Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 43 , Issue 6
Showing 1-50 articles out of 83 articles from the selected issue
  • Hiroshi Yoneyama, Hideo Tamura
    1970 Volume 43 Issue 6 Pages 1603-1607
    Published: 1970
    Released: March 27, 2006
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    The redox reactions of the Ce3+/Ce4+, Fe2+/Fe3+ and Fe(CN)64−/Fe(CN)63− systems on lithiated nickel oxide electrodes in a H2SO4 medium were studied. For the Fe2+/Fe3+ and Fe(CN)64−/Fe(CN)63− systems, the reactions were controlled by an activation process when the electrode was polarized anodically, while the current tended to saturation as the current was increased in the cathodic direction. The apparent exchange current densities of these systems were distinctly dependent on the resistivity of the electrode. These phenomena were discussed qualitatively from a consideration of the energy states of the charge carriers in the electrode and redox systems, and it was concluded that all the reactions had proceeded through only hole transfer.
  • R. Gopalakrishnan
    1970 Volume 43 Issue 6 Pages 1607-1610
    Published: 1970
    Released: March 27, 2006
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    Magnetic susceptibilities of nine typical liquid mixtures were determined as a function of concentration. Deviations from an additive law were observed for these mixtures of chloroform with triethylamine, aniline, pyridine, α-picoline, 2,4-lutidine, diphenyl ether, toluene, nitrobenzene and chlorobenzene. The observed deviations are explained on the basis of hydrogen bond formation.
  • R. D. Srivastava, G. Prasad
    1970 Volume 43 Issue 6 Pages 1611-1614
    Published: 1970
    Released: March 27, 2006
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    Charge transfer complexes between 2,3-dichloro-5,6-dicyano-p-benzoquinone and various methyl and phenyl substituted benzenes have been studied. The spectral characteristics and equilibrium constants of o-, m-, and p-xylenes and those of o-, m-, and p- terphenyls are reported. The results have been interpreted in terms of Mulliken’s charge transfer theory. From the spectral data, the electron affinity of 2,3-dichloro-5,6-dicyano-p-benzoquinone has been estimated to be 1.974 eV. The energy of the first CT band has been found to be related to the ionization potential of the donors by the expression hϑCT=0.7ID−3.86.
  • Suresh Chandra, Dina Nath
    1970 Volume 43 Issue 6 Pages 1614-1617
    Published: 1970
    Released: March 27, 2006
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    Permittivity and dielectric loss of four nitroalkanes have been measured in solution in three solvents viz., n-heptane, benzene and cyclohexane at 9.8 GHz and 30°C. The variation of the relaxation time calculated from the data, with the viscosity of the solutions has been discussed. It has been found that the results cannot be explained on the basis of known relations between relaxation time and viscosity. It is expected that some other interactions such as proton-proton interaction are responsible for the relaxation time in cyclohexane lower than in benzene. The loss tangents are found to vary linearly with the concentration of the solution. Dipole moments have also been evaluated in all the three solvents and are in good agreement with the values in literature within experimental error.
  • Ayako Torikai, Shuzo Sawada, Kenji Fueki, Zen-ichiro Kuri
    1970 Volume 43 Issue 6 Pages 1617-1621
    Published: 1970
    Released: March 27, 2006
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    Elementary processes in the radiolysis of ethyl mercaptan has been investigated by both spectrophotometric and electron spin resonance (ESR) methods. Ethyl mercaptan (C2H5SH) forms a glassy solid at 77°K, and when irradiated with γ-rays from Co-60, it develops a deep orange color; this color fades upon illumination with visible light, leaving a clear yellow color. The ESR spectrum of γ-irradiated C2H5SH at 77°K consists of two components; one is a complex spectrum which has been identified with the spectrum of C2H5S·, while the other is a photobleachable broad singlet which has been assigned to the ionic species. The C2H5S· radical shows an absorption spectrum with λmax=405 nm. The G-values for the formation of the radicals and the ionic species were 0.5 and 2.9 respectively. Studies of 2-methyltetrahydrofuran and butyl chloride solutions of C2H5SH were performed to identify these ionic species. Some significant elementary processes will be discussed on the basis of these results.
  • Tanekazu Kubota, Yoshiko Oishi, Koichi Nishikida, Hiroshi Miyazaki
    1970 Volume 43 Issue 6 Pages 1622-1634
    Published: 1970
    Released: March 27, 2006
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    The hydrogen-bonding effects of ethanol, phenol, and water on the electron-spin-resonance spectra of the anion radicals of 4-nitro- and 4-cyano-pyridine N-oxides, pyrazine mono- and di-N-oxides, and 4-nitropyridine electrochemically generated in dimethylformamide have been studied quantitatively. The equilibrium constant, K, pertinent to the hydrogen-bonding systems was determined on the basis of analyses of the variation in the hyperfine coupling constant caused by the addition of a proton donor. The active site in a radical anion participating in the hydrogenbonding interaction and the K values were then discussed on the basis of the theoretical calculation of the spin density and the coupling constant of the radicals in the hydrogen-bonding interaction. It has been pointed out that this sort of experiment in hydrogen bonding interaction is also useful for assigning the hyperfine coupling constant to a definite atom in a radical. Last, these K values are used to explain the mechanism of radical formation by the controlled potential electrolysis at different reduction potentials of pyrazine mono- and di-N-oxides in dimethylformamide-ethanol mixed solvents.
  • Koichiro Nakanishi, Hideko Shirai
    1970 Volume 43 Issue 6 Pages 1634-1642
    Published: 1970
    Released: March 27, 2006
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    Excess volumes of mixing have been determined at 25.00°C by pycnometry for eleven binary solutions of methanol and two binary solutions of ethanol with organic liquids. The second components include three aliphatic amines, n-butyraldehyde, ethyl acetate, isopropyl ether, anisol, chlorobenzene, acetonitrile, pyridine and nitromethane. The excess volumes of binary solutions containing aliphatic alcohols, which are evaluated from the available density data, were critically reviewed and compared with the present results.
  • Fumihiko Hirota, Saburo Nagakura
    1970 Volume 43 Issue 6 Pages 1642-1649
    Published: 1970
    Released: March 27, 2006
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    For the purpose of evaluating approximate SCF-MO’s for systems including all valence electrons, two semi-empirical methods are presented. One of them (method I) uses non-empirical Coulomb integrals and the other (method II) empirical ones. The orbital energies, charge distributions, and excitation energies are calculated for ethylene, acetylene formaldehyde, carbon monoxide and hydrogen cyanide, and are compared with those obtained by the other semi-empirical and non-empirical calculations and also with the corresponding experimental values. The present methods are found to give rather satisfactory results. The calculated orbital energies are improved by the present methods compared with those by the CNDO type calculation. Calculated charge distributions are well coincident with those of the non-empirical SCF calculation. Calculated dipole moments change in parallel with experimental values from a molecule to another, though the former values are generally larger than the latter.
  • Satoru Tsuda, Akira Yokohata, Michihiro Kawai
    1970 Volume 43 Issue 6 Pages 1649-1656
    Published: 1970
    Released: March 27, 2006
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    The negative ion mass spectra of alkyl (methyl, ethyl, n- and iso-propyl) chlorides, with emphasis on their relative abundance to the positive ions under 80, 40, 20 and 15 eV electron energies, and the ionization efficiency (IE) curves of Cl ions to the extent of 30 eV electron energies were measured. In every sample, the electron impacts of 80 eV and 40 eV gave almost the same distribution of m/e for negative ion mass spectra, in which, besides the intense peaks of m/e 35 and 37 (Cl), a relatively strong peak of m/e 25 (C2H) in ethyl chloride and n- and iso-propyl chlorides was characteristic. For 20 eV and 15 eV, Cl ions predominated other negative ions. The ratio of the abundance of negative ions to positive ions was the order 102–103 for CH3Cl+/Cl, C2H5Cl+/Cl, C3H6+/Cl and C3H7+/Cl throughout the range of electron energies. Each onset value observed in IE curves was interpreted to correspond to the appearance of the following reactions, the reaction scheme for second process being tentative. For the first process RCl+e→R+Cl, for the second process CH3Cl+e→H+CH2+Cl, C2H5Cl+e→H2+H+C2H2+ Cl, C3H7Cl(n- or iso-)+e→H+C2H4+CH2+Cl. For the third process the possibility of ion pair formation was pointed out. For the fourth process in ethyl chloride a brief discussion was made in view of the overlapping phenomena of a complicated dissociative electron capture process with an ion pair formation.
  • Toyoaki Kimura, Kenji Fueki, Zen-ichiro Kuri
    1970 Volume 43 Issue 6 Pages 1657-1661
    Published: 1970
    Released: March 27, 2006
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    Hydrogen yields have been determined for thirteen saturated hydrocarbons (n-pentane, cyclopentane, methylcyclopentane, 3-methylpentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, 2,2,4-trimethylpentane, n-nonane, n-decane and polyethylene) γ-irradiated at 20°C, −72°C and −196°C. The decrease in hydrogen yield with decreasing temperature from 20°C to −196°C has been correlated with the yield of thermal hydrogen atoms, which was obtained by adding ethylene as a scavenger at 20°C; the decrease in most cases was nearly equal to a half of the thermal hydrogen atom yield. Evidence of thermal hydrogen atom production at −196°C has also been demonstrated by ESR measurement. It has been concluded that thermal hydrogen atoms abstract hydrogen atoms from solvent molecules at 20°C, but they mostly recombine with each other to form hydrogen molecules at −196°C. An empirical formula based on the C–H bond parameter has been presented which is adapted for the hydrogen yield from normal alkanes.
  • Kenji Furue, Toshihide Kimura, Noritake Yasuoka, Nobutami Kasai, Masao ...
    1970 Volume 43 Issue 6 Pages 1661-1667
    Published: 1970
    Released: March 27, 2006
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    The molecular structure of dimethyltin chloride N,N-dimethyldithiocarbamate, [(CH3)2-SnCl(S2CN(CH3)2)], has been determined from three-dimensional X-ray diffraction data. The unit-cell dimensions are a=12.67, b=7.64, c=12.11 Å, and β=110.3°. The space group is P21/c. Four formula units are contained in a unit-cell. The structure was established by the heavy-atom method. The coordination around the tin atom is a distorted trigonal bipyramid with the following bond distances: Sn–C, 2.17(5) and 2.20(5) Å, Sn–Cl, 2.46(1) Å and Sn–S, 2.48(1) and 2.79(1) Å. Two methyl groups are both in equatorial positions.
  • Masaru Mitsuishi, Mieko Hashizume, Akira Katayama, Nobuhiko Kuroki
    1970 Volume 43 Issue 6 Pages 1667-1670
    Published: 1970
    Released: March 27, 2006
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    The visible absorption spectra of Alizarine Saphirol SE in water-dioxane mixtures were obtained, and the spectral changes were considered on the basis of the results of the conductance measurements of the dye. In the spectra of the dye in the mixtures containing less than 60% dioxane, the absorption was found to increase with an increase in the dioxane content. This spectral change was attributed to the decrease in the tendency of the dye to aggregate. In the spectra of the dye in the mixtures containing more than 70% dioxane, however, the absorption found to decrease with an increase in the dioxane content, i.e., with a reduction in the dielectric constant of the solvent. This spectral change was considered to be characteristic of the increase in the electrostatic interaction between the dye ion and the counter ion.
  • Takeshi Imura, Naoto Yamamoto, Hiroshi Tsubomura
    1970 Volume 43 Issue 6 Pages 1670-1675
    Published: 1970
    Released: March 27, 2006
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    A technique is described for the study of the photocurrent due to the transient ionic species produced by the flash photolysis of aromatics in solutions at room temperature. The technique has proved to give valuable information in a way complementary to conventional flash spectrometry. The photo-ionization of N,N,N′,N′-tetramethyl-p-phenylenediamine was studied by this method in polar and non-polar solvents. The photocurrents of the solutions of some electron donor-acceptor systems were also measured, and the results were compared with that obtained from flash spectrometry. The recombination rate constants of the ionic species were estimated from the decay of transient photocurrents.
  • Hideyuki Konishi, Hiroshi Kato, Teijiro Yonezawa
    1970 Volume 43 Issue 6 Pages 1676-1682
    Published: 1970
    Released: March 27, 2006
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    Using a semi-empirical SCF MO method for valence electron systems proposed previously by the present authors, the electronic structures of norbornadiene (NBD), norbornene (NBE), and their 7-cations are discussed, together with the configurational problem of the 7-cations. In NBE and NBD, the interaction between the π AO’s in the double bond and the AO’s of the other parts of the molecules is made clear by the charge densities and the bond orders. For the first electronic transition assigned to a π–σ* or σ–π* in NBD, the present calcuation gives a rather larger excitation energy than does the experiment. For 7-norbornenyl and 7-norbornadienyl cations, the presence of structures distorted from NBE and NBD respectively can theoretically be concluded. The delocalization of the positive charge and the bonding interaction between the bridged carbon atom and the double bond carbon atoms support the concept of the so-called non-classical carbonium ions.
  • Haruo Nakayama
    1970 Volume 43 Issue 6 Pages 1683-1686
    Published: 1970
    Released: March 27, 2006
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    The heats of solution of poly(ethylene glycol) and of related compounds (1,4-dioxane, tetra-hydrofuran, ethylene glycol, diethylene glycol, and several ethyl ethers of ethylene glycol and of diethylene glycol) have been measured as a function of the temperature. The change in the partial molar heat capacity of the solute molecule in the dissolution process, Δ\barCp2, is obtained from the temperature coefficient of the heat of solution. The Δ\barCp2 for poly(ethylene glycol) is 15 cal/deg per –CH2CH2O– chain unit. This value is in good agreement with those obtained for other low-molecular-weight compounds. The effect of the polar groups (the ethereal oxygen atom and the hydroxyl group) on the iceberg formation around the nonpolar residues has been discussed. From the results obtained, it seems likely that the iceberg formation around the –CH2CH2O– group is somewhat suppressed by the orientation-dependent interactions (hydrogen bond formation) between the ethereal oxygen atom and the water molecule.
  • Shoichi Ikeda
    1970 Volume 43 Issue 6 Pages 1686-1692
    Published: 1970
    Released: March 27, 2006
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    Potentiometric titration curves have been determined for aqueous solutions of poly-S-carboxymethyl-L-cysteine. A pH-induced transition of the polymer conformation is manifest from the occurrence of a transition region around pH 5, where the solution has an essentially infinite buffer action. The titration curve at higher ionization corresponds to that of a random coil. At lower ionization the polymer is associated to form a β-structure and its titration behavior is qualitatively accounted for by the Gouy model for a uniformly charged sheet. Deviation from the model would partly be ascribed to the aggregation of sheets in the β-form. The standard free energy of transition from random coil to β-form has been estimated for the unchanged polymer and is found to depend on the molecular weight of polymer. It is suggested that fine structure of the β-form and its mode of aggregation vary with polymer chain length.
  • Shigehiro Konaka, Masao Kimura
    1970 Volume 43 Issue 6 Pages 1693-1703
    Published: 1970
    Released: March 27, 2006
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    The thermal-average distances and mean amplitudes of AsCl3 and AsF3 have been determined by gas electron diffraction. The sources of experimental errors have been discussed in detail. The observed molecular parameters are rg(As–Cl)=2.1621±0.0033 Å, θg(ClAsCl)=98°34′±34′, l(As–Cl)=0.0470±0.0024 Å, l(Cl–Cl)=0.0945±0.0063 Å, rg(As–F)=1.7089±0.0016 Å, θg(FAsF)=95°53′±22′, l(As–F)=0.0433±0.0022 Å, and l(F–F)=0.0689±0.0044 Å. The results have been compared with the structures of other trihalides of the Vb-group elements.
  • Hsiu Chi
    1970 Volume 43 Issue 6 Pages 1703-1707
    Published: 1970
    Released: March 27, 2006
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    Gadolinium oxalate hydrate crystallizes isomorphously as La2(C2O4)3·10H2O, with two molecules in a unit cell of dimensions: a0=11.61+0.05, b0=9.656+0.020, c0=10.22+0.05 Å and β=119.0+0.1°. A detailed study of the d-spacings for the coprecipitates of varying composition in the La-Gd oxalate system was made, and 46 nearest-neighbor pairs were selected for Van Vleck second moment calculation. Agreement of the results of the calculation with those of the experiment justifies the suggested model representing the location of the gadolinium ions in the hydrated oxalate salt.
  • Yoshihisa Matsui, Yukio Kurosaki, Yoshio Date
    1970 Volume 43 Issue 6 Pages 1707-1714
    Published: 1970
    Released: March 27, 2006
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    The polarographic behavior of the iodide ion, the triiodomercurate ion, and mercuric iodide at the dropping mercury electrode was investigated in dimethylformamide, using d.c. polarography, controlled potential electrolysis, and oscillographic polarography with a multi-triangular voltage sweep. The iodide ion gives two well-defined anodic waves: the first wave corresponds to the reversible oxidation of mercury to the triiodomercurate ion, and the second, to the reversible oxidation of mercury to mercuric iodide. A maximum arises on the reduction wave of the triiodomercurate ion, but it is suppressed by the addition of a small amount of polyvinyl chloride. The oscillographic polarograms and electrocapillary curves suggested that the iodide ion, like the triiodomercurate ion and mercuric iodide, is strongly adsorbed on the dropping mercury electrode. The maximum on the wave due to the reduction of the triiodomercurate ion to mercury and the iodide ion was ascribed to the convection of the mercury drop, which was itself probably caused by the abrupt desorption of the iodide ion formed successively with an increase in the negative potentials. The adsorption phenomena of the corresponding bromides and chlorides are also discussed.
  • Seiichiro Utsumi, Shuko Fujieda
    1970 Volume 43 Issue 6 Pages 1714-1718
    Published: 1970
    Released: March 27, 2006
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    Sodium potassium tungsten bronzes, NaxKyWO3, having various values of x and y were prepared by electrolytically treating a fused mixture of carbonates of the two alkali metals and tungsten-(VI) oxide. Lattice constants, a and c, of the tetragonal crystals were estimated by the X-ray powder method. Similarity of the crystal lattice of these bronzes to that of potassium tungsten bronzes, instead of to that of sodium tungsten bronzes, suggests that the lattice constants of the sodium potassium bronzes are by far more influenced by the potassium content than by the sodium content.
  • Yuko Hasegawa, Hiroshi Kawashima, Tatsuya Sekine
    1970 Volume 43 Issue 6 Pages 1718-1722
    Published: 1970
    Released: March 27, 2006
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    The complex formation of calcium(II) and strontium(II) with carbonate ions in 1M sodium chloride media at 25°C has been determined by a liquid-liquid distribution method. The metal ions in the aqueous phase were extracted with a mixture of benzoylacetone and tributylphosphate in hexane as adduct chelate complexes. The distribution ratio was determined by radiometry as a function of the carbonate-ion concentration in the aqueous phase. The decrease in the metal distribution caused by the addition of carbonate ions to the aqueous phase has been explained in terms of the complex formation, and the stability constants have been determined from these data by a “curve-fitting” method. It has been concluded from the results that the stabilities of these complexes are about the same magnitude of those of the sulfate complexes of these metal ions and that the concentration of the carbonate complexes in usual natural waters is probably negligibly small.
  • Yuki Fujii
    1970 Volume 43 Issue 6 Pages 1722-1728
    Published: 1970
    Released: March 27, 2006
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    A mixed cobalt(III) complex containing both bis(acetylacetone) ethylenediimine and acetylacetone anions, [Co(bean)(acac)] (bean=dianion of bis (acetylacetone) ethylenediimine, acac=anion of acetylacetone), was newly prepared and its electrophilic substitution reaction at the chelate ring protone was studied by means of NCS, NBS, and NIS (NCS, NBS and NIS are the abbreviated forms of N-chloro-, N-bromo- and N-iodosuccinimide). The structures of this complex, [Co(baen)-(acac)], and of the halogenated complex were both determined to be of the β-form (cis with respect to the coordinated two oxygen atoms of baen) on the basis of their NMR spectra. The ring protons of the imine chelates were found to be more reactive than that of the acetylacetone chelate in the chlorination reaction. Then, a bi-substituted complex, [Co(baen-Cl2)(acac)], in which two chlorine atonies were attached to the two imine chelate rings, was prepared. Tri-substituted complexes, [Co(baen-X2)(acac-X)] (X=Cl, Br and I), were also prepared. The quasiaromaticity of both the acetylacetone and imine rings was considered on the basis of their NMR spectra. A new complex, [Co(baen)(OH)(H2O)], was also prepared in order to assign the NMR spectrum of the complex, [Co(baen)(acac)]. The IR, UV, and visible absorption spectra were also considered.
  • Hisashi Okawa, Hiroyuki Koyama, Takahiko Inazu, Tamotsu Yoshino
    1970 Volume 43 Issue 6 Pages 1729-1733
    Published: 1970
    Released: March 27, 2006
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    Two quadridentate chelating agents, 4,4′-dimethyl-2,2′-bis(salicylideneaminomethyl)diphenyl ether and 4,4′-dimethyl-2,2′-bis(salicylideneaminoinethyl)diphenylarnine, which may form a metal complex with a ten-membered chelate ring, were synthesized by a sequence of steps. The cobalt(II), nickel(II), copper(II), and zinc(II) complexes could be derived from the ligands. Their configurations around the central divalent metal ion were explored on the basis of the absorption in the ligand field in a solution. A tetrahedral configuration for cobalt(II) complexes as well as the zinc(II) complexes, and a pseudo-tetrahedral configuration for the nickel(II) and copper(II) complexes, were concluded.
  • Takayuki Saito, Junzo Otera, Rokuro Okawara
    1970 Volume 43 Issue 6 Pages 1733-1736
    Published: 1970
    Released: March 27, 2006
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    2 : 1 complexes of trimethylstibine sulfide (TMSS) with zinc(II), cadmium(II), mercury(II) and cobalt(II) halides were prepared. 1 : 1 complexes were also obtained with cadmium bromide and mercuric iodide. On the basis of infrared spectra, it was found that TMSS coordinates to the metal through the sulfur atom and that Hg(TMSS)I2 has a sulfur-bridged structure. The electronic spectral parameters of the tetrahedral Co(TMSS)2X2 (X=Cl, Br and I) complexes are quite close to those of trimethyl-phosphine and -arsine sulfide complexes. These results indicate that for Co–S interactions, polarizability of the thioxo ligand is more important than polarity.
  • Norio Koine, Naokazu Sakota, Jinsai Hidaka, Yoichi Shimura
    1970 Volume 43 Issue 6 Pages 1737-1743
    Published: 1970
    Released: March 27, 2006
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    Eight new complexes, trans(N) or cis(N) isomers of (L- or D-alaninate-N,N-diacetato) (aminoacidato)cobaltate(III) ions, have been synthesized as their potassium salts, where the amino acids are glycine, L-alanine and L-proline. Stereoselective formation of a limited number of the isomers with respect to the geometrical arrangement of the coordinated nitrogen and oxygen atoms and with respect to the position of the chelate ring containing the methyl group of the coodinated alaninate-N,N-diacetate ion, were confirmd from the results of the studies by ion-exchange column chromatography, proton magnetic resonance and circular dichroism spectra. The additivity of vicinal circular dichroism contributions from the two different optically active ligands in a complex has been discussed for the complexes without the configurational chirality.
  • Shoichiro Yamada, Kuniko Yamanouchi
    1970 Volume 43 Issue 6 Pages 1744-1746
    Published: 1970
    Released: March 27, 2006
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    Gold complexes (abbreviated as [AuIII(X-SAL·alkyl)2][AuICl2]) with salicylideneimine derivatives were prepared as red-brown crystals, where X denotes H, 5,6-benzo and 5-Cl. Since all these complexes are diamagnetic and exhibit similar electronic absorption spectra, the complexes of the [Au(X-SAL·R)2]+type are considered to have a similar configuration, namely a square-planar one. It should be noted that the complexes of the [Au(X-SAL·i-C3H7)2]+ type are also planar. The result is found to be similar to that for the palladium(II) and platinum(II) complexes, but different from that for the nickel(II) complexes.
  • Hiroshi Takeuchi, Toshikazu Nagai, Niichiro Tokura
    1970 Volume 43 Issue 6 Pages 1747-1751
    Published: 1970
    Released: March 27, 2006
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    The decomposition of phenylazotriphenylmethane (I) in the presence of SO2 and O2 in benzene at 60°C gives p-hydroxytetraphenylmethane (II) by the reaction of the trityl cation and the phenol formed in the reaction system. However, in the absence of O2 or SO2, the above-mentioned reaction produces trityl phenyl sulfone (III) or bistrityl peroxide (IV), without forming any II. Also, 1-diphenylmethylene-4-trityl-2,5-cyclohexadiene (Gomberg’s trityl) (V) has been chosen as the trityl radical source, and reacted with phenol in the presence of SO2 and O2 to give II as the product. However, in the absence of SO2, IV and a trace of II are formed. Moreover, in the absence of O2 in the above system, p-benzhydryltetraphenylmethane (VI) and a small amount of II are formed. The benzene solution of VI is stable on exposure to air at 60°C. Further, the UV spectrum of V in the liquid SO2-O2 system shows λmax at 405 mμ (logε 4.1) and 434 mμ (logε 4.1) (trityl chloride in 98% H2SO4: λmax 430 mμ (logε 4.58)). However, the UV spectrum of VI in the liquid SO2-O2 system has no absorption in this range. The NMR spectrum in the liquid SO2-O2 system of V exhibits only aromatic protons (2.6–3.1 τ). These facts indicate that the trityl radical generated from V is transformed into the trityl cation in the SO2-O2 system at room temperature, whereas VI does not dissociate into the trityl radical even at 60°C in benzene.
  • Takeki Matsui, Niichiro Tokura
    1970 Volume 43 Issue 6 Pages 1751-1762
    Published: 1970
    Released: March 27, 2006
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    The reaction rates and equilibrium constants for quaternization of N,N-dimethylaniline and its derivatives with methyl iodide have been measured in acetonitrile, acetone, tetrahydrofuran, nitrobenzene, benzene, benzyl alcohol, and methanol at various temperatures. There is an approximate tendency for the solvent dependence of the reaction rates to diminish linearly with increasing reactivity of nucleophile. This could be interpreted in terms of the theory of an absolute reaction rate and of the concept of the rise of interaction term. In this connection it was proposed that such a problem must be considered in terms of the unitary term of rates. Using the data of rates of the reaction between pyridine and methyl iodide in various solvents, the activity coefficients of dimethylaniline and its derivatives in methanol relative to that of pyridine are estimated. Some inferences have been drawn concerning the nature of SN2 transition state from effects of solvents on both rates and equilibria.
  • Tran Dinh Tuong, Mitsuhiko Hida
    1970 Volume 43 Issue 6 Pages 1763-1768
    Published: 1970
    Released: March 27, 2006
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    Kinetic studies of the Ullmann condensation of an aryl halide, sodium 1-amino-4-bromoanthraquinone-2-sulfonate and an amine, aniline, were undertaken. Cupric copper was used as the catalyst. The reaction was found to be first order in monomeric aryl halide and first order in amine, and to depend hyperbolically on the concentration of the catalyst. It was shown by ESR measurements that the copper catalyst exists largely as cupric species. The experimental results were discussed mechanistically.
  • Kunio Okamoto, Issei Nitta, Haruo Shingu
    1970 Volume 43 Issue 6 Pages 1768-1777
    Published: 1970
    Released: March 27, 2006
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    In acetic acid, aqueous methanol, and phenol solvents, 2,6-di-t-butyl-4-methyl-4-(1-phenylethyl)-cyclohexadien-1-one (I) did not undergo a typical dienone-phenol rearrangement in the presence of sulfuric or perchloric acid, but yielded the solvolysis products, viz., 1-phenylethyl acetate, 1-phenylethyl methyl ether, and 1-phenylethyl phenyl ether, in the respective solvents, along with 2,6-di-t-butyl-4-methylphenol (II). The reactions carried out with the optically-active dienone (Ia) yielded solvolysis products which were predominantly racemized, but accompanied by a net inversion of the configuration. The polarimetric rate constant of racemization, measured in acetic acid containing sulfuric acid at 25°C, is in agreement with the spectrophotometric rate constants for the decrease in the dienone Ia and for the increase in the phenol II, essentially within the limits of experimental error. These stereochemical results can be accomodated by a typical SN1 mechanism, in which the dienone I, protonated on the carbonyl-oxygen, acts as a substrate, and the phenol II, as a leaving group.
  • Masamatsu Hoshino, Seiji Ebine
    1970 Volume 43 Issue 6 Pages 1778-1782
    Published: 1970
    Released: March 27, 2006
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    On diazo coupling and nitration, 6-hydroxy-2,3-benzotropone (I) and its 5-bromo derivative (II) gave their 7-azo (V and VI) and 7-nitro substitution products (VII and VIII), respectively. In the same reactions, 7-bromo-6-hydroxy- (III) and 5,7-dibromo-6-hydroxy-2,3-benzotropones (IV) replaced their 7-bromo substituent to give the same 7-azo and 7-nitro substitution products as above. On nitration of III and IV, 2,2-dibromo- (IX) and 2,2,7-tribromo-4,5-benzocyclohepta-4,6-diene-1,3-diones (X) were also formed. Hydrogenation of V, VI, VII and VIII gave 7-amino-6-hydroxy-2,3-benzotropone (XI), diazotization of which gave 2-diazo-4,5-benzocyclohepta-4,6-diene-1,3-dione (XII). 7-Chloro-6-hydroxy-2,3-benzotropone (XV) was brominated to 2-bromo-2-chloro-4,5-benzocyclohepta-4,6-diene-1,3-dione (XVII) at room temperature, to 5-bromo-7-chloro-2,3-benzotropone (XVI) at 100°C, and to 2-chloro-2,7-dibromo-4,5-benzocyclohepta-4,6-diene-1,3-dione (XVIII) with excess bromine at 100°C. XVII and XVIII were easily debrominated to XV and XVI, respectively, on heating with hydrochloric or hydrobromic acid. XV changed into a mixture of I and II on heating with hydrobromic acid.
  • Shigehiro Ooba, Masaki Ohta, Hiroshi Kato
    1970 Volume 43 Issue 6 Pages 1782-1788
    Published: 1970
    Released: March 27, 2006
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    1-Acetyl- and 1-isopropenyl-3-methylenecyclobutane (I and II) were prepared and then subjected to pyrolysis. The pyrolysis of I at 304–340°C gave 2-methyl-5-methylene-Δ2-dihydropyrane, which was then converted to 4-methylenecyclohexanone at this temperature. The pyrolysis of II at 255–340°C gave 1-methyl-4-methylenecyclohexene, which was disproportionated at this temperature to p-xylene and 1,4-dimethylcyclohexene. In neither case was fragmentation to olefins observed. These results were interpreted by a two-step biradical mechanism.
  • Masanao Oya, Keikichi Uno, Yoshio Iwakura
    1970 Volume 43 Issue 6 Pages 1788-1791
    Published: 1970
    Released: March 27, 2006
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    It has been found that, when the polymerization of NCA is initiated with n-butylamine in acetonitrile, the amino end group in the polymer produced which is insoluble in the solvent is active (Y. Iwakura, K. Uno and M. Oya, J. Polym. Sci., Part A-1, 8, 2165 (1968)). The amino end group in the polymer isolated without drying could initiate the polymerization of NCA in acetonitrile. By using this characteristic of the polymer, block copolypeptides consisting of various kinds of α-amino acid and of various chain lengths were synthesized. The solubility of the block copolypeptides in a solvent was different from that of the random copolypeptides obtained by the usual copolymerization of a mixture of NCA in acetonitrile. Sometimes the infrared spectra of the block copolypeptides were different from those of the random copolypeptides.
  • Yoshiharu Izumi, Hidemitsu Takizawa, Kunio Nakagawa, Ryushichi Imamura ...
    1970 Volume 43 Issue 6 Pages 1792-1795
    Published: 1970
    Released: March 27, 2006
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    The hydrogenation process of ethyl 2-acetoximinopropionate was investigated by means of a novel technique using asymmetric hydrogenation with an asymmetrically modified R–Ni catalyst. It was found that the hydrogenation of ethyl 2-acetoximinopropionate to ethyl alaninate proceeded in two steps through ethyl acetoxyalaninate, and that the asymmetric hydrogenation was performed in the step of the formation of ethyl acetoxyalaninate from ethyl 2-acetoximinopropionate. Besides, the asymmetric reductive amination of ethyl pyruvate was tested with an asymmetrically modified R–Ni catalyst.
  • Yoshiyuki Kawase, Setsuko Takata, Toshio Miwa
    1970 Volume 43 Issue 6 Pages 1796-1803
    Published: 1970
    Released: March 27, 2006
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    The migration of the 5-alkyl groups of 2,3-dimethyl-5-alkyl-6-benzofuranyl methyl ketones by aluminum chloride was studied further, and an analogous migration was observed in the cases of methyl 2,3-dimethyl-5-alkyl-6-benzofurancarboxylates. The 5-ethyl-, 5-n-propyl-, and 5-isopropyl-ketones were converted to the corresponding carboxylic acids by the bromoform reaction and then, further, to the esters. The action of aluminum chloride on the 5-n-propyl-ketone and the esters in carbon disulfide at room temperature afforded the corresponding 4-alkyl-compounds as a result of the migration of the 5-alkyl groups to the 4-position, analogously to the way in which the 5-ethyl- and 5-isopropyl-ketones had afforded two 4-alkyl-ketones. The structures of the compounds were confirmed by converting both the ketones and the esters to the same carboxylic acids and from the data of their IR, UV and NMR spectra and gas chromatograms. It was found that the 5-alkyl groups were less likely to migrate in the cases of the esters than the corresponding alkyl groups in the cases of the ketones, while the n-propyl groups of the ketone and the ester were less likely to migrate than the other alkyl groups, and that the migration seemed to be intramolecular, as the n-propyl group was not isomerized to an isopropyl group during the migration.
  • Masahiro Kise, Shigeru Oae
    1970 Volume 43 Issue 6 Pages 1804-1808
    Published: 1970
    Released: March 27, 2006
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    Diaryl sulfoxides undergo oxygen exchange and racemization reaction with acetic anhydide. The rate of racemization of p-tolyl phenyl sulfoxide was found to be twice that of oxygen exchange. The remarkably small substituents effect is also in keeping with the SN2 type mechanism. Addition of acetic acid increases the rate of both the racemization and oxygen exchange. Racemization of sulfoxides is also known to be catalyzed markedly by a small amount of Lewis acid. When the reaction was carried out in the presence of a small amount of both acetic acid and Lewis acid, the ratio of the rate constants, kexkrac becomes unity. This may mean that the presence of both Brönsted and Lewis acids facilitates the cleavage of S–O bond by easy protonation (or hydrogen-bonding) or coordination on the sulfoxide oxygen, and the assistance of the nucleophilic attack by acetate becomes less important in the reaction. The larger substituent effect is also in keeping with the SN1 type mechanism.
  • Tetsushi Yamashita, Nobuo Nakamura
    1970 Volume 43 Issue 6 Pages 1809-1811
    Published: 1970
    Released: March 27, 2006
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    The chromatographic resolution of several racemic amines was investigated by using three types of copolymers composed by N-acroylated α-amino acid and N,N′-dimethacroylhexamethylenediamine. The anilides of DL-phenylalanine and DL-valine, and of DL-phenylglycine and DL-1,2-diphenylethylamine, were partially resolved. The combination of substrate and sorbent giving the most efficient resolution was anilide of phenylglycine and the copolymer involving L-phenyl-alanine.
  • Takashi Abe, Shunji Nagase, Kazuo Kodaira, Hajime Baba
    1970 Volume 43 Issue 6 Pages 1812-1816
    Published: 1970
    Released: March 27, 2006
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    Chlorofluoromethanes and sulfur hexafluoride were obtained in good yields by the electrochemical fluorination of carbon disulfide in the presence of chlorine. The yields and compositions of the products were altered by the amount of chlorine fed in during electrolysis and also by the concentration of sulfur or carbon tetrachloride dissolved in carbon disulfide. Tetrafluoromethane, trifluoromethylsulfur pentafluoride, difluoromethylene bis-(sulfur pentafluoride), bistrifluoromethyl disulfide, and chlorodifluoromethylsulfur pentafluoride were also among the products. Further, the electrochemical fluorination of elementary sulfur was accomplished by the application of the technique of chlorofluorination, and sulfur hexafluoride was obtained in a reasonable yield. The chlorofluorinations of methyl sulfide and methyl disulfide were also attempted, but they afforded only chlorotrifluoromethane in poor yields.
  • Heimei Yuki, Koichi Hatada, Kazuhiko Nagata
    1970 Volume 43 Issue 6 Pages 1817-1820
    Published: 1970
    Released: March 27, 2006
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    The vinyl interchange reaction of methyl vinyl ether and methanol, methanol-d4, or ethanol catalyzed by mercuric acetate has been studied. Some organomercuric compounds have been isolated from the reaction mixture, and their catalytic activity for the interchange reaction has been examined. From these results, the mechanism proposed by Watanabe and Conlon (J. Amer. Chem. Soc., 79, 2828 (1957)) has been confirmed and further details of the reaction mechanism are discussed.
  • Tadashi Sasaki, Shoji Eguchi, Takeshi Toru, Katsumi Ito
    1970 Volume 43 Issue 6 Pages 1820-1824
    Published: 1970
    Released: March 27, 2006
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    The Ritter reactions of 1-hydroxymethyladamantane (1) and 3-homoadamantanol (14) with acetonitrile in coned, sulfuric acid were investigated. Two products, N-3-homoadamantyl acetamide (2) and N-1-adamantylmethyl acetamide (3) were isolated. Their total- and relative yields were determined in various reaction conditions by GLG analysis, indicating the facile conversion of N-3-homoadamantyl acetonitrilium cation (12) into N-1-adamantylmethyl acetonitrilium cation (13).
  • Shoei Ito
    1970 Volume 43 Issue 6 Pages 1824-1828
    Published: 1970
    Released: March 27, 2006
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    The lithium aluminum hydride reduction of 7-methoxychromanone oxime (I) and 7-methoxy-3-methylchromamone oxime (II) gave only the rearrangement product (the 2,3,4,5-tetrahydro-1,5-benzoxazepine derivative). 7-Methoxy-2-methylchromanone oxime (III) and 7-methoxy-2-isopropylchromanone oxime (IV) gave a mixture of the rearrangement product (secondary amine) and the normal reduction product (primary amine). 7-Methoxy-2-t-butylchromanone oxime (V) gave only the normal reduction product. The main conclusions to be drawn from these results are as follows: (1) The chromanone oximes without a C2 substituent give only the rearrangement product. (2) The chromanone oximes with a C2 substituent give a mixture of the normal reduction product and the rearrangement product. (3) The more bulky substituent at C2 gives the more normal reduction product and the smaller quantity of the rearrangement product.
  • Nobuo Mitsuyasu, Shuji Matsuura, Michinori Waki, Motonori Ohno, Satoru ...
    1970 Volume 43 Issue 6 Pages 1829-1834
    Published: 1970
    Released: March 27, 2006
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    The synthesis of cyclic decapeptide, cyclo-L-phenylalanyl-D-phenylalanyl-L-asparaginyl-L-glutaminyl-L-phenylalanyl-L-valyl-L-ornithyl-L-leucyl-D-phenylalanyl-L-prolyl, which has the amino acid sequence designated as tyrocidine E by Kurahashi, and the chemical and biological properties of the synthetic product, have been described. The degree of the activity of the synthetic product toward the Gram positive microorganisms is nearly the same as that of tyrocidine A. The results indicate that the L-tyrosine residue in the molecule of tyrocidine A can be replaced by L-phenylalanine without influencing activity.
  • Kosaku Noda, Motoaki Bessho, Tetsuo Kato, Nobuo Izumiya
    1970 Volume 43 Issue 6 Pages 1834-1839
    Published: 1970
    Released: March 27, 2006
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    The reaction mixture of glycylglycine with formaldehyde in an alkaline aqueous solution containing cupric ion at 100°C gave seven ninhydrin positive components which were identified as follows; α-hydroxymethylserine, serine, glycine, 3-carboxymethyl-4-imidazolidone, α-hydroxymethylseryl-glycine, serylglycine and glycylglycine. The yield of serylglycine increased in proportion to the amount of cupric ion, whereas the yield of 3-carboxymethyl-4-imidazolidone was maximum when no cupric ion was added. A single-step synthesis in preparative scale of serylglycine or 3-carboxymethyl-4-imidazolidone under the best condition was achieved in a good yield.
  • Takumi Ishiwaka, Mitsuo Yonemoto, Kakuzo Isagawa, Yasaburo Fushizaki
    1970 Volume 43 Issue 6 Pages 1839-1843
    Published: 1970
    Released: March 27, 2006
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    The reaction of 2-aminobenzophenones with aliphatic acids, such as acetic acid, propionic acid, n-butyric acid, and bromoacetic acid, in the presence of polyphosphoric acid afforded 6-substituted 2-anilino-4-phenylquinoline derivatives in fairly good yields. Some of these quinolines were acetylated in the usual way, and the products, 2-(N-acetylanilino) quinolines, were treated with sodium ethoxide to give 1-quinolyl-2(1H)-quinolone derivatives. 2-Amino-5-chlorobenzophenone (Ic) reacted with an equimolar amount of 2-acetamido-5-methylbenzophenone to give 2-(2-benzoyl-4-methylanilino)-6-chloro-4-phenylquinoline, which was also obtained from the reaction of 2,6-dichloro-4-phenylquinoline with Ib in the presence of copper powder. It was found that the reaction mechanism in the formation of 2-anilinoquinolines is similar in type to that in Friedländer’s reaction. Furthermore, the structures of the 2-anilinoquinolines are discussed on the basis of our NMR spectral study.
  • Tetsuo Suami, Seiichiro Ogawa, Hiroshi Sano
    1970 Volume 43 Issue 6 Pages 1843-1846
    Published: 1970
    Released: March 27, 2006
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    Hydrazinolysis of 2,4,5,6-tetra-O-acetyl-1,3-di-O-p-toluenesulfonyl-myo-inositol, followed by catalytic hydrogenation afforded myo-inosadiamine-1,3 via an intermediary 6,7-diazabicyclo[3.2.1]-octane-2,3,4,8-tetrol. In this reaction, the use of N,N′-dimethylhydrazine and N-methylhydrazine, instead of hydrazine, gave actinamine: a component of an antibiotic spectinomycin, and N-methyl-myo-inosadiamine-1,3: an important intermediary compound for a synthesis of DL-hyosamine, respectively. Details of the convenient syntheses of actinamine and DL-hyosamine are described.
  • Yuzuru Takagi, Shigeo Nishimura, Kozo Hirota
    1970 Volume 43 Issue 6 Pages 1846-1849
    Published: 1970
    Released: March 27, 2006
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    Isomeric cresols have been hydrogenated over ruthenium and palladium catalysts at elevated temperature and pressure. The yields of the methylcyclohexanone intermediates formed were estimated by application of a kinetic method. Hydrogenation with ruthenium catalyst gave 77, 61 and 60% of the ketone as the intermediate for o-, m- and p-cresol, respectively, while with palladium catalyst all isomeric cresols yielded the ketone intermediates quantitatively. The hydrogenation pathways leading to the formation of methylcyclohexanones were discussed. The stereochemistry of hydrogenation of isomeric cresols and methylcyclohexanones were also studied, and the results were interpreted on the basis of the estimated yields of the ketone intermediates.
  • Michio Kondo, Nobuo Izumiya
    1970 Volume 43 Issue 6 Pages 1850-1854
    Published: 1970
    Released: March 27, 2006
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    Analogs of gramicidin S, 1,1′-L-leucine-gramicidin S (XI) and 1-L-leucine-cyclosemigramicidin S (XII), have been synthesized and tested for antibacterial properties. The cyclization reaction of a linear decapeptide active ester, in which δ-amino functions of ornithine residues were protected with benzyloxycarbonyl groups, yielded exclusively a protected cyclic decapeptide which was hydrogenated to afford the dihydrochloride of XI. A linear pentapeptide active ester afforded a mixture of protected cyclic penta and decapeptide. The pure protected cyclic pentapeptide was obtained with the use of a Sephadex LH-20 column, and the hydrogenolysis of the product afforded the hydrochloride of XII. The decapeptide analog (XI) was as active as natural gramicidin S, whereas the pentapeptide (XII) showed no activity toward any of the microorganisms tested.
  • Heimei Yuki, Yutaka Taketani, Shuzo Yamashita, Hiroshi Okuno, Hiromich ...
    1970 Volume 43 Issue 6 Pages 1855-1860
    Published: 1970
    Released: March 27, 2006
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    α-Phenyl-, β-phenyl-, and α,β-diphenyl-β-aminopropionic acid were synthesized. Their polymers were obtained in good yields when the p-nitrophenyl esters of β-amino acids were polymerized at 60°C. The ethyl esters gave low-molecular-weight polymers in poor yields at 150°C in vacuo. By the thermal polycondensation of β-amino acids themselves at 250°C, polymers were not obtained, but the corresponding cinnamic acid derivatives were obtained by the intramolecular β-elimination reaction. Poly(α-phenyl-β-amino acid), and poly(β-phenyl-β-amino acid) were soluble in trifluoroacetic acid, and chloroform containing a small amount of dichloroacetic acid. On the other hand, poly(α,β-diphenyl-β-amino acid) was soluble only in cone, sulfuric acid, while it was insoluble in usual organic solvents. The DP of poly(β-phenyl-β-amino acid) was about 18. None of the polymers showed any melting point below 300°C.
  • Masaru Sato, Izumi Motoyama, Kazuo Hata
    1970 Volume 43 Issue 6 Pages 1860-1863
    Published: 1970
    Released: March 27, 2006
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    The reaction of bromoferrocene with copper(I) chloride - pyridine complex was found to be second-order, that is, first-order in each of bromoferrocene and copper(I) chloride-pyridine complex. The results obtained from the competitive reactions between bromoferrocene and bromobenzene indicated that bromoferrocene was 103 times more reactive than bromobenzene in the halogen-exchange reaction. The effects of the pyridine bases on the halogen-exchange reaction of bromoferrocene were examined, and the trend of the results was found to be different from that of bromobenzene. The reason for this was discussed on the basis of the reaction mechanism.
  • Takeshi Nakai, Makoto Okawara
    1970 Volume 43 Issue 6 Pages 1864-1869
    Published: 1970
    Released: March 27, 2006
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    The reactions of 2-dialkylamino-1,3-dithiolanylium perchlorates with a variety of nucleophilic species including oxygen, sulfur and nitrogen nucleophiles have been investigated. Examination of the isolated products reveals that these trihetrosubstituted carbonium ions behave as ambident electrophiles toward nucleophiles with two reactive sites, i.e., the electron-deficient centered carbon (a) and the ring-methylene carbon atom (b), and that the nature of nucleophiles greatly affects the reaction course in a straightforward manner. The reaction course may be classified as follows. If the nucleophile is basic, the reaction at the site (a) (mode A) is favored, but if it has large sub-stituents, the initial proton abstraction reaction (mode C) is predominant, while if the nucleophile is polarizable, the reaction at the site (b) (mode B) is favored. The major factor deciding the reaction course is discussed in terms of the schematic energy profile of the overall reaction.
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