Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 3
Showing 1-50 articles out of 67 articles from the selected issue
  • Dale K. Cabbiness, Edward S. Amis
    1967 Volume 40 Issue 3 Pages 435-440
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Nickel(II) and iron(III) have been found to complex with chloranilic acid in 1 : 1 and 1 : 2 ratios, respectively. The complexes were studied spectrophotometrically by the method of continuous variations in aqueous solutions at an ionic strength of 0.15 and at different values of pH and temperature. Formation constants and other thermodynamic properties have been determined. It is proposed that these complexes are chelates.
  • Yoshiharu Usui, Masao Koizumi
    1967 Volume 40 Issue 3 Pages 440-446
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An example is presented in which the complicated photochemical behavior of a system involving dye, a reducing agent, and oxygen is interpreted on the basis of the rate constants of the elementary reactions, which predict the change in mechanism from a D–D (or D–O) to a D–R mechanism. The dye chosen is eosine, and the reducing agent is EDTA. Investigations have been made of the quantity of oxygen consumed by the aerated aqueous dye solution, of the rate of oxidative photobleaching, and of the photochemical yield of hydrogen peroxide; the influence of the EDTA concentration on these quantities has been studied in particular. This influence was especially remarkable on the third phenomenon; the yield of hydrogen peroxide shows a sharp maximum at a certain EDTA concentration, ∼1×10−2 M for 1.0×10−3 M and 1.0×10−4 M of dye, and ∼6×10−2 M for 1.0×10−5 M of dye. To give a quantitative account of the above phenomena, the rate constants for the following elementary reactions have been determined tentatively by the flash technique:
    (Remark: Graphics omitted.)
    Although further evidence for the existence of D+···O2 and D+···D would be desirable, the above data as well as those already reported by Lindqvist and by our group, are well correlated with the present results.
  • Yukimasa Fukui, Hideo Takaoka, Jukichi Ishii, Kenji Hirai, Toshiro Tak ...
    1967 Volume 40 Issue 3 Pages 446-451
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The vapor-phase alkylation of benzene with ethylene over the various metal sulfates supported on the silica-alumina (SA) catalysts has been studied by a flow method under a pressure of 30 kg/cm2 and within the temperature range of 230–450°C. The metal sulfate supported on the SA catalyst showed a relatively higher activity than the SA used as a carrier, and the activity of the metal sulfate as the modifier of SA is in the order of; manganous sulfate>zinc sulfate>chromic sulfate>cupric sulfate. Under the optimum conditions, in which benzene and ethylene were brought to reaction at the molar ratio of 2.5, a LHSV of benzene of 1.2 hr−1, under a pressure of 30 kg/cm2 and a reaction temperature of 300°C over the manganous sulfate supported on a SA catalyst (the weight ratio of manganese to SA is 1/10), the conversion of ethylene was 56.7% and the selectivity to ethylbenzene and diethylbenzene was 94.0%.
  • Naoto Yamamoto, Yoshihiro Nakato, Hiroshi Tsubomura
    1967 Volume 40 Issue 3 Pages 451-455
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A mixture of N, N, N′, N′,-tetramethyl-p-phenylenediamine (TMPD) and pyrene in some rigid matrices was illuminated at a low temperature in the near ultraviolet region. It was found that TMPD+, pyrene anion, and solvated electrons are formed in the medium. The ratio of the formation of pyrene anion and TMPD+ has been studied at various concentrations of pyrene. The behavior of the photo-ejected electron, particularly its extent of migration has then been discussed on the basis of the experimental results. The thermoluminescence spectrum of the UV-irradiated matrix containing TMPD and pyrene was measured after it had been illuminated in the infrared region. The luminescence may tentatively be assigned to the charge transfer fluorescence. The emission spectra were investigated for a mixture containing TMPD and α-methylnaphthalene in several solvents by exciting the TMPD. It was found that a new emission band appeared at 480 mμ. It was assigned to the charge transfer fluorescence.
  • Teijiro Yonezawa, Kiyoshi Shimizu, Hiroshi Kato
    1967 Volume 40 Issue 3 Pages 456-460
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Extended LCAO MO investigations into the physico-chemical properties of cycloalkanes and their derivatives are carried out. The bond natures of C–C and C–H in cycloalkanes, the electronic distributions of the lowest vacant orbital, the electron-attracting powers of the ring, and the relative reactivity of the ring cleavage are successfully explained. Further, their ionization potentials and electron affinities are discussed. In addition, the electronic distributions on the equatorial and axial forms of monosubstituted cyclobutane and cyclohexane are made explicit.
  • Mitsunori Sukigara, Shin-ichi Kikuchi
    1967 Volume 40 Issue 3 Pages 461-466
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electronic states of benzene diazonium cation were calculated by a method similar to that of Pariser and Parr. On the basis of the calculations, the 259 mμ and 295 mμ absorption bands were attributed to 1A11A1 and 1A1-1B1 transitions respectively. When the sample was irradiated in an alcoholic solution by a 295 mμ light, no ESR signal was detected, but fluorescence and phosphorescence were observed; the fluorescence and the absorption spectrum of 1A11B1 transition have the correlation of a mirror image to each other. On the other hand, upon irradiation by a 259 mμ light, this sample showed an ESR spectrum which was attributed to the phenyl σ-radical, but no fluorescence or phosphorescence was observed. From the above experimental results and theoretical considerations, it was concluded that the electronically-excited benzenediazonium salt releases its excess energy by the following processes: (1) From the excited 1B1 state, there occur radiative transition to the ground state and intersystem crossing to the phosphorescent state, though it is as yet uncertain whether 3B1 or any other triplet states are involved. The photodecomposition does not proceed from the excited 1B1 state. (2) From the excited 1A1 state, neither the radiative transition to the ground state nor a nonradiative transition to any fluorescent or phosphorescent states occurs. The molecule decomposes rapidly to give phenyl σ-radical after excitation to this electronic state.
  • Masaji Miura, Yukio Kubota
    1967 Volume 40 Issue 3 Pages 466-472
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The interaction of sodium polyphosphates with acridine orange has been studied by means of absorption spectra, fluorescence, and viscosity measurements. Polyphosphates with a variety of molecular weights were used in order to investigate the effect of the degree of polymerization (\barn) on the interaction. No spectral change was observed in the case of polyphosphates with \barn<5. In the case of \barn=9, an absorption band corresponding to the dye dimer was observed, whereas in the case of larger \barn values those corresponding to higher aggregates were also found. The maximum metachromasy occurred at PD=3–6. Fluorescence quenching was observed, accompanied by an absorption change. Such behavior may be considered to be characteristic of the dye molecules bound to the long-chain polyphosphates; the bound-dye molecules seem to exhibit almost no fluorescence. The quenching constants of the fluorescence increased with the increase in \barn values. The binding energies were estimated to be 5–6 kcal/mol independent of the \barn values. In the presence of acridine orange, the reduced viscosity of Kurrol’s salt decreased remarkably, probably as a result of the neutralization of the charged phosphate groups. Further, its reduced viscosity decreased remarkably with time; this may be attributed to the catalytic action of the dye on the hydrolytic degradation of polyphosphates.
  • Mineo Watase, Kiyoshi Arakawa
    1967 Volume 40 Issue 3 Pages 472-475
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A stress-relaxation experiment on hydrogels of agar-agar has been made over the range of concentration of about 3—11% by weight. A chainomatic balance relaxometer was used for the measurement of the relaxation Young’s modulus, and the temperature was varied over the range of about 20—70°C. The obtained relaxation curves have been analyzed using a mechanical model composed of three parallel Maxwell models. The relaxation times obtained for the gels of different concentrations at the same temperature have been found to be independent of the concentration. The elastic Young’s modulus, which may be attributed to the main network structure in the gels, has been found to be proportional to the 1.8 power of concentration. From the temperature dependence of the longest relaxation time, the activation energy for the relaxation process attributed to the destruction of junctions in the main network structure has been determined to be about 5 kcal/mol, irrespective of the concentration, over the whole range; this is of the order of the activation energy for the hydrogen bonds.
  • Tamaichi Ashida, Yoshio Sasada, Masao Kakudo
    1967 Volume 40 Issue 3 Pages 476-487
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of (+)-2-benzylglutamic acid hydrobromide dihydrate has been determined using three-dimensional X-ray intensity data. The crystal is orthorhombic, with four formula units in a unit cell with the dimensions: a=8.38, b=10.54, and c=17.68 Å, the space group being P212121. The structure was solved by the heavy atom method, and its parameters were refined by the least-squares method using anisotropic thermal parameters, the final R being 0.073. The absolute configuration of the glutamic acid has also been determined to be D-(+)-2-benzylglutamic acid, [α]D20+1.65° (c 10, 4 N HCl). The conformation of the carbon skeleton of the glutamic acid is different from any of the glutamic acids so far analyzed, due to the internal rotations of the C–C bonds. A detailed comparison of the conformations of several glutamic acids and glutamines will be given. Nine independent hydrogen bonds make a rather unique and complicated three-dimensional network. Among these, two between the carboxyl groups (donor) and the water molecules (acceptor) are found to be fairly strong, their bond lengths being 2.55 and 2.51 Å.
  • Teijiro Yonezawa, Isao Morishima, Mutsuo Fujii, Hiroshi Kato
    1967 Volume 40 Issue 3 Pages 487-490
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Molecular orbital calculations of proton-proton coupling constants are made for simple hydrocarbons and some other compounds with heteroatoms using the equation proposed by Pople and Santry. In the present treatment, a molecular orbital is given by a linear combination of valence atomic orbitals. The calculations for protons separated by two and three bonds lead to positive or negative constants, nearly all of which are compatible with the experimental values.
  • Hiroshi Yaji, Taiichi Higuchi, Akira Shimada, Yoshiyuki Namba, Tsutomu ...
    1967 Volume 40 Issue 3 Pages 491-494
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of 1, 6-dimethoxy phenazine was solved by the method of the molecular Fourier transform, and a refinement based on the two-dimensional data was achieved by the Fourier method and also by the least-squares method. The space group is P21/n with two molecules in the unit cell. The lattice constants are a=8.60 Å, b=12.59 Å, c=5.17 Å, and β=93.5°. The molecule has an exact center of symmetry and lies approximately on a plane, with the exception of the methyl groups, which are 0.21 Å outside the plane of the molecule. As for the phenazine ring, almost all the bond distances and angles exhibit normal values. The bond distances around the oxygen atom seem to indicate that the lone-pair electrons in this atom flow into the π-electron system of a phenazine ring. The planar molecules are stacked parallel to each other along the c axis, with an inter-planar spacing of 3.41 Å.
  • Tatsuo Nakahara, Kinsi Motomura, Ryohei Matuura
    1967 Volume 40 Issue 3 Pages 495-497
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The effects of temperature on the surface pressure of monolayers of polymethacrylates with n-alkyl groups containing from 9 to 18 carbon atoms have been studied. Two kinds of phase transitions have been observed in the surface pressure-area isotherms. On the basis of the bulk properties of the polymers, these phase changes have been interpreted as the transition of the monolayer to a three-dimensional fluid state and as side-chain crystallization.
  • Kozo Kuchitsu
    1967 Volume 40 Issue 3 Pages 498-504
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    General expressions and their practical approximations are presented for the molecular intensity of gas electron diffraction and the radial distribution function for an atom pair in the molecule which exerts moderately anharmonic intramolecular motion in thermal equilibrium. The calculations are based on a polynomial expansion of the probability distribution function of the internuclear distance around a Gaussian function representing harmonic vibration. The coefficients of the expansion for a diatomic system are calculated by the second-order perturbation method in terms of the coefficients of the potential energy expanded to the fourth order of the displacement in the internuclear distance. The structural parameters under various definitions (the mean internuclear distances, the mean square amplitudes, and the phase parameters) of a number of diatomic molecules are tabulated by the use of the spectroscopic values ωe, αe, and χe taken from the literature. The temperature dependence of the structural parameters is discussed.
  • Kozo Kuchitsu
    1967 Volume 40 Issue 3 Pages 505-510
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A method has been presented for calculating the first, second, and third moments of the displacement of an internuclear distance in a polyatomic molecule, ⟨Δr⟩, ⟨Δr2⟩, and ⟨Δr3⟩. The moments, which depend on the frequencies of normal vibrations, the cubic potential constants, and the temperature of the system, have been related to the extent of distortion of the probability distribution function of the internuclear distance from a Gaussian function caused by the anharmonicity in the potential function. An approximate expression has been obtained for the phase parameter κ in the molecular intensity of gas electron diffraction in terms of the moments. Numerical results are given for CO2, CS2, SO2, H2O, D2O, CH4, and CD4 by the use of experimental or estimated cubic potential constants. The phase parameters for bonded distances agree with simple estimates based on “diatomic approximation” to the accuracy of current experimental studies, while the phase parameters for nonbonded distances are similar in magnitude to those for bonded distances in spite of their larger mean-square amplitudes of vibration.
  • Akiyoshi Masuko, Teruo Nomura, Yoshihiko Saito
    1967 Volume 40 Issue 3 Pages 511-515
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of trans-diaquo-bis(pyridine-2-carboxamide)nickel(II) chloride, [Ni-(H2O)2(piaH)2]Cl2, was determined by X-ray diffraction and refined by three-dimensional least-squares method. The crystals are monoclinic with space group P21a, a=13.567, b=10.067, c=6.355 Å and β=113.73°. There are two formula units in the unit cell. The structure is built up of centrosymmetric complex ions and chloride ions. Two ligand molecules are coordinated to the nickel atom in trans position with amide oxygen atoms and ring nitrogen atoms. (Ni–N, 2.02 Å, Ni–O, 2.05 Å). The ligand molecules are nearly planar and they are approximately in one plane with the nickel atom. Two water molecules are coordinated at a distance of 2.14 Å and complete the octahedral arrangement around the nickel atom.
  • Yoshiharu Nawata, Hitoshi Iwasaki, Yoshihiko Saito
    1967 Volume 40 Issue 3 Pages 515-521
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The orange-red, diamagnetic crystals of [Ni(pia)2]·2H2O (piaH: pyridine-2-carboxamide) have been subjected to X-ray crystallographic analysis. They are orthorhombic, space group Pm21b-C2v2, with two formula units in a cell of dimensions: a=7.61, b=20.19 and c=4.46 Å. The crystals consist of planar molecules in which Ni(II) exhibits a square planar coordination and the two ligands are coordinated to the central nickel atom with four nitrogen atoms in trans-configuration. The molecules are tilted about 40° with respect to the plane (001), and are piled up above one another along the c-axis to form columns. These columns are linked with each other by intermolecular hydrogen bonds of N–H···O type, thus forming layers parallel to the plane (010). The layers are piled up along the b-axis by way of two water molecules which are hydrogen-bonded to the oxygen atoms of the amide groups. There exist stacking faults along this direction.
  • Akira Imamura, Hiroko Fujita, Chikayoshi Nagata
    1967 Volume 40 Issue 3 Pages 522-526
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electronic structures of adenine-thymine and guanine-cytosine pairs of DNA were calculated using the semi-empirical self-consistent field molecular orbital method. The calculations were carried out for two models, that is, one including hydrogen 2pπ orbitals and the other not. The obtained π electron densities and the π bond orders were then discussed in comparison with those of the corresponding bases. Further, the π electronic stabilization energies due to the hydrogen bond formations were calculated; the π stabilization energy of the G-C pair was found to be larger than that of A-T pair, in agreement with the experimental data. The π electronic structures in the excited states were discussed in connection with the biological behavior of DNA, that is, the misduplication of DNA leading to mutation by irradiation.
  • Gentaro Yamaguchi, Yoshiaki Kakinoki, Hiroshi Tsubomura
    1967 Volume 40 Issue 3 Pages 526-531
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The absorption and emission spectra of p-aminoacetophenone (PAAP) were measured in various solvents at different temperatures. Several interesting facts have been revealed: PAAP, which is non-fluorescent in other solvents, fluorescences strongly in the ethanol matrix at 77°K; the ratio of the intensity of fluorescence to that of phosphorescence varies according to the wavelength of the exciting light; the phosphorescence band shifts largely by changing the temperature. Explanations for these observed results have been given by considering that the lowest 1(π→π*) level and the 1(n→π*) level lie fairly close to each other in this molecule and a reversal of the energy levels occurs by changing the solvent and the temperature. The lowest triplet state of PAAP is concluded to be 3(π→π*) and not 3(n→π*).
  • Masakatsu Kochi, Yoshiya Harada, Hiroo Inokuchi
    1967 Volume 40 Issue 3 Pages 531-536
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The external photoelectric effect of the molecular crystals in the vacuum ultraviolet region was observed. The ionization potential of tetrathiotetracene, indanthrone and perylene, as estimated by the threshold values of their spectral responses, were 4.55, 5.10 and 5.40 eV respectively. The band-gap energies, calculated on a band model, were 0.62, 0.68 and 1.72 eV respectively. These values were in fairly good agreement with those obtained from the temperature dependency measurements of their electrical resistivities. By analyzing the photocurrent-voltage relation for tetracene and pentacene, the kinetic energy distribution curves were obtained. From an analysis of those curves, it turned out that the one-electron process plays a dominant role in the emission processes and that illumination with a short-wavelength light (1200 Å—1500 Å) can excite electrons from the deeper levels of the valence band to a vacuum. The observed positions of the filled π-electron levels were almost consistent with the results obtained using the LCAO method; for tetracene the depths of lower levels in order from the uppermost one, were 1.52, 2.48, 2.96, 3.46 and 3.92 eV from the observations and 1.60, 2.34, 2.98, 3.32 and 3.89 eV from the calculations.
  • Teijiro Yonezawa, Kaichiro Yamaguchi, Hiroshi Kato
    1967 Volume 40 Issue 3 Pages 536-541
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A semi-empirical SCF method for valence electron systems is presented. In the present method, the one-center integrals are estimated by means of the empirical values, while the two-center Coulomb integrals are calculated by the Ohno approximation. The other electronic repulsion integrals are evaluated by the Mulliken approximation. All overlap integrals in the secular equation are taken into account. By the present method, the electronic structures of several small polyatomic molecules are then studied. The calculated results are compared with the full SCF calculations and with the experimental values. The agreements between them are almost entirely satisfactory. The limitations of this method and the values of the parameters used are also discussed briefly.
  • Hiroshi Takahashi, Kazuo Tsutsumi
    1967 Volume 40 Issue 3 Pages 542-545
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The changes in the secondary properties of zinc oxide upon mechanical treatment were studied. In the process of the mechanical treatment of zinc oxide, the Blaine specific surface area, the sedimentation volume, and the particle size distribution changed periodically with the treatment time. Such periodical changes are characteristic of the state of association of the particles, and can be interpreted as the changes in the total energy content of the solid.
  • Nobuyuki Tanaka, Kenzo Nagase
    1967 Volume 40 Issue 3 Pages 546-550
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The thermal decomposition reactions of amminecobalt(III) complexes in solid state were studied mainly by the polarographic, the manometric and the infrared spectroscopic methods. The decomposition processes of [Co(NH3)6]Cl3, [Co(NH3)6]Br3, [Co(NH3)6]I3, [CoCl(NH3)5]Cl2, [CoBr(NH3)5]Cl2, [CoCl(NH3)5]Br2 and [CoBr(NH3)5]Br2 in vacuo, in air atmosphere and in sealed tube were investigated. In all cases, the decomposition of these complexes was initiated by electron transfer from an outer-sphere anion or a ligand to the central cobalt(III) cation. The reaction processes and products were found to be much different with the different environments, but little different with the different halide ions. The rate constants, frequency factors and activation energies for the electron transfer reactions were obtained.
  • Seizo Misumi, Noriko Iwasaki
    1967 Volume 40 Issue 3 Pages 550-554
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared spectra of tris-(acetylacetonato) complexes of praseodymium(III), neodymium-(III), europium(III), gadolinium (III), dysprosium(III), and erbium(III) have been measured in the range between 4000 and 100 cm−1 in order to obtain information about the nature of lanthanide metal-oxygen bond; some properties of these complexes were studied, also. The calculated frequencies and assignments were used to elucidate the complex spectra and to show the relations between the calculated force constants and some physicochemical properties. Although the molecules of each complex were 1 : 3 complexes, the calculation of the vibrational frequencies was made by using a simplified model of the 1 : 1 complex (C2v), because it may be supposed that this tris-(acetylacetonato) complex does not always have a regular octahedral symmetry in spite of the composition of Ln(acac)3. The calculated frequencies were in good agreement with the observed ones; the lanthanide metal-oxygen stretching vibrations were found at 420–432 cm−1 (A15) and 304–322 cm−1 (B114). The lanthanide metal-oxygen stretching force constant increases with an increase in the atomic number, while the corresponding C=O stretching frequency (A11) decreases in the same order. For example, the values of K(Pr–O) and K(Er–O) are 2.10 and 2.29 md/Å respectively. As the result of the lanthanide contraction, the force constant of the lanthanide metal-oxygen bond increases with a decrease in the M–O bond length, thus increasing the stability constant, log β, and slightly increasing the electronegativity.
  • Bunji Iwasaki, Takashi Katsura
    1967 Volume 40 Issue 3 Pages 554-561
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The solubility of hydrogen chloride in volcanic rock melts was experimentally determined at temperatures of 1200°C and 1290°C with the variation in the partial pressure of hydrogen chloride mixed with nitrogen under one atmosphere. The solubility of hydrogen chloride decreases not only with a rise in the temperature, but also with an increase in the silica content of volcanic rock melts, while it increases with an increase in the partial pressure of hydrogen chloride. The equilibrated concentration of chlorine obtained by experiments was compared with those in natural basalts collected from Japan and Hawaii.
  • Takashi Katsura, Masahiro Hasegawa
    1967 Volume 40 Issue 3 Pages 561-569
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Phase equilibria in the V2O3-VO2 system were established at 1600°K by varying the oxygen partial pressures from 10−13 to 10−3atm. The phases of V2O3, V3O5, V4O7, V5O9, V6O11 and VO2 are stable under these conditions. The only phases of V2O3 and V6O11 have extensive ranges of solid solution. The stability ranges of vanadium oxides with respect to the oxygen partial pressure were determined: V2O3, from 10−13 to 10−6.36atm; V3O5, from 10−6.36 to 10−4.90atm; V4O7, from 10−4.90 to 10−4.20atm; V5O9, from 10−4.20 to 10−4.04atm; and V6O11 from 10−4.04 to 10 −3.53atm, while VO2 is in equilibrium with V6O11 at the oxygen partial pressure of 10−3.53atm. The oxygen partial pressures were measured accurately by means of a solid electrolyte cell composed of (ZrO2)0.85(CaO)0.15; these pressures were then compared with the values calculated from the thermochemical data. On the basis of the equilibrium oxygen partial pressures, the standard free energies of oxidation of various vanadium oxides were calculated.
  • Tomozo Koh, Iwaji Iwasaki
    1967 Volume 40 Issue 3 Pages 569-575
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A study was made aimed at devising a new spectrophotometric method for the determination of ultramicro amounts of thiocyanate. A methylene blue is slightly extracted into a dichlo-roethane layer from an acid aqueous solution. However, if methylene blue is added to an acid aqueous solution containing thiocyanate, the complex formed in a 1 : 1 ratio between methylene blue and thiocyanate is well extracted into dichloroethane, the amount of extraction being proportional to the amount of thiocyanate present. Thiocyanate is determined by measuring the absorbancy of the dichloroethane solution of the complex at the wavelength of 657 mμ. This method is suitable for the determination of thiocyanate within the concentration range from 2.0×10−7 to 6.0×10−6 M by employing a 5.0-ml portion of dichloroethane for extraction, and in the range from 3.0×10−7 to 1.0×10−5 M by employing a 10.0-ml portion of it.
  • Yoshinaga Oka, Toyoaki Kato, Koichi Nomura, Tatsuya Saito
    1967 Volume 40 Issue 3 Pages 575-579
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The yields of radioactivities resulting from the (γ, n) reactions on 37 elements covering the periodic table have been determined by means of 20 MeV linear accelerator bremsstrahlung and gamma-ray spectrometry. The yield values, as measured in the number of photodisintegrations per mole per roentgen for each of the (γ, n) reactions, increase in the main regularly with atomic number from 103 through 107 order of magnitude. Anomalously small yield values are obtained in the irradiation of the nuclides with neutron or proton number of the magic numbers. The present results permit studies of general behavior of the photoneutron reactions and of the application of their products to the photoactivation analyses of many elements distributed throughout the periodic table.
  • Masaki Ohta, Hiroshi Kato, Takashi Kaneko
    1967 Volume 40 Issue 3 Pages 579-583
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The methods of preparing 2,4-dihydro-1,3,4-thiadiazole-2-thiones are discussed. The structure of the reaction products of these compounds or their methiodides with amines is determined to be 1,3-dihydro-1,2,4-triazole-3-thiones.
  • Etsuo Niki, Yoshio Kamiya
    1967 Volume 40 Issue 3 Pages 583-587
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The oxidation of α-methylstyrene in the presence of benzaldehyde was studied at 40°C, with and without added metal salt catalysts, from the viewpoint of the products obtained. The products were α-methylstyrene oxide, acetophenone, formaldehyde, α-methylstyrene polyperoxide, perbenzoic acid, and benzoic acid; few side reactions between these products were observed under the reaction conditions employed here. Emphasis was laid on the effect of metal salt catalysts and of the initial composition of the oxidants on the cleavage products from α-methylstyrene. Manganese and copper salts were found to have little effect, while cobalt salt showed a characteristic effect on the formation of the cleavage products. In the presence of cobalt salt, the formation of acetophenone was accelerated. The increase in the formation of α-methylstyrene oxide in this system compared with the oxidation of α-methylstyrene alone may well be attributed to the polar reaction of α-methylstyrene with perbenzoic acid formed from benzaldehyde. The consumption of perbenzoic acid in various systems was also examined. The increase in the initial concentration of benzaldehyde increased the yield of α-methylstyrene oxide and decreased that of acetophenone.
  • Takashi Toda
    1967 Volume 40 Issue 3 Pages 588-590
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The main products from the reaction of 3-bromotropolone and 7-bromohinokitiol with caustic alkali are proved not to be 3-hydroxytropolone and 7-hydroxyhinokitiol, but 4-hydroxy-tropolone and 6-hydroxyhinokitiol. The mechanism of this abnormal substitution reaction is then discussed.
  • Takashi Toda
    1967 Volume 40 Issue 3 Pages 590-594
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    3-Formyl-1-azaazulan-2-one was synthesized in a good yield from 1-azaazulan-2-one by means of a Vilsmeire reaction and its chemical properties were investigated. The synthesis of the tryptophan analogue from the formyl compound was also attempted.
  • Shu Furukawa, Kiyoshi Naruchi, Shigetake Matsui, Michio Yuuki
    1967 Volume 40 Issue 3 Pages 594-596
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Hunsdiecker reaction of silver acrylate and methacrylate has been investigated; 1, 1, 2-tribromoethane was obtained from the former, and bromoacetone from the latter. Since bromoacetone has also been obtained by the reaction of 2-bromopropene-l with acetyl hypobromite, it is conceivable that, in the case of the Hunsdiecker reaction of silver methacrylate, methacryloyl hypobromite (the intermediate of the Hunsdiecker reaction) oxidized 2-bromopropene-l (the primary product of the Hunsdiecker reaction) to bromoacetone, with an accompanying rearrangement of the bromine atom.
  • Naoko Tsubaki, Kiichi Nishimura, Yoshio Hirose
    1967 Volume 40 Issue 3 Pages 597-600
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An analytical study of patchouli oil was carried out, and the following compounds were identified; α- and β-pinene, limonene, camphene, β-elemene, caryophyllene, α- and β-patchoulene, α-guaiene, α-bulnesene, allo-aromadendrene, and α-gurjunene. The last six hydrocarbons were hydrogenated in order to complete the identification and to ascertain their spatial configurations by correlating the saturated skeletons with each of these or with known ones.
  • Meiko Fujimoto, Takeo Sato, Kazuo Hata
    1967 Volume 40 Issue 3 Pages 600-605
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The nitration reaction of [2.2]metacyclophane was carried out using dilute nitric acid or benzoyl nitrate under various conditions. Dilute nitric acid afforded 2-nitro-4, 5, 9, 10-tetrahydro-pyrene as the sole product, confirming Allinger’s original experiments, whereas benzoyl nitrate furnished a complex mixture consisting of 4, 5, 9, 10-tetrahydropyrene, 4, 5-dihydropyrene and pyrene, together with the nitration product. A series of experiments established that 4, 5, 9, 10-tetrahydropyrene, which was formed by the 1, 4-elimination reaction of Allinger’s intermediate, was the initial product of the reaction. Two competitive reactions, nitration and dehydrogenation reactions of the tetrahydropyrene, were assumed to be occurring, thus accounting for the experimental results.
  • Kensuke Takahashi, Ichi Ito, Yasuo Matsuki
    1967 Volume 40 Issue 3 Pages 605-607
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    PMR data on seventeen compounds, including all of the iodosubstituted derivatives of 2-, 3-methyl and 2, 3-dimethylthiophenes, were given. The signals of β-hydrogens appear at a rather higher applied magnetic field than those of α-hydrogens, while the β-methyl signals appear at a higher field than do the α-methyl signals. The coupling constants between two ring hydrogens, between ring and methyl hydrogens, and between two methyl hydrogens were described.
  • Shigeji Mishima
    1967 Volume 40 Issue 3 Pages 608-611
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reactivities of ethyl halides with active lead or sodium were investigated. The reactivities of ethyl halides with sodium-lead alloys were quite analogous to those of ethyl halides with sodium. The analysis of the gases produced in the reaction of sodium-lead alloys with ethyl halides revealed the presence of ethane, somewhat smaller amounts of ethylene and propane, etc. In the reaction of a sodium-lead alloy with ethyl halide in the presence of isopropylbenzene, 2, 3-dimethyl-2, 3-diphenylbutane was formed. In the reaction of ethyl bromide or ethyl iodide with sodium dispersed in isopropylbenzene, 2, 3-dimethyl-2, 3-diphenylbutane was also formed. On the basis of these results, it may be concluded that, in the reaction of sodium-lead alloys with ethyl halides, the initial step in the reaction is the formation of ethyl radicals by the reaction of ethyl halides with sodium in the alloys; then these radicals are combined with lead.
  • Yûkichi Takashi
    1967 Volume 40 Issue 3 Pages 612-617
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    As a study of the roles of the electron-donor compounds in the three-component Zieglertype catalysts, the reactions of triethylaluminum with various electron donor compounds, e. g., triethylamine, pyridine, diethyl ether, tetrahydrofuran, dioxane, and triethylstibine, have been investigated by means of the proton magnetic resonance. The internal chemical shifts between the α- and β-protons of the substituent groups bound to key atoms in the reaction mixtures have indicated that (1) each donor gives only one type of complex which is ordinarily expected, and (2) the coordination of the donor to triethylaluminum lowers the electronegativity of the aluminum atom. Qualitative information about the ligand exchange reactions of the donor complexes has also been obtained. All the complexes obtained showed remarkable electrical conductivities, indicating ionic structures.
  • Masajiro Kawana, Sakae Emoto
    1967 Volume 40 Issue 3 Pages 618-623
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The methoxy-mercurations of cinnamic esters of 1, 2; 5, 6-di-O-isopropylidene- and -cyclohexylidene-D-glucose, 5-deoxy-1, 2-O-isopropylidene-D-xylose, (−)-menthol, and (+)-borneol with mercuric acetate in methanol, followed by the reductive demercuration of the 3-acetoxymercuri-2-methoxyhydrocinnamic esters with sodium borohydride, gave, after the hydrolysis of the demercurated esters, IV, with alkali, 3-methoxy-3-phenylpropionic acid (V) in 1—27% optical yields, depending on the methoxy-mercuration time. When the methoxy-mercuration time was extended, the specific rotation of V decreased, but there was no corresponding decrease in the synthetic yield in the presence of nitric acid as a catalyst. This shows that an equilibrium in the methoxy-mercuration has been completed. The demercurated esters, IV, were reduced with lithium aluminum hydride to afford 3-methoxy-3-phenylpropan-1-ol (IX) in 6—22% optical yields. The absolute configurations of both V and IX were established to be (S)(−)-configurations. In the methoxy-mercuration, it seems likely that no oxygen atoms of sugar derivatives act as a co-ordinating group to keep the acetoxymercuri-group onto one side of the carbon-carbon double bond of cinnamate.
  • Kunio Okamoto, Masayuki Hayashi, Koichi Komatsu, Haruo Shingu
    1967 Volume 40 Issue 3 Pages 624-628
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The competitive SN1 hydrolysis and SN1 phenolysis of optically-active α-phenylethyl chloride in aqueous phenols (75 to 90 wt% phenol) give partially-retained α-phenylethyl alcohol and α-phenylethyl phenyl ether in the presence of added triethylamine at 14 and 30°C. The extent of the retention of the configuration is almost independent of the reaction temperature, whereas it shows a tendency to increase from 13 to 23% for the alcohol and from 5 to 20% for the ether with an increase in the phenol concentration. A predominant four-center (SNi-like) attack of a water molecule, with the assistance of a specific solvation of phenol molecules, has been suggested as a possible interpretation for the unusual hydrolysis with a retained steric course for this simple secondary alkyl system. In connection with the nature of the specific solvation of phenol molecules, the applicability of the concept of the back-side shielding of the SN1 ion-pair intermediate by a phenol molecule has been discussed.
  • Yojiro Tsuzuki, Koko Tanabe, Masuo Akagi, Setsuzo Tejima
    1967 Volume 40 Issue 3 Pages 628-632
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rotatory dispersions and ultraviolet absorption spectra of six homologs of 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl alkylxanthates have been measured, and the effects of the alkyl groups on the rotatory dispersion have been discussed by comparison with the case of the sugar xanthates already studied by Tsuzuki et al. (Bull. Chem. Soc. Japan, 37, 162, 730 (1964)). All show positive Cotton effects, the molecular amplitude of which diminishes with an increase in the number of carbon atoms of the alkyl group, while the molecular extinction coefficient decreases as the carbon number of the alkyl group increases from 1 to 4. These facts agree with the earlier findings and can be interpreted in terms of the relation, R=μcosθ\sqrtD, between the electron transition, the rotational strength, and the dipole strength given by S. F. Mason (Quart. Rev., 17, 20 (1963)).
  • Michiyo Morishita, Tsuneo Sowa, Fumio Sakiyama, Kozo Narita
    1967 Volume 40 Issue 3 Pages 632-639
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A few γ-oxoacyl amino compounds, such as N-levuloyl-L-phenylalanine, N-(3-benzoylpropionyl)-L-phenylalanine and -L-leucyl glycine, and N-α-N-δ-dibenzoylamino-γ-oxo-L-ornithyl-L-phenylalanine, were synthesized by the conventional method for peptide synthesis. The deacylation of the acyl group with hydrazines was studied in an attempt to establish the procedure for the second step in the newly-developed principle for the non-enzymatic cleavage of the C-tryptophyl and C-histidyl peptide bonds. The quantitative release of the amino group was accomplished by heating the γ-oxoacyl amino acid or peptide with the unsubstituted hydrazine in an acid solution. In this reaction the tetrahydropyridazone derivative was formed. The mechanism of the deacylation reaction was also considered.
  • Hideaki Kawashima, Izumi Kumashiro
    1967 Volume 40 Issue 3 Pages 639-641
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Hypoxanthine 1-N-oxide was treated with phosphoryl chloride in the presence of organic bases to give 2,6-dichloropurine. Adenosine 1-N-oxide was converted to inosine 1-N-oxide by deamination with nitrous acid. Inosine 1-N-oxide was acetylated with acetic anhydride in pyridine to yield 2′,3′,5′-tri-O-acetylinosine 1-N-oxide. The latter compound was similarly converted to 9-(2′,3′,5′-tri-O-acetyl-β-D-ribofuranosyl)-2,6-dichloropurine by treating it with phosphoryl chloride in the presence of organic bases.
  • Tadahiro Yamamoto
    1967 Volume 40 Issue 3 Pages 642-645
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The polymerizations of styrene in a series of nuclear-substituted cumenes, using α, α′-azobisisobutyronitrile as an initiator, have been carried out at 60°C, and the chain transfer constants, Cs, for the substituted cumenes have been determined. It has been found that the Cs values for cumenes with electron-repelling groups are smaller than that for an unsubstituted cumene, while those for cumenes with electron-attracting groups are greater. The plot of log (kk0) against the corresponding Hammett’s σ-constants failed to give a linear relationship. The modified Hammett’s equation including the resonance effect for radical reactions, the equation which was proposed by the author and Azumi, i.e.,: log(kk0)=ρσ+γER, could be adopted to the transfer with the usual precision, giving γ=1 and ρ=0.7. It is considered that the effects of substituents on the transfer reactivities of cumenes to the attack of the polystyryl radical depend on the contributions of polar and resonance factors.
  • Shumpei Sakakibara, Masumi Itoh
    1967 Volume 40 Issue 3 Pages 646-649
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Formation of unexpected by-products was observed when t-amyloxycarbonyl-(AOC) amino acid esters were prepared according to the previously published method from some specific amino acid esters using AOC-chloride as the reagent. Further, it was observed that the weaker the basicity of the amino acid ester used, the more by-product was formed under the same conditions. Analyses of the infrared and NMR spectra of the by-products revealed their structures to be ureid-type compounds of the respective amino acid esters. Use of excess AOC-chloride together with triethylamine was found to be the main cause of the ureid-formation, and the side-reaction could be almost entirely suppressed by the use of N, N-diethylglycine ethyl ester in place of triethylamine.
  • Ryokichi Tarao, Saburo Takeda
    1967 Volume 40 Issue 3 Pages 650-655
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The redistribution reactions of ethyl groups and chlorine atoms in the 2AlEtnCl3−n+ether system were studied by the Raman spectroscopic method. It was found that the reaction of AlEtCl2 with Et2O (molar ratio, 2:1) gave rise to AlEt2Cl and AlCl3·Et2O, although not quantitatively. On the contrary, the reaction of AlEt2Cl with Et2O (molar ratio, 2:1) did not produce any AlEt3 or AlEtCl2·Et2O at all. These and several related observations demonstrate that, by the reaction between AlEtnCl3−n and AlEtmCl3−m·Et2O (n, m=0, 1, 2, 3), AlEt2Cl is preferentially produced as long as there is any possibility of its formation.
  • Shumpei Sakakibara, Masumi Itoh
    1967 Volume 40 Issue 3 Pages 656-661
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Base catalyzed racemization of N-carbobenzoxy-S-benzyl-L-cysteine p-nitrophenyl ester was studied with various tertiary amines; N, N-dialkylglycine esters and N-ethylmorpholine were found to induce less racemization than triethylamine. Furthermore, these mild bases were strong enough in many cases to liberate free amino acid or peptide esters from their salts. It was also confirmed that a mixture of an amino acid or peptide ester salt and such a mild base could be used in the place of a previously prepared free ester for peptide synthesis, and practically no racemization was observed during the coupling reaction with an acylamino acid active ester. Anderson’s racemization test was also carried out by the mixed anhydride procedure with these mild bases instead of triethylamine; the mild bases were found to give better results in optical purity.
  • Takashi Joh, Nobue Hagihara, Shunsuke Murahashi
    1967 Volume 40 Issue 3 Pages 661-664
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    New complexes (III) have been found to be formed in the reaction between aromatic azo compounds and cyclopentadienyl cobalt derivatives. The same complexes have also been obtained from the reaction of o-quinonediimine or o-phenylenediamine derivatives with cyclopentadienyl cobalt dicarbonyl. These complexes reacted with carbon monoxide to yield benzimidazolone derivatives, and with hydrogen to give o-phenylenediamine derivatives. The structure of the complexes has been formulated on the basis of the infrared spectra, the proton magnetic resonance, and chemical evidence.
  • Hiroyuki Nohira, Kenji Inoue, Hirotoki Hattori, Toji Okawa, Teruaki Mu ...
    1967 Volume 40 Issue 3 Pages 664-668
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    2, 2, 5-Tri-substituted-1, 3, 4-dioxazoles have been prepared by the reactions of benzhydroxamic acids with the diethylketals of such ketones as acetone, cyclohexanone, acetophenone and benzophenone. These dioxazoles decompose at elevated temperatures (above 150°C) into phenylisocyanates and ketones. A kinetic study of the decomposition reaction in nitrobenzene has been attempted, and the first-order rate constants have been obtained.
  • Tadashi Suehiro, Akio Kanoya, Humihiro Hara, Tetsuro Nakahama, Muneki ...
    1967 Volume 40 Issue 3 Pages 668-674
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Die Geschwindigkeiten der Umsetzung von m, m′- und p, p′-symmetrisch substituierten Benzoylperoxyden mit Triphenylmethyl in aromatischen Lösungsmitteln wurden durch Messung der Abnahme der Absorption vom Triphenylmethyl bei 15–35°C bestimmt. Die Umsetzung von Peroxyd in Benzol wird durch die Elektron Acceptor Substituenten beschleunigt (rho=+1.45, r=0.975) und die isokinetische Temperatur ist ca. 180°K. Die Reaktionsgeschwindigkeit von Peroxyd mit Triphenylmethyl wird wieder durch die Polarität der aromatischen Lösungsmitteln beschleunigt und bei dem nicht substituierten Benzoylperoxyd erhält man die isokinetische Temperatur von ca. 390°K. Daraus. wird geschlossen, dass im Übergangszustand polaren Strukturen eine grosse Rolle spielen.
  • Tadashi Suehiro, Hideki Tsuruta, Shuji Hibino
    1967 Volume 40 Issue 3 Pages 674-679
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Benzoylphenylacetylperoxyd zersetzt sich in Benzol anscheinend nach 1. Ordnung und bei 25°C erhält man Geschwindigkeitkonstant, Aktivierungsenergie und Aktivierungsentropie je (2.05±0.04)×10−4 Sek−1, 21.7 kcal·Mol−1 und −5.0 cal·Grad−1. Die Bildung von freien Radikalen während der Zersetzung beträgt, nach der spektroskopischen Bestimmung mittels Diphenylpikrylhydrazyl, erst unter 10 Mol%. Produktenanalyse der Umsetzung vom Peroxyd in Lösung durch Gaschromatographie zeigt das Auftreten von Benzyl-Kation und die monomolekulare Entstehung von Benzoesäurebenzylester, und durch Infrarot-Spektrum, die Bildung von Benzylkohlensäurebenzoesäureanhydrid. Die Zersetzung wird beschleunigt durch Säure unter gleichzeitiger Zunahme des Produktes Diphenylmethanderivates in Aromaten mit Elektron-Donator Substituent, und auch durch die Poläritat von Lösungsmitteln. Alle diese bedeuten, dass Peroxyd zerfällt in keiner normaler Weise der homolytischen Spaltung von O–O Bindung, sondern zersetzt sich in drei parallel laufenden Reaktionen 1) zum Benzyl-Kation, 2) zum Benzoesäurebenzylester und 3) zum Benzylkohlensäurebenzoesäureanhydrid in ungefähr gleichen Massen.
feedback
Top