Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 46 , Issue 9
Showing 1-50 articles out of 97 articles from the selected issue
  • Kenichi Okamoto, Shigekazu Kusabayashi, Hiroshi Mikawa
    1973 Volume 46 Issue 9 Pages 2613-2619
    Published: 1973
    Released: March 27, 2006
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    The photoconductivity and fluorescence spectra of poly(N-vinylcarbazole) (PVCz) films doped with various materials were investigated. The photoconductive properties of doped films may be grouped into three classes according to the kind of dopant. The doping of an electron donor, such as tetramethyl-p-phenylenediamine and 1,5-diaminonaphthalene, reduced the photocurrent in all the wavelength regions by a factor of 102 to 104 because of the hole-trapping effect of the dopant molecule. The exciplex formed between the donor and PVCz does not seem to contribute to the photocurrent. The doping of an acceptor, such as TCNE and dimethyl terephthalate, on the other hand, enhanced the photocurrent. The field-assisted thermal dissociation of an excited CT complex formed between PVCz and an acceptor seems to be a carrier generation process. The doping of anthracene or perylene quenched the fluorescence of PVCz by a factor of 10 to 30 and reduced the photocurrent in the UV region by a factor of 2 to 7, while it enhanced the photocurrent in the absorption region of the dopant.
  • Tadao Kenjo, Seishi Yajima
    1973 Volume 46 Issue 9 Pages 2619-2625
    Published: 1973
    Released: March 27, 2006
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    Some doping effects on the semiconducting properties of the Gd2CuO4 compound were investigated. The ZrO2 or ThO2 (0.5 mol%) lowered the resistivity of the Gd2CuO4 at room temperature by a factor of 104. The thermoelectric powers of the same samples were negative. These were explained as being due to the Cu+ ions formed by the dopants. The CaO dopant lowered the resistivity by a factor of ten and converted the sign of the thermoelectric power from negative to positive. The resistivity of the BaO-doped samples increased with an increase in the dopant concentration up to 0.5 mol%, and decreased with an increase in the dopant concentration in the concentration region lower than that. This suggested that the dopant of BaO was less effective on the resistivity-lowering than was the CaO. The samples doped with the ZrO2 and CaO simultaneously gave a trend similar to those doped with the BaO in the concentration dependence of the resistivity. Silver oxide and indium oxide were also employed as dopants, but no doping effects were observed on either resistivity or the lattice parameters.
  • Takeshi Takemura, Hiroaki Baba, Masahisa Fujita
    1973 Volume 46 Issue 9 Pages 2625-2629
    Published: 1973
    Released: March 27, 2006
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    The kinetics of triplet-triplet (T-T) energy transfer in fluid solution has been studied by means of laser pulse photolysis with acetophenone as the energy donor and naphthalene as the acceptor. Decay curves of phosphorescence of the donor and rise-and-decay curves of sensitized T-T absorption of the acceptor were obtained. These were analyzed to determine the unimolecular and bimolecular rate constants (denoted by k1 and k2 respectively) for the deactivation processes of the triplet state of donor or acceptor and the rate constant (kt) for the T-T energy transfer. In isooctane at room temperature these rate constants were found to be: k1=0.67×106 sec−1 and k2=2.0×1010 M−1 sec−1 for acetophenone, k2′=1.6×1010 M−1 sec−1 for naphthalene, and kt=1.0×1010 M−1 sec−1. The kt value obtained from the donor phosphorescence is in good agreement with that from the acceptor T-T absorption. The experimental results suggest that T-T transfer and T-T annihilation processes are not strictly diffusion-controlled.
  • Yukio Kubota
    1973 Volume 46 Issue 9 Pages 2630-2633
    Published: 1973
    Released: March 27, 2006
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    The motion of the DNA–acridine complexes in solution was studied by the fluorescence depolarization method. Five derivatives of 3,6-diaminoacridine were used in order to investigate the effect of amino substituion on the depolarization results. A linear relation between the reciprocal polarization (1/P) and T/η was obtained by varying the temperature of a native DNA–acridine solution. The limiting polarization (P0) and the mean rotational relaxation time (ρh) of the complex were evaluated from these data. The ρh value of the complex (30–50 nsec) was much larger than the value of free acridine in water, but it was much too small to correspond to the rotation of the whole DNA molecule. Further, it was found that the values of P0 and ρh for 3,6-bis(diethylamino)acridine are much smaller than those for other acridines. This may result from some steric hindrance of the binding by bulky diethylamino groups.
  • Masuo Aizawa, Shuichi Suzuki
    1973 Volume 46 Issue 9 Pages 2634-2637
    Published: 1973
    Released: March 27, 2006
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    The states of water in lyotropic liquid crystals of the polyoxyethylene–nonylphenylether and water system were investigated by means of near-infrared spectroscopic measurements. The states of water were classified into nonbonded, singly-hydrogen-bonded, and doubly-hydrogen-bonded states, and their relative concentrations were calculated from the intensities of the combination bands of 2ν13 and ν123 in the temperature range from 25 to 50 °C. An increase in the hydrogen-bonded water species was found for the liquid crystal. Furthermore, the nonbonded and singly-hydrogen-bonded water species decreased, while the doubly-hydrogen-bonded water species increased in the liquid crystal structure, as compared with ordinary water. The structural properties of the liquid crystal are discussed.
  • Teiichiro Ogawa, Masaharu Tsuji, Minoru Toyoda, Nobuhiko Ishibashi
    1973 Volume 46 Issue 9 Pages 2637-2642
    Published: 1973
    Released: March 27, 2006
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    The emission spectra of gaseous aromatic hydrocarbons under electron impact excitation (60–300 eV) were measured in the 220–450 nm region at very low pressures. A characteristic band was observed in all cases in the 240–340 nm region; this band was assigned to the transition from the lowest excited singlet state to the electronic ground state. Photoemissions from the fragment species, such as H (Balmer series) and CH (A→X, B→X), were also observed. The excited species were concluded, from the relations of the emission intensities to the electron-beam current and to the gas pressure, to be produced by one-electron processes. The relative intensity and the vibrational structure of the observed spectra were examined and compared with those of the fluorescence spectra produced by photo-excitation.
  • Hideo Yamazaki, Kyoji Shinsaka
    1973 Volume 46 Issue 9 Pages 2642-2646
    Published: 1973
    Released: March 27, 2006
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    The relations of the integral transforms and the integral form between various distribution functions have been discussed in the prescribed diffusion approximation for the Smoluchowski equation. The initial electron distribution from the central-ion cluster in a spur or a track, ω(r, 0); the time dependence of the central value of the electron distribution, ω(0, t); the time dependence of the space-averaged electron concentration, N(t), after pulse irradiation, and the scavenger-concentration dependence of the relative G-value of electron scavenging, Gs(ksCs), as a function of the scavenger concentration, Cs, and the rate constant, ks, are shown to be connected by this diagram of the Laplace transforms and the integral form:
    (Remark: Graphics omitted.)
    By the use of this relation, the various distribution functions are evaluated from the generalized Gaussian initial distribution. The square-root relationship of the Gs(ksCs) to the scavenger concentration is discussed.
  • Yoshiki Sato, Akira Amano
    1973 Volume 46 Issue 9 Pages 2646-2650
    Published: 1973
    Released: March 27, 2006
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    Rates of gas phase thermal hydrogen exchange and hydrogenolytic demethylation of toluene-2-d1, -3-d1, and -4-d1 are evaluated using flow apparatus at temperatures 675–750 °C in the presence of a large excess molecular hydrogen. Both the exchange and the demethylation obey three-halves order rate law indicating the chain mechanism carried by hydrogen atom, the former being found slightly faster than the latter. Rate parameters of the two reactions taking place concurrently are then correlated with the extended Hückel superdelocalizability values appropriate to methylcyclohexadienyl transient formation. Overall applicability of the dynamic index as a measure of reactivity of deuteriotoluenes toward hydrogen atom attack is taken as an additional support for the generally accepted chain mechanism whose rate-determining step consists of electroneutral hydrogen atom addition to aromatic nucleus.
  • Katsutoshi Ohkubo, Hiroyuki Sakamoto, Futoshi Kitagawa, Akira Ohyoshi
    1973 Volume 46 Issue 9 Pages 2651-2654
    Published: 1973
    Released: March 27, 2006
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    The mechanism of the acid-catalyzed hydrolysis of (NH3)5RuO2CR2+ (R=H, CH3, C2H5, (CH3)2CH, CH2OH, and/or CH2NH2) has been established by the trapezoidal simulation analyses with a computer. The proposed reaction sequences of SN1 combined with SN2 mechanisms involving a quasi-stable intermediate (NH3)5Ru3+ have proved to be plausible, and the kinetic parameters (rate constants, ΔH\ eweq, ΔS\ eweq, etc.) have been given for all of the elementary reactions. The aquation rate has been determined by the solvent-assisted, heterolytic dissociation of (NH3)5RuO2CR2+ and follows this order: formato>acetato>propionato>isobutyrato>glycolato>glycinato.
  • Shigeru Tsunashima, Tsutomu Toyono, Shin Sato
    1973 Volume 46 Issue 9 Pages 2654-2659
    Published: 1973
    Released: March 27, 2006
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    The possibility of the cadmium-photosensitized luminescence of NH3, CO2, CO, and CH4 was examined at 250 °C. In the case of NH3, a very strong band emission was observed at 432 nm, with a band width of about 100 nm. The sensitized luminescence of NH3 was attributed to the emission from an excited complex between triplet cadmium and NH3. In the case of CH4, a weak emission was observed at about 420 nm. In the cases of CO2, CO, and N2, however, no positive evidence of the sensitized luminescence was obtained. From the pressure dependence of the quenching of the 326.1 nm resonance line, the efficiencies of CO2, CO, NH3, and N2 for quenching the triplet cadmium atoms were estimated to be 0.16, 0.03, 3.3×10−4, and 4.9×10−5, respectively, the efficiencies of cis-2-butene being assumed to be unity.
  • Hiromasa Hirakawa, Yoshinobu Kamei, Masayasu Sugisaki, Yasumichi Oishi
    1973 Volume 46 Issue 9 Pages 2659-2662
    Published: 1973
    Released: March 27, 2006
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    Self-diffusion coefficients of oxygen and interdiffusion coefficients were measured for the O2–He system at 25 °C under 760 Torr. The interdiffusion coefficients obtained were compared with theoretical values calculated by the kinetic theory and by Darken’s phenomenological theory. The phenomenological equation was tested in comparison with the kinetic theory by making use of the results and the data reported by other investigators. A criterion determining the magnitude or error of the phenomenological equation was given.
  • Hisao Negita, Kaoru Shibata, Yoshihiro Furukawa, Koji Yamada
    1973 Volume 46 Issue 9 Pages 2662-2664
    Published: 1973
    Released: March 27, 2006
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    The charge transfer in acetonitrile-halogen complexes was examined by means of the nuclear quadrupole resonances resulting from the relevant nuclei. 14N NQR parameters (|e2Qq|=3.6000 MHz and η=0.0183) and 35Cl NQR parameters (|e2Qq|=107.44 and 108.50 MHz) were obtained for the acetonitrile-chlorine complex, whereas 14N NQR parameters (|e2Qq|=3.5439 MHz and η=0.0043) and a 81Br NQR parameter (|e2Qq|=640.52 MHz) were obtained for the acetonitrile-bromine complex. From these parameters, the charged states of the nitrogen, chlorine, and bromine atoms in these charge-transfer complexes were calculated by means of the Townes and Dailey theory. In the case of the acetonitrile-bromine complex, the charge loss at the nitrogen atom was not equal to the gain at the bromine atom, as long as the charge was assumed to be transferred only to the p-orbital of the latter. This discrepancy was explained by assuming some d-hybridization at the bromine atom. The charged states of the nitrogen atoms in these complexes were qualitatively in good agreement with the electron affinities of the chlorine and bromine molecules. Moreover, the temperature dependences of the 14N and 81Br nuclear quadrupole coupling constants in the acetonitrile-bromine complex were investigated in the range from −196 to −60 °C.
  • Tatsuo Ishikawa, Katsuya Inouye
    1973 Volume 46 Issue 9 Pages 2665-2668
    Published: 1973
    Released: March 27, 2006
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    The relationship between the activity of ferric oxyhydroxides (α-, β-, and γ-FeOOH) and structural changes has been investigated by determining the heat of immersion in H2O and H2O vapor adsorption. For each ferric oxyhydroxide, the monolayer capacity of H2O adsorption and the heat of immersion decreased with the progress of transformation into α-Fe2O3. Above the transformation temperature the heat of immersion increased with the outgassing temperature. The heat of immersion of α-Fe2O3 obtained by outgassing each ferric oxyhydroxide at 400 and 500 °C increased with the accompanying increase in crystallite size. β-FeOOH showed higher heat of immersion and larger monolayer capacity per unit surface area than other ferric oxyhydroxides. It is presumed that the higher heat of immersion and larger monolayer capacity observed for β-FeOOH are ascribed to micropores in β-FeOOH crystals produced by the removal of molecular water originally contained.
  • Fusao Takusagawa, Ken Hirotsu, Akira Shimada
    1973 Volume 46 Issue 9 Pages 2669-2675
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of cinchomeronic acid (3,4-pyridinedicarboxylic acid) has been determined by the method of X-ray diffraction. The crystals are orthorhombic, with a space group of P212121, and with cell dimensions of a=11.211, b=11.206, and c=5.285 Å. The structure was determined by the method of symbolic addition. The final R value was 5.90% for 828 observed reflections. The molecule takes the form of a zwitter ion in the crystal. The pyridine ring has, approximately, the C2v symmetry. One carboxyl group consists of C=O and C–O (H) groups, while the other consists of two O(Remark: Graphics omitted.)O groups. These carboxyl groups twist out of the plane of a pyridine ring by 39.6° and 73.0° respectively. The hydrogen bonds are in the forms of two spirals around the two-fold screw axes parallel to the c axis, thus linking the molecules three-dimensionally. There are four molecules per turn of the spiral along the c axis. The carbonyl oxygen atom O(2) is free from the hydrogen bond, while the nitrogen atom N(l) in the pyridine ring participates in it. The relations between the C–N–C bond angle of the pyridine ring and the N···H distance, and also between the net charge on the nitrogen atom calculated by the “complete neglect of differential overlap” (GNDO) method and the O···N distance for a hydrogen bond are discussed in connection with five pyridine-carboxylic acids.
  • Hayao Kobayashi
    1973 Volume 46 Issue 9 Pages 2675-2683
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of the 1:1 complex of carbazole–TCNQ was investigated by X-ray diffraction. Analysis of sharp spots and diffuse streaks in the diffraction patterns revealed that the crystal is composed of an ordered domain and a disordered one. The ordered domain is made up from two types of ordered molecular arrangements, whereas the disordered one consists of a one-dimensionally disordered structure. The structures of the two ordered domains are closely related with each other. They both contain mixed stack columns of alternating carbazole and TCNQ usually observed in charge transfer (CT) complexes. The existence of various types of domain structures as shown by diffraction patterns of many crystals grown from acetone, acetonitrile and tetrahydrofuran solutions can be interpreted in terms of the combinations of ordered and disordered domains. No CT band appears in the visible absorption spectra of the acetone solution of carbazole–TCNQ, whereas the spectra of the powdered crystals show a CT band at about 18000 cm−1. The calculation of SCF-MO-CI of the system of the carbazole–TCNQ, pair indicates a weak CT interaction.
  • Fumikatsu Tokiwa, Kaoru Tsujii
    1973 Volume 46 Issue 9 Pages 2684-2686
    Published: 1973
    Released: March 27, 2006
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    The solubilization behavior of the complexes composed of a surfactant and polyethylene glycol (PEG) toward an oil-soluble dye, Yellow OB, has been studied in relation to the degree of polymerization, n, of PEG. The solubilizing powers of the anionic surfactants, sodium dodecyl sulfate and sodium p-octylbenzene sulfonate, become greater on the addition of PEG, the extent depending on n. They increase as n increases. It is proposed that there are at least two different types of complexes, i.e., “oligomeric” and “polymeric” PEG–surfactant complexes. The boundary between the oligomeric and polymeric PEG’s is estimated to be around an n value of 10–15. With an oligomeric PEG–surfactant complex, the solubilization of Yellow OB would occur mainly in the hydrocarbon part of the surfactant micelle. With a polymeric PEG–surfactant complex, on the other hand, the solubilization would take place in the region of a complex rich in PEG. Electrical-conductivity and absorption-spectral data on the complexes are also included in this paper.
  • Masatoshi Hirayama, Yoshiaki Hanyu
    1973 Volume 46 Issue 9 Pages 2687-2690
    Published: 1973
    Released: March 27, 2006
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    1H and 13C paramagnetic shifts induced by Eu(DPM)3 and Pr(DPM)3 in acridine, quinoline, and isoquinoline in CCl4 are observed. It has been found that, while the 1H shifts can be interpreted solely in terms of a pseudo-contact interaction, there is a much larger contact-term contribution to 13C shifts induced by Eu(DPM)3 than by Pr(DPM)3 in these compounds; this contribution to the 13C shifts cannot be explained by a simple combination of σ- and π-contact terms.
  • Michiro Hayashi, Kazunori Kuwada
    1973 Volume 46 Issue 9 Pages 2691-2698
    Published: 1973
    Released: March 27, 2006
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    The microwave spectra of four isotopic species of bromomethylsilane have been measured, viz., the 79Br and 81Br species of BrCH2SiH3 and BrCH2SiD3. The observed rotational constants have been well explained by a model of which the structural parameters have been transferred from the corresponding parameters determined for ethylbromide and chloromethylsilane. The principal quadrupole coupling constants have been determined through the analysis of the first- and second-order effects of quadrupole coupling on the hyperfine structure of the observed spectra. It was concluded, within the experimental error, that the quadrupole coupling constants tensor of this molecule has the cylindrical symmetry around the largest principal axis, the direction of which coincides approximately with the C–Br internuclear line.
  • Tadayoshi Sakata, Toshihiro Okai, Hiroaki Sugimoto, Hiroshi Tsubomura
    1973 Volume 46 Issue 9 Pages 2698-2701
    Published: 1973
    Released: March 27, 2006
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    Electronic spectra of the cation radicals of some aromatic diamines in triethylamine were found to differ remarkably from those in other solvents such as ether or alcohol as regards (1) swelling of the absorption at around 25000 cm−1, (2) broadening of the first band system and (3) red shift of the same system. It was concluded that these phenomena are due to the charge transfer interaction between cation radicals and triethylamine.
  • Reita Tamamushi
    1973 Volume 46 Issue 9 Pages 2701-2708
    Published: 1973
    Released: March 27, 2006
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    The Donnan membrane equilibria arising across permselective collodion matrix membranes were studied both by a static and a flow method in systems which contain only simple strong electrolytes at relatively high concentrations, up to 0.4 equiv/l. Experimental details of the flow method and its advantage in studying the ion activity behavior are presented. From the measurements of equilibrium concentrations and Donnan membrane potentials the ratios of ion activity coefficients were calculated for the following pairs of electrolytes in mixed solutions: sodium chloride–sodium nitrate, sodium sulfate–ammonium sulfate, potassium oxalate–ammonium sulfate, and potassium oxalate–ammonium oxalate. The experiments prove the feasibility of determining the ratios of ion activity coefficients in mixed solutions at concentrations where other methods lose their usefulness.
  • Hiroshi Maeda, Takashi Inoue, Masa-aki Tsunoda, Shoichi Ikeda
    1973 Volume 46 Issue 9 Pages 2708-2711
    Published: 1973
    Released: March 27, 2006
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    Conformation of poly(S-benzyl-L-cysteine) was investigated by measurements of optical rotatory dispersion, infrared absorption and viscosity in dichloroacetic acid (DCA)–chloroform mixtures. Transition from random coil to the β-structure was confirmed to occur when DCA content of the solvent was reduced below 40% (v/v). Both dispersion parameters a0 and b0 increased as the polymers were transformed into the β-structure. Viscosity of the polymer solution changed only slightly with accompanying the transition. This was interpreted in terms of the formation of intramolecular β-structure. In the region where the β-structure was dominant both optical rotatory parameters and viscosity were independent of solvent composition. Such behavior has been rarely observed in the β-coil transition of other polypeptides. The β-structure of poly(S-benzyl-L-cysteine) was shown to be more stable than that of poly(O-benzyl-L-serine) as referred to respective random coil conformations.
  • Nobuhiko Muto, Tsuyoshi Komatsu, Tsurutaro Nakagawa
    1973 Volume 46 Issue 9 Pages 2711-2715
    Published: 1973
    Released: March 27, 2006
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    The potentiometric titration of poly(maleic acid) (PMaA) in aqueous solutions containing alkali metal salts and a tetramethylammonium salt was carried out at 25 °C, and the effect of the counterions on the titration behavior of PMaA was examined in detail. The acidity of the primary carboxylic groups of PMaA increases in the order of (CH3)4N+<Li+<Na+<K+, whereas that of the secondary carboxylic groups increases with the decrease in the crystallographical radius of the counterions, in agreement with the results for ordinary polycarboxylic acids. The order of K+>Na+>Li+ for the binding strength to the primary carboxylate groups of PMaA is interpreted in terms of the radius of the hydrated cations; it can be attributed to the stable ring structure of the monoanion of the maleic acid residue, resulting from the hydrogen bonding between two adjacent carboxylate groups.
  • Taitiro Fujinaga, Yasuo Deguchi, Kisaburo Umemoto
    1973 Volume 46 Issue 9 Pages 2716-2721
    Published: 1973
    Released: March 27, 2006
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    In order to examine the effect of solvents on the hyperfine splittings of anion radical the electron spin resonance spectra of substituted nitrobenzene anion radicals were studied. The effect of hydroxylic solvent is enhanced when the nitro group is forced out of the plane of the benzene ring due to the steric influence of the bulky functional group at the ortho position. The effect is reduced when the nitro group forms intramolecular hydrogen bond with the hydroxyl group at the ortho position. A model for the solvent effect considering the hindered rotation of the nitro group in the radical molecule caused by the formation of intermolecular hydrogen bond with solvent is found to be reasonable from a molecular orbital calculation, taking account of changes in molecular orbital parameters resulting from hydroxylic solvation. The shifts in polarographic half wave potentials with the solvent system as well as the dehalogenation reaction in the course of electrochemical reduction of halonitrobenzenes is interpreted by means of the model.
  • Toshio Nagatani, Kenji Yoshihara, Takanobu Shiokawa
    1973 Volume 46 Issue 9 Pages 2721-2723
    Published: 1973
    Released: March 27, 2006
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    Gross sections of methylamine and methanol for ion-molecule reactions with various rare gases have been studied by means of a charge spectrometer used as a double mass spectrometer. The results differed from those predicted by the Gioumousis-Stevenson theory. The difference was most pronounced for helium ion, the lightest ion.
  • Hirokazu Miyoshi, Hiroaki Ohya-Nishiguchi, Yasuo Deguchi
    1973 Volume 46 Issue 9 Pages 2724-2728
    Published: 1973
    Released: March 27, 2006
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    The magnetic transition from the ferro- to the para-magnetic state of manganese(II) phthalocyanine (C32H16N8Mn) has been observed by measurements of the magnetic susceptibility, the magnetization and the proton magnetic resonance in the low-temperature range. The positive Weiss constants were obtained from the static susceptibility measurements and the proton magnetic measurements. Moreover, the magnetic-field dependences of the experimental results were found in the low-temperature range. All of those findings confirm the ferromagnetic behavior of this substance in the lower-temperature region. From the measurements of the frequency shift in the resonant circuit of the proton magnetic resonance apparatus, the transition temperature was determined to be 8.6 K. A possible mechanism of long-range ordering was also discussed on the basis of the crystal structure of this substance.
  • Nagao Azuma, Jun Yamauchi, Kazuo Mukai, Hiroaki Ohya-Nishiguchi, Yasuo ...
    1973 Volume 46 Issue 9 Pages 2728-2734
    Published: 1973
    Released: March 27, 2006
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    The static magnetic susceptibility and the ESR spectra from 1.6 to 300 K have been measured on a powder sample of the titled free radical. The broad maximum in the susceptibility which indicates an antiferromagnetic interaction has been observed at 6.9 K. The broadening of the ESR absorption line and the shift of the g-value have been found in the temperature region below Tmax, in which the susceptibility reached its round maximum. There appeared anomalies in the slope of the susceptibility, the linewidth, and the g-value versus temperature curves in the vicinity of 1.7 K. These anomalies may imply a magnetic-phase transition from the short-range ordered state to the long-range ordered state at about 1.7 K. The existence of a ferromagnetic interaction between the magnetic chains in the triphenylverdazyl radical solid is discussed on the basis of the susceptibility, the spin distribution, and the crystal structure. It is understood qualitatively that the radical with a negative spin density has a latent ferromagnetic interaction in or between the magnetic chains, and that the obsrevation of this interaction greatly depends upon the molecular and crystal structure.
  • Shoji Kaneshina, Mitsuru Tanaka, Tatsuhiko Kondo, Tomoaki Mizuno, Koic ...
    1973 Volume 46 Issue 9 Pages 2735-2738
    Published: 1973
    Released: March 27, 2006
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    The binding isotherms of bovine serum albumin (BSA) with cationic detergents, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, and tetradecyltrimethylammonium bromide have been determined at temperatures 8 and 25 °C for pH 6.8. The isotherms have also been determined at pH 3.0 and 25 °C. The effect of KBr on the binding of dodecyltrimethylammonium bromide to BSA has been examined at 25 °C for pH 6.8. The results obtained are as follows. (a) The average number of detergent cations bound, \barv, increased with the increase in the length of hydrocarbon chain, (b) the standard free energy changes −ΔG°, calculated from the intrinsic association constants K, were comparable with the cohesive energy change when one methylene group is transferred from the aqueous phase to the hydrocarbon environment on micellization, (c) values of \barv at pH 3.0 differ only slightly from those at pH 6.8 in a wider range of detergent concentration, and (d) the presence of the salt shifted the binding isotherms to the lower detergent concentrations. These results are discussed as regards the nature of micellization of detergents.
  • Katsutaka Sasaki, Kiyoshi Arakawa
    1973 Volume 46 Issue 9 Pages 2738-2741
    Published: 1973
    Released: March 27, 2006
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    Ultrasonic absorption and sound velocity were measured for aqueous solutions of tetramethylurea at temperatures 10–30 °C. Excess compressibility and partial molar volume were obtained. The curves for the concentration dependence of density, viscosity, and absorption show a maximum at about 60 vol% (20 mol%). The excess compressibility curve shows a minimum at the same concentration. It is concluded that a molecular complex of the molar ratio 4: 1 (water: tetramethylurea) linked with hydrogen-bonds is formed at 20mol%. In a dilute solution (below 4mol%), the magnitude of ultrasonic absorption of tetramethylurea solutions is equal to that of 1,3-dimethylurea solutions, but is less than that of 1,3-diethylurea solutions. The tetramethylurea–water interaction is of a similar nature to that between 1,3-dimethylurea and water in a dilute solution.
  • Yoshiharu Usui, Haru Enokido
    1973 Volume 46 Issue 9 Pages 2741-2744
    Published: 1973
    Released: March 27, 2006
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    The rate constant for an electron transfer reaction between triplet eosine and potassium tris(oxalato)cobaltate(III) was estimated. The experimental results from flash photolysis indicate that a transient semioxidized eosine exists in a free state. When a substrate was added to the deaerated eosine and complex solution at an optimum concentration, the original dye was restored by electron transfer from a substrate to the semioxidized eosine, sensitized oxidation occurring efficiently. Choosing indole and its derivatives as a substrate, we have obtained the elementary rate constants of the eosine recovery process.
  • Shigeru Yamashita, Kuniyasu Okumura, Teruo Hayakawa
    1973 Volume 46 Issue 9 Pages 2744-2747
    Published: 1973
    Released: March 27, 2006
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    The direct photolyses in the two wavelength regions and the biacetyl-photosensitized decomposition have been studied for l,l′-azo-n-propane and 2,2′-azo-isopropane. The value of kd/kc, the ratio of the disproportionation rate to the combination rate of free radicals, has been found to be slighlty dependent on the exciting wavelength as for n-propyl and isopropyl radicals. The higher the exciting energies, the larger the ratio kd/kc. From the quenching study of biacetyl phosphorescence, it was found that the energy of the excited biacetyl molecule was transferred to the azopropane molecule at every collision.
  • Kazuaki Harata, Jiro Tanaka
    1973 Volume 46 Issue 9 Pages 2747-2751
    Published: 1973
    Released: March 27, 2006
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    Crystals of (−)-2,2′-bisbromomethyl-l′-binaphthyl have been subjected to crystal structure analysis in order to determine the absolute configuration of optically active 1,1′-binaphthyl derivatives. The crystals are orthorhombic, space group P212121 with Z=4 and the lattice constants are; a=10.360, b=13.052, c=13.178 Å. The structure was solved by the heavy atom method and the final R index was 0.064. The absolute configuration was determined as (S)-configuration by utilizing the anomalous dispersion effect of bromine atom.
  • Hiromu Sugeta, Tatsuo Miyazawa
    1973 Volume 46 Issue 9 Pages 2752-2755
    Published: 1973
    Released: March 27, 2006
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    The infrared absorption intensities of torsion-rotation transitions were theoretically derived on the basis of torsion-rotation interactions of molecules with symmetric internal rotor. The theoretical intensities depend upon molecular structure parameters and molecular dipole moment. Implications of the present theory are discussed on absolute intensities, orientations of dipole transition moment, band types (A, B, or C), and deuteration effects on absorption intensities of methyl torsional transitions. For propylene oxide and propylene sulfide, the far infrared spectra of the gaseous state were measured, and the experimental absorption intensities of methyl torsional vibrations were compared with theoretical intensities.
  • Yoshinori Hasegawa, Takehiro Abe
    1973 Volume 46 Issue 9 Pages 2756-2758
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The initial interactions of m-dinitrobenzene, 2,4-dinitroanisole, 2,4-dinitrofluorobenzene, and 2,4-dinitrochlorobenzene with hydroxide ion in aqueous dimethyl sulfoxide were studied with a rapid scan spectrophotometer. In all the cases, the first transient colored-species assigned to 1-hydroxy-3-substituted-2,6-dinitrocyclohexadienates were observed at initial stages before the formations of the second colored-species having the π-electronic structures of 1,3-dinitropentadienyl anion were complete.
  • Emiko Ohyoshi
    1973 Volume 46 Issue 9 Pages 2758-2761
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An attempt was made to estimate the amount of the cationic complex MA+ adsorbed on a cation exchanger. This method is based on the fact that the ratio of the distribution coefficients of M2+ and MA+ should vary with the ionic strength of the medium. The Ni(II) acetate system studied by Fronaeus has been reexamined. The results show that the distribution coefficient of NiAc+ (Ac=acetate) is negligible compared with that of Ni2+ upon the variation of the ionic strength from 0.2 to 1.0. It was found that Fronaeus overestimated the distribution coefficient of NiAc+ and that this caused the value of β2 to be much greater. In conclusion, the two functions, \varphi1 and f, introduced by Fronaeus could not be determined with high accuracy; for the stability constants obtained by Fronaeus’s method, they must be confirmed by conducting the experiment at a different ionic strength.
  • Tadashi Iwachido
    1973 Volume 46 Issue 9 Pages 2761-2765
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    As regards the distribution of alkali metal picrates between water and methyl isobutyl ketone, distribution ratios of alkali metals and acid species were determined in the pH range 1.5–8.5. The extraction curves are almost the same for each alkali metal. Association constants of the picrates and the dissociation constant of picric acid in the organic phase were determined conductometrically. The association constants of picrates in the aqueous phase were determined with distribution coefficients by means of a solvent extraction method. The results obtained show that the picrates exist mainly in a dissociated form in both phases, whereas picric acid exists in a weakly dissociated form in the organic phase. The extractability of picrates is discussed on the basis of the extraction parameter proposed and compared with that of the nitrobenzene system.
  • Hiroshi Yokoi, Shigeru Ohsawa
    1973 Volume 46 Issue 9 Pages 2766-2768
    Published: 1973
    Released: March 27, 2006
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    Single-crystal ESR studies have been carried out on bis(L-alaninato)copper(II). Only one symmetric absorption peak has been obtained in any direction of the magnetic field, regardless of the fact that there are two molecules per unit cell. The principal values and the directions of the principal axes of the g tensor have been determined, and a correlation between those components of the g tensor and the crystal structure has been confirmed on the basis of the effect of the spin-exchange interaction between the dissimilar copper(II) ions. The absorption linewidths have been examined in order to estimate the spin-exchange energy.
  • Akira Misono, Yasuzo Uchida, Masanobu Hidai, Takamichi Yamagishi, Hiro ...
    1973 Volume 46 Issue 9 Pages 2769-2771
    Published: 1973
    Released: March 27, 2006
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    The electroreduction reaction of the zero-valent iron-2,2′-bipyridine complexes (Fe(bipy)2 and Fe(bipy)3) was studied in a hexamethylphosphoric triamide solution by polarography and ESR measurements. In the polarography, Fe(bipy)2 was first reduced at a very less negative potential (E1⁄2=−0.76V vs. Hg pool) than the first wave potential of free bipyridine (−2.37 V vs. Hg pool). In the presence of excess bipyridine, Fe(bipy)2was first reduced at −1.10 V vs. Hg pool corresponding to the second reduction step of the solution of Fe(bipy)2. The visible spectra of the solution of Fe(bipy)2 in the presence of excess bipyridine was different from that of the solution of Fe(bipy)2 only. The signal with hyperfine structure attributable to the anion radical of bipyridine was observed by means of ESR analysis of the solution electrolyzed at the potential corresponding to the second reduction step. From these results, it was concluded that [Fe(bipy)(HMPT)m] was reduced at the first step, and [Fe(bipy)2(HMPT)] was reduced at the second.
  • Kenyu Kina, Nobuko Maekawa, Nobuhiko Ishibashi
    1973 Volume 46 Issue 9 Pages 2772-2773
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Drug ion-selective electrodes with a liquid membrane have been developed which are sensitive to methacholine, neostigmine, N-1-methyl nicotinamide, diphenhydramine, vitamin B1, vitamin B6, p-aminosalicylic acid (PAS), and salicylic acid. Crystal violet or ferroin-compound cations and dipicrylamine or tetraphenylborate anions were used as the ion-exchange sites in the liquid membrane. Each liquid membrane was prepared by using the solvent-extraction method and exhibited an appropriate Nernstian response to the respective ion down to 10−4 or to 10−5 M. The electrode performances, including the selectivity coefficients, are summarized in Table 1.
  • Taira Imamura, Masatoshi Fujimoto
    1973 Volume 46 Issue 9 Pages 2774-2776
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The kinetics of the non-complementary reactions of Ce(IV) and Co(III) with Variamine Blue perchlorate were studied under nitrogen atmosphere in aqueous perchlorate media of ionic strength μ=2.0 M. The iminoquinone form of Variamine Blue was spectrophotometrically followed at 550 nm by stopped-flow technique. The rate constants of the stepwise reaction, Mn++(V.B.)\oversetkα\undersetkγ\ ightleftharpoonsM(n−1)++(V.B.)sox,Mn++(V.B.)sox\xrightarrowkβM(n−1)++(V.B.)ox+2H+ were evaluated at 25°C to be kα=1.7×105 and kβ=2.4×105 M−1 sec−1 for Ce4+ and kα=1.35×104 and kβ=1.53×104 M−1sec−1 at [H]=1.0 M for Co3+. The rates of Ce4+ were not affected by [H]. The [H]-dependece of kα and kβ for Co3+ gives the mechanism Coaq3++B\oversetk1\ ightleftharpoons product, CoOHaq2++B\oversetk2\ ightleftharpoons product, Coaq3+\oversetKh\ ightleftharpoonsCoOHaq2++H+, with K2\simeq107 M−1sec−1, suggesting an outer-sohere mechanism for the electron transfer with CoOH2+.
  • Kazuyo Matsuzawa, Kazuo Saito
    1973 Volume 46 Issue 9 Pages 2777-2779
    Published: 1973
    Released: March 27, 2006
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    Isotopic exchange kinetics between [Al(dbm)3] and Hdbm–14C (dbm, anion of dibenzoylmethane in enol form) has been studied in tetrahydrofuran (THF) at 30 to 55°C. During several half lives the McKay plot gives straight lines, the AB spectrum remaining unchanged. The rate is very small in the absence of catalysts, and accelerated by water and trichloroacetic acid, but not by weak acids and pyridine. The rate is expressed by
    R = [complex](k_2[H_2O]+k_3’[acid]+k_3[acid][H_2O])
    The Arrhenius plots of k2, k3′, and k3 give an equal Δ\ eweq value 25.6 kcal/mol. It appears one of the ligands is present as unidentate in the intermediate state, and the break of the remaining bond is the rate-determining step.
  • Yoshio Kamiya, Masayoshi Kotake
    1973 Volume 46 Issue 9 Pages 2780-2784
    Published: 1973
    Released: March 27, 2006
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    The rate of oxidation of cyclohexanone catalyzed by manganese salt increases remarkably in the presence of acetic acid, and is about one hundred times as high as the limiting rate of oxidation kp2(RH)2/2kt. However, manganese concentration does not affect the rate of oxidation much in a wide range. The oxidation of cyclohexanone by manganic ion should be the rate determining step, since the rate of oxidation, which is of first order in cyclohexanone but independent of manganous ion, corresponds to the rate of oxygen absorption of cyclohexanone with the same manganese concentration. The oxidation of cyclohexanone by manganic ion seems to proceed through enol intermediates, since the rate of oxidation increases in the presence of alkali acetates. The rate equation including enolization step and the subsequent oxidation of enol intermediate with manganic ion agrees with the experimental results. A remarkable synergistic effect of metal salts was observed in a mixture of manganese and cobalt. The oxidation products were also analyzed and discussed.
  • Shukichi Sakuraba, Soichi Mimura, Ryoka Matsushima
    1973 Volume 46 Issue 9 Pages 2784-2787
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A comparative study of the photokinetic behaviors of aliphatic alcohols and related substrates was made for the photooxidation with uranyl ions. Ethylene glycol, glucose, sucrose and some other substrates showed abnormal results compared to a series of simple aliphatic alcohols: the photoredox quantum yields φ for the former substrates decreased with substrate concentration (at their higher concentrations) and temperature rise, in contrast to simple aliphatic alcohols. In aqueous acetone solution φ increased with the increase in acetone content, the reaction constant ρ* being more negative than in aqueous solution. In 40% aqueous acetone solution the φ values for simple aliphatic alcohols varied in a complicated way with temperature. The abnormal results were interpreted in terms of the relative importance of physical quenching competing with the primary chemical process.
  • Katumitu Hayakawa, Shoko Minami, Sumio Nakamura
    1973 Volume 46 Issue 9 Pages 2788-2791
    Published: 1973
    Released: March 27, 2006
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    The kinetics of the oxidation of ascorbic acid by the copper(II) ion has been studied spectrophotometrically by a stopped-flow technique. At pH 4–6, the initial rate of the decrease in the monohydroascorbate anion is of the second-order with respect to the total concentration of the copper(II) ion and of the first-order with respect to the concentrations of the monovalent and divalent ions of ascorbic acid:
    -(d[HA^-]/dt)_t=0=k_1[Cu(II)]_T^2[HA^-]+k_2[Cu(II)]_T^2[A^2-]
    where HA and A2− are the monovalent and divalent ions of ascorbic acid respectively. k1, k2, and the activation parameters are obtained as follows: k1=3.1×104, k2=6.1×1010 M−2 s−1, ΔH\ eweq=17 kcal/mol, ΔS\ eweq=8.3 cal/deg mol, and ΔG\ eweq=15 kcal/mol. The EPR signal from the ascorbate radical is not observed in the kinetic run by either a flow technique or a quenching technique. Some discussions of the mechanism of the reaction are given.
  • Ken-ichi Watanabe, Shigeo Komiya, Shinnichiro Suzuki
    1973 Volume 46 Issue 9 Pages 2792-2794
    Published: 1973
    Released: March 27, 2006
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    The catalytic effects of various transition metal complexes on the hydration of 2-pyridinecarbonitrile have been investigated. In these homogeneous catalytic reactions, free 2-pyridinecarboxamide was obtained as the sole reaction product. The transition metal species of the complexes used were Cu(II), Ni(II), Co(II), Co(III), and Pt(IV), while the ligands were ethylenediamine, bipyridine, glycine ion, and 2-pyridinecarboxamide. The complexes of Cu(II), Ni(II), and Co(II) were all catalytically active for the hydration, but those of Co(III) and Pt(IV) were inactive. No reaction occurred with 3- and 4-pyridinecarbonitriles under the same reaction conditions. The effect of the pH was remarkable. The active complex catalysts were classified into three types.
  • M. Atreyi, R. C. Gupta
    1973 Volume 46 Issue 9 Pages 2795-2797
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    pH and conductometric titration curves of copolypeptides containing L-lysine and either L-glutamic acid or L-aspartic acid residues have provided necessary evidence to believe that in the copolypeptides the zwitterion formation is complete at the isoionic point. The amounts of acid/alkali used up at the final inflexion/break in the titration curves agreed with the analytically determined quantity of basic/acid groups in the copolypeptides. Besides, the titration curves showed additional inflexions/breaks which distinguished between the various kinds of acid/basic groups present.
  • Masahiko Yasumoto, Koshin Yanagiya, Masahiro Kurabayashi
    1973 Volume 46 Issue 9 Pages 2798-2803
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    When a mixture of benzonitrile and methanol is kept under a high pressure of a few thousand atoms at an elevated temperature, methyl benziminoether is produced and trimerized to triphenyl-1,3,5-triazine. In the present study it was confirmed that the addition of ammonium salts or some nucleophiles with an active hydrogen atom such as water, amines, and ammonia at several per cents in the molar fraction increases the rate of the formation of this triazine by several times. It was found that the nucleophilic benzamidines produced by the reaction of benziminoether with amines attacked the second molecule of the iminoether and successively took the third iminoether molecule to form a triazine ring. The addition of water to the nitrile-methanol mixture produced amidine, methyl ester, amide, and amidinium carboxylate, of which the carboxylate exhibited the highest promotive effect. Some benzamidines were obtained in fairly good yields from amines and benzonitrile under similar high-pressure conditions. It is thought that this could be useful for synthesizing amidines.
  • Koshin Yanagiya, Masahiko Yasumoto, Masahiro Kurabayashi
    1973 Volume 46 Issue 9 Pages 2804-2808
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The examination of the simultaneous formation of symmetrically tri-substituted 1,3,5-triazines, 4-amino-2,5,6-substituted pyrimidines and N-pyrimidylamidines in mixtures of lower alcohol and nitrile with more than two hydrogen atoms on the α-position under pressures of a few thousand atm afforded the following information: (1) the triazine is formed by the cyclo-trimerization of the iminoether which is derived from the nitrile and the alcohol; (2) the pyrimidine is formed by the rearrangement of the previously-formed triazine. This rearrangement is caused by an attack of the nucleophilic iminoether on a carbon atom of the triazine ring; and (3) the amidine is assumed to be formed, together with the pyrimidine, by the same attacking mechanism.
  • Koshin Yanagiya, Masahiko Yasumoto, Masahiro Kurabayashi
    1973 Volume 46 Issue 9 Pages 2809-2814
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It was found that, when some symmetrically 2,4,6-tri-substituted 1,3,5-triazines are kept with an iminoether or an amidine under high pressures and at elevated temperatures, unsymmetrically 2,4,6-tri-substituted 1,3,5-triazines are produced by way of the replacement of one or two (Remark: Graphics omitted.) groups of the triazines with the (Remark: Graphics omitted.) group of the iminoether or that of the amidine. Several mixtures of nitriles and methanol can be used for this replacement reaction in place of iminoethers or amidines at 4000–8000 atm and 100–150 °C. In these mixtures, equilibrium amounts of methyl iminoethers are rapidly formed. Increases in the size of the substituents of the original triazine and in their electron-releasing power inhibit this replacement reaction. Nitriles with an electron-releasing moiety give tri-substituted triazines replaced selectively by one of the original substituents.
  • Akira Hosono, Kiyohisa Fujii, Toshizo Tada, Hisayuki Tanaka, Yohko Ohg ...
    1973 Volume 46 Issue 9 Pages 2814-2820
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A kinetic study of the fusion reaction and the reaction in dimethyl sulfoxide of 2,6-dichloropurine with 1,2,3,5-tetra-O-acetyl-β-D-ribofuranose was undertaken, and both of them were proved to be of the second order. The activation energy and the activation entropy of the reaction in dimethyl sulfoxide were obtained: Ea=38.0 kcal/ mol and ΔS\ eweq=+15.3 cal · mol. The reaction was thus concluded to be bimolecular involving a considerable unimolecular character. Subsequently, the fusion reactions of 2,6-dichloro- and 2,6,8-trichloropurine with 1,2,3,5-tetra-O-acetyl-α- and -β -D-ribofuranose were examined by NMR spectroscopy with respect to the relative content ratios of all the materials and products in each reaction mixture; the results were found to be in good agreement with those obtained by the above kinetic study. On the basis of these results, the mechanism of the fusion reaction was discussed.
  • Koji Kudo, Michito Sato, Masanobu Hidai, Yasuzo Uchida
    1973 Volume 46 Issue 9 Pages 2820-2822
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Oxidative addition reactions of alkyl halides to Pd(CO)(PPh3)3 were studied. Vinyl chloride, allyl chloride, allyl bromide, methallyl chloride, benzyl bromide, methyl iodide, and iodobenzene react with Pd(CO)(PPh3)3 to afford the corresponding acyl complexes of the type to the type trans-PdX(COR)(PPh3)2. The reactions proceed rapidly when the dissociation energy of carbon-halogen bond in the saturated alkyl halides is smaller than about 60 kcal/mol. In the case of the unsaturated alkyl halides the more inert carbon-halogen bond can be activated by initial formation of π complexes.
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