distorted octahedron, with the coordination of CN through the carbon atom. The cobalt atoms of the anions occupy the special positions. Two cations in the unit cell are connected by these anions through hydrogen bonds to form a three-dimensional network typical of an ionic crystal.
  • Keiji Matsumoto, Shun’ichiro Ooi
    1979 Volume 52 Issue 11 Pages 3307-3310
    Published: 1979
    Released: April 19, 2006
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    The crystal structure of (−)589-[Cr(acac)2(tn)]I·H2O has been determined from the X-ray diffraction data collected on a diffractometer. The crystal is orthorhombic, with the space group P212121 and with a=20.834(6), b=12.015(3), c=7.621(2) Å, and Z=4. Block-diagonal least-squares refinement for 1426 independent reflections with Fo2>3σ(Fo2) converged to R=4.91%. The complex cation has the Λ absolute configuration. The 1,3-propanediamine ligand assumes a chair conformation. One of the 2,4-pentanedionato chelate rings is almost planar, while in the other the 2,4-pentanedionato plane is bent away from the plane defined by Cr and 2 O donor atoms because of the intramolecular repulsion, the interplanar angle being 9.4°. The interrelation between the absolute configuration and the circular dichroism was discussed for the [Cr(acac)n(tn)3−n](3−n)+-type complexes.
  • Akio Yasuhara, Keiichiro Fuwa
    1979 Volume 52 Issue 11 Pages 3311-3313
    Published: 1979
    Released: April 19, 2006
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    Analytical studies on phenol, o-cresol, m-cresol, p-cresol, and p-ethylphenol from liquid swine manure were performed with selected ion monitoring in computer-controlled gas chromatography-mass spectrometry. Phenol, p-cresol, and p-ethylphenol in effluent gas from liquid swine manure and in the head-space gas over liquid swine manure were determined.
  • Masao Kubo, Takeo Sato
    1979 Volume 52 Issue 11 Pages 3314-3317
    Published: 1979
    Released: April 19, 2006
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    Peri interaction in several naphthalene ketones was investigated using the carbon-13 NMR, IR, and UV spectra. The carbonyl carbon resonances for 7H, 14H-cycloocta[1,2,3-de:5,6,7-de′]dinaphthalene-7,14-dione and its 7-oxa analog were found to be shifted upfield by 27 and 24 ppm respectively compared with those of model compounds. The anomalous shift for the former was attributed to π-orbital compression, which inhibited the polarization of carbonyl groups because of a forced parallel geometry, while the latter was attributed to field effects. The conclusion was supported by UV and IR data.
  • Mikio Watanabe, Kozo Shirai, Takanobu Kumamoto
    1979 Volume 52 Issue 11 Pages 3318-3320
    Published: 1979
    Released: April 19, 2006
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    The addition reaction of lithium benzenethiolate to 2-buten-4-olide in the presence of aldehydes and ketones afforded α-substituted β-phenylthio-γ-butyrolactones (4af). The dehydrosulfenylation of 4ad proceeded smoothly to give 2-substituted 2-buten-4-olide by the reflux of α-substituted β-phenylsulfinyl-γ-butyrolactone, which was prepared by the oxidation of 4ad, in the presence of triethylamine.
  • Toshihiko Okada, Yoshio Kamiya
    1979 Volume 52 Issue 11 Pages 3321-3325
    Published: 1979
    Released: April 19, 2006
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    The liquid-phase oxidation of toluene catalyzed by the cobalt(II) ion and the bromide ion in the presence of the copper(II) ion has been studied. Benzyl acetate was obtained in a good yield (50–70%) with mixed catalysts of metal acetates and sodium bromide in acetic acid at 100–150 °C, accompanied by small amounts of benzaldehyde and benzoic acid. The product distribution was greatly dependent on the NaBr concentration, which can be explained in terms of the high oxidizing ability of the copper(II) ion coordinated by the bromide ion. A synergistic effect was found on the yield of benzyl acetate upon the addition of copper(II) acetate with a high NaBr concentration, the maximum yield being obtained at the Co:Cu:NaBr ratio of 1:1:5–10. A change in the oxygen partial pressure also varied the product distribution, suggesting that the competitive reaction of the copper(II) ion with the oxygen molecule for the benzyl radical was simultaneously taking place at a diffusion-controlled rate. Benzyl acetate was considered to result from the oxidation of the benzyl radical by cop-per(II) bromide and the subsequent solvolysis by acetic acid. The addition of acetic anhydride had a negative effect on the formation of benzyl acetate.
  • Shigeru Kuwata, Takashi Yamada, Tatsuya Shinogi, Naoki Yamagami, Fumio ...
    1979 Volume 52 Issue 11 Pages 3326-3328
    Published: 1979
    Released: April 19, 2006
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    (+)-β-(2-Furyl)-β-alanine and (+)-β-(2-thienyl)-β-alanine were obtained by resolving the N-benzyloxycarbonyl-DL-amino acids with quinine and by removing the protecting group from them. It was concluded, from the changes in their ORD curves depending on the pH, and also from the sign of the Cotton effects of their DCHA salts of the N-ethylthiocarbonothioyl derivatives, that both the compounds belong to the L-series. This conclusion was supported by the fact that the aspartic acid obtained by the oxidation of these amino acids belongs to the D-series.
  • Takashi Matsumoto, Makoto Takahashi, Yutaka Kashihara
    1979 Volume 52 Issue 11 Pages 3329-3336
    Published: 1979
    Released: April 19, 2006
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    All stereoisomers (3a, b–6a, b) of monocrotalic acid have been synthesized. Methylation of (±)-cis-2,3,4-trimethyl-2-pentenedioic acid with diazomethane followed by cis-hydroxylation with potassium permanganate afforded two epimeric γ-lactone esters in a ratio of ca. 1:5. These esters were then hydrolyzed with dilute hydrochloric acid to the corresponding acids, (±)-3 and racemic monocrotalic acid (4). Optical resolution of (±)-3 with brucine afforded 3a (2R,3R,4S) and 3b (2S,3S,4R). The racemic monocrotalic acid was also resolved by means of brucine to give natural monocrotalic acid (4a: 2R,3R,4R) and its enantiomer (4b: 2S,3S,4S). Subsequently, (±)-trans-2,3,4-trimethyl-2-pentenedioic acid was resolved with cinchonidine to give 8a and 8b, whose stereochemistry was assigned respectively as S- and R-configuration by correlation to the known (R)-(−)-2-phenylpropanoic acid. Methylation of 8a followed by cis-hydroxylation and hydrolyses afforded γ-lactone acids, 5a (2R,3S,4S) and 6b (2S,3R,4S). Similarly, the enantiomer 8b was also converted into the corresponding acids, 5b (2S,3R,4R) and 6a (2R,3S,4R). The stereochemical course of the above hydroxylations with potassium permanganate was well explained by a modification of Gram’s rule of asymmetric induction. The CD spectra of 3a,b–6a,b were also discussed.
  • Akira Oku, Shingo Arita
    1979 Volume 52 Issue 11 Pages 3337-3341
    Published: 1979
    Released: April 19, 2006
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    The reactions of enolizable acyl cyanides (acetyl, propionyl, isobutyryl, and diphenylacetyl cyanide) with acid chlorides (acetyl, propionyl, benzoyl, p-nitrobenzoyl, diphenylcarbamoyl, and dimethylcarbamoyl chloride) in the presence of tertiary amines gave the corresponding 1-cyano-l-alkenyl carboxylates or carbamates in good yields. Among several solvents and amines examined in the reaction of acetyl cyanide with propionyl chloride, benzene and pyridine seem to be most appropriate. The maximum yield (98%) of the ester was attained in benzene when both the chloride and pyridine were used in excess amounts (1.2–1.4 times the amount of the cyanide). The rate of reaction depended little on the concentration of the chloride but on both the cyanide and the amine being of first order in each reactant; it was also influenced by the basicity of tertiary amines and, in the case of weak bases, additionally by their nucleophilic power.
  • Tokuzo Kawase, Shigeo Yoneda, Zen-ichi Yoshida
    1979 Volume 52 Issue 11 Pages 3342-3345
    Published: 1979
    Released: April 19, 2006
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    Aliphatic thiones were found to react with trialkyl phosphites to give (alkylthio)- and/or mercapto-alkylphosphonic esters. The reaction is interpreted in terms of the carbophilic attack with trialkyl phosphites at the carbon atom of the thiocarbonyl group, and the subsequent migration mechanism via the betaine intermediate.
  • Masao \={O}kubo, Sonoko Ueda
    1979 Volume 52 Issue 11 Pages 3346-3348
    Published: 1979
    Released: April 19, 2006
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    The methoxyl group of the title imine was replaced by the phenyl group on treatment with PhMgBr, the same group of N-benzylidene-o-anisidine remaining. The result was discussed on the basis of radical chain mechanism involving the initial electron-transfer.
  • Minoru Suzuki, Etsuro Kurosawa
    1979 Volume 52 Issue 11 Pages 3349-3351
    Published: 1979
    Released: April 19, 2006
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    Several brominated sesquiterpene phenols and the related ethers were isolated from the red alga Laurencia glandulifera Kützing. The structures of these compounds were determined on the basis of spectroscopic evidence and chemical correlation.
  • Minoru Suzuki, Etsuro Kurosawa
    1979 Volume 52 Issue 11 Pages 3352-3354
    Published: 1979
    Released: April 19, 2006
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    The taxonomic reexamination of the red alga ‘L. intermedia Yamada,’ previously collected at Oshoro Bay, Hokkaido, showed that this alga consistd of a mixture of L. intermedia Yamada, L. capituliformis Yamada, and L. okamurai Yamada. Within the Japanese species of genus Laurencia, laurinterol and debromolaurinterol were found to be characteristic metabolites of L. okamurai, not of L. intermedia. In the course of this examination, dibromophenol and debromoaplysinol were newly isolated.
  • Tadao Uyehara, Yoshio Kitahara
    1979 Volume 52 Issue 11 Pages 3355-3357
    Published: 1979
    Released: April 19, 2006
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    2-Chloro-, 2-methoxy-, 2-phenyl-, and 2-methyltropones (2,4,6-cycloheptatrien-1-ones) and benzoate of tropolone (2-hydroxy-2,4,6-cycloheptatrien-1-one) reacted with ethylene affording Diels-Alder type 1,4-addition products, bicyclo[3.2.2]nona-3,6-dien-2-ones. The regioselectivities of the cycloaddition are quite random, while they are reproduced by the calculated interaction energies based on Salem’s PMO equation which includes the closed-shell repulsion term.
  • Hiroaki Takayanagi, Haruo Ogura, Keinosuke Matsuzaki, Koji Kitajima, T ...
    1979 Volume 52 Issue 11 Pages 3358-3361
    Published: 1979
    Released: April 19, 2006
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    The crystal and molecular structure of (±)-2-rnethylarnino-4,5-bis(p-chlorophenyl)-4-hydroxy-4H-imidazole has been determined by the single-crystal X-ray diffraction method. The crystals are monoclinic with space group P21/c, cell dimensions: a=14.872(5), b=9.216(7), c=12.945(11) Å, β=99.53(5)°, and Z=4. The structure was determined by the symbolic addition method and refined by the least-squares method to give the final R factor of 0.072 for 1616 non-zero reflections.
  • Takeo Shimidzu, Akira Murakami, Kazushige Yamana, Yoshiyuki Konishi
    1979 Volume 52 Issue 11 Pages 3362-3365
    Published: 1979
    Released: April 19, 2006
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    Cationic mononucleotide analogs were synthesized through a quaternization reaction of N-halogenoethylated derivatives of nucleic acid bases or 5′-halogeno-5′-deoxynucleoside. When they interacted with polynucleotide and polynucleotide analogs with negative charges, base-base interactions were observed. The interactions between complementary bases were stronger than the others. It is suggested that an anionic field originating from the polynucleotide or polynucleotide analog contributes to the interaction of complementary bases.
  • Takeo Kobayashi, Tetsuo Hiraoka
    1979 Volume 52 Issue 11 Pages 3366-3370
    Published: 1979
    Released: April 19, 2006
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    The o-nitrobenzeneselenenamides were oxidized with active manganese dioxide to give the irnines, which were converted to the 7α-methoxycephalosporins 3 by the reaction with lithium methoxide. The selenenamides 3 were acylated with phenoxyacetyl chloride to afford the desired cephamycin derivatives 4 via tertiary amide 5, which was not isolable. This methoxylation reaction was also carried out in penicillin series to give the desired 6α-methoxypenicillin 8 although the ring opening compound 9 was a major product. The difference between sulfenamides and selenenamides in their acylation reactions was discussed.
  • Kenso Soai, Teruaki Mukaiyama
    1979 Volume 52 Issue 11 Pages 3371-3376
    Published: 1979
    Released: April 19, 2006
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    Optically active oxiranes, β-hydroxy nitrile, β-Hiydroxy N-nitrosoamine, and thiirane were obtained (up to 72% optical purity) by the enantioface-differentiating addition of lithium derivatives of methyl phenyl sulfide, acetonitrile, N-nitrosodimethylamine, and 2-methylthiothiazoline to aldehydes using (2S,2′S)-2-hydroxymethyl-1-[(1-alkyl-2-pyrrolidinyl)methyl]pyrrolidines (1af) as chiral ligands. Optical purity of the products depended greatly on the reaction medium (dimethoxymethane or dimethyl ether gave the best results) and the structure of pyrrolidine moieties of 1af.)
  • Akio Takaoka, Hiroshi Iwakiri, Nobuo Ishikawa
    1979 Volume 52 Issue 11 Pages 3377-3380
    Published: 1979
    Released: April 19, 2006
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    The reaction products of F-propene and dialkylamines, mixtures of α,α-difluoroalkylamine and α-fluoro enamine, were found to be useful fluorinating agents for alcohols and carboxylic acids. These reagents were superior to the adduct of chlorotrifluoroethene and diethylamine, the so-called Yarovenko reagent, for their readier preparation and higher stability.
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