Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 46 , Issue 2
Showing 1-50 articles out of 113 articles from the selected issue
  • Kosaku Kishi, Shigero Ikeda
    1973 Volume 46 Issue 2 Pages 341-345
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Reactions of evaporated iron with O2 and H2O have been investigated by X-ray photoelectron spectroscopy. Binding energies of Fe2p3⁄2 and Ols electrons were measured during the course of reactions and their variation was discussed in terms of the positive and negative charges of the iron and oxygen of the surface oxide formed, respectively, assuming a simple charge-chemical shift relation. They are compared with the binding energies of the Ols in SiO2 Al2O3, Fe2O3, Cd(OH)2, KOH, and Ni(OH)2 and those of Fe2p3⁄2 in various iron compounds High reactivity of the surface oxide with H2O and the resulting hydroxyl group formation were observed. A rough estimation of the Fe to O atomic ratio of the surface oxide was also carried out from the ratio of the Fe and O peak areas.
  • Kenshi Numakura, Enzo Tachikawa
    1973 Volume 46 Issue 2 Pages 346-351
    Published: 1973
    Released: March 27, 2006
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    In order to examine the relative importance of the thermal ionic process in the reactions of 80Br from the (I. T.) process with C3H8, we chose C2H6 or CH3Br as diluents. Some assumptions have made in estimating the yield-variation of products from the diluents: 1) the rate of the reduction of the yields of the products from C3H8caused by the addition of the diluent is the same for all of the products and 2) the ionic yield is zero over the whole range of concentrations of C3H8. With these assumptions, the analysis of the results shows that the contribution of the thermal ionic process in these binary systems has only minor importance; the products are, essentially, formed via energetic processes. It is also found that the ratio of n-C3H780Br/i-C3H780Br per bond basis seems to decrease from 1.1±0.1 on the addition of the diluent. This indicates that the formation of i-C3H780Br is a lower energy process, relative to that of n-C3H780Br in the present reaction system.
  • Ken-ichi Maruya, Atsumu Ozaki
    1973 Volume 46 Issue 2 Pages 351-354
    Published: 1973
    Released: March 27, 2006
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    A new catalyst for ethylene polymerization NiO–NiSO4, was found from a study of NiO–SiO2, and NiCl2 catalysts. The Ni–NiSO4 catalyst prepared from mixtures of formate and sulfate is much less active than NiO–NiSO4 prepared from mixtures of hydroxide and sulfate. Poisoning behavior of carbon monoxide and water is quite similar to NiO–SiO2 catalyst. An equimolar mixture of NiO–NiSO4 gives maximum activity. The active species is postulated to be hydroxy sulfate of nickel. The structure of the active site is discussed.
  • Kazuya Suzuki, Shinsaku Maruyama, Kunio Araki
    1973 Volume 46 Issue 2 Pages 355-358
    Published: 1973
    Released: March 27, 2006
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    A generalized method for numerically calculating Löwdin orbitals is proposed, the method being an application of Frobenius’ theorem in algebra. Löwdin transformation matrix T=S−1⁄2 (S is overlap matrix) is calculated as T=US0−1⁄2 Ut, where S0 is a diagonal matrix whose diagonal elements are eigen values of S, U is a matrix whose column vectors are eigen vectors of S and Ut is the transposed matrix of U. It is proved that the eigen values of the overlap matrix of S are always positive for any choice of linearly independent atomic orbitals and that S−1⁄2, the inverse square-root of S, exists within the range of real numbers. This method is useful for computer calculation by applying Jacobi’s method.
  • Shigeki Yoshimoto, Kenichi Okamoto, Hirotaka Hirata, Shigekazu Kusabay ...
    1973 Volume 46 Issue 2 Pages 358-363
    Published: 1973
    Released: March 27, 2006
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    A new vinylmonomer with a large pendant π-electron group was synthesized. α-Naphthylmethylvinylether and 3-pyrenylmethylvinylether were polymerized in good yields, although their polymers have fairly low molecular weights. Both polymers have a fairly high isotacticity. Poly-3-pyrenylmethylvinylether showed a large photocurrent in its absorption region and a small photocurrent even above 500 to 1000 mμ. The doped TCNE significantly sensitized its photoconductivity.
  • Mitsuru Tanaka, Shoji Kaneshina, Wataru Nishimoto, Hiroyuki Takabatake
    1973 Volume 46 Issue 2 Pages 364-368
    Published: 1973
    Released: March 27, 2006
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    The viscosities of aqueous solutions of sodium alkylsulfate and alkyltrimethylammonium bromide have been measured at various temperatures from 5 to 55°C. The viscosity data have been interpreted in terms of the Jones-Dole equation, and the viscosity B coefficients for the alkylsulfate and alkyltrimethylammonium ions at various temperatures have been calculated. The B values for these ions are all positive; they decrease with an increase in the temperature and increase linearly with an increase in the alkyl-chain length. The increment of B is found to be 0.076/–CH2– at 25°C. The energy and the entropy of activation for the viscous flow at 25°C have been calculated for these ions; they increase with an increase in the alkyl-chain length. This behavior of the B coefficient, and the energy and the entropy of activation for the viscous flow may be interpreted by saying that the longer-chain ions promote the hydrogen-bond structure of water around the hydrocarbon chain of these ions, while shorter-chain ions, e.g., ethylsulfate and ethyltrimethylammonium ions, behave instead as structure breakers because of the predominance of the disordering effect on the water around the ionic head. The viscosities of micellar solutions have also been measured. The volume of micelles as a hydrodynamic moving unit in solution has been estimated.
  • Tamotsu Matsumoto, Masanori Sato, Satoshi Hirayama
    1973 Volume 46 Issue 2 Pages 369-373
    Published: 1973
    Released: March 27, 2006
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    The electrochemiluminescence (ECL) of 9,10-dichloroanthracene in methylene chloride was investigated at temperatures as low as −60°C. The cation was quite stable and the anion was unstable at room temperature. The anion, however, increased its stability as the temperature decreased and below ca. −40°C it was essentially stable. Temperature was also found to have great influence on the relative intensity of the two spectral components of the ECL of 9,10-dichloroanthracene. By lowering the temperature the components at the longer wavelength increased strongly compared with the other component. When the ECL was observed by applying a rectangular potential, the intensities of the two components decayed exponentially with the same decay constant. Therefore, it was concluded that the emission at the longer wavelength originated not from the products of electrolysis but from the excimer and that the primary process to produce these two emissions was the same.
  • Katsumi Kimura, Shunji Katsumata, Yohji Achiba, Hiroshi Matsumoto, Sab ...
    1973 Volume 46 Issue 2 Pages 373-380
    Published: 1973
    Released: March 27, 2006
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    High-resolution photoelectron spectra of alkyl halides RX (R=ethyl, n-propyl, and n-butyl; X=C1, Br, and I) were measured with the 584 Å line of helium. In the region below about 17 eV, six bands were observed for each of the ethyl halides, eight bands for each of the n-propyl halides, and ten bands for each of the n-butyl halides. All the observed vertical ionization energies were plotted against Pauling’s electronegativity of the halogen atom, indicating that there are approximate linear relationships. Assuming Koopmans’ theorem, total and partial sums of experimental orbital energies were calculated using the observed ionization energies for the individual alkyl halides and found to be well reproduced by calculating the sums of empirical orbital-energy values for several localized orbitals such as n(X.), n′(X), σ(C–X), σ(C–C), π(CH3), π′(CH3), and π(CH2). From a comparison of the experimental and calculated partial orbital-energy sums, assignments of the photoelectron bands to the localized molecular orbitals were made for each of the alkyl halides.
  • Hiroyasu Inoue, Toshihiko Hoshi, Junko Yoshino, Yoshie Tanizaki
    1973 Volume 46 Issue 2 Pages 380-384
    Published: 1973
    Released: March 27, 2006
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    The polarized absorption spectra of 2-hydroxy-, 2-amino-, and 2,3-diaminoanthraquinones were measured in stretched PVA sheets below 47 kK, and semiempirical ASMO-SCF-CI calculations, including the variable β method, were carried out for these compounds. By a comparison of the observed and the calculated results, the π–π* bands of these compounds were assigned. Each of these compounds has six bands in the observed wave number region, four of which correspond to those of anthraquinone; the other two bands can be assigned to the intramolecular charge-transfer transitions.
  • Mitsuo Kitano, Tsutomu Fukuyama, Kozo Kuchitsu
    1973 Volume 46 Issue 2 Pages 384-387
    Published: 1973
    Released: March 27, 2006
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    The bond distances (rg) and angles (rα) in N-methylacetamide have been determined by gas electron diffraction as follows: C–C=1.520±0.005 Å, N–C (methyl)=1.469±0.006 Å, N–C (carbonyl)=1.386±0.004 Å C=O=1.225±0.003 Å, C–H (average)=1.107±0.005 Å, ∠N–C=O=121.8±0.4°, ∠C–N–C=119.7±O.8°, ∠C–C–N=114.1±1.5°, ∠H–C–H(average)=110.4±2° and ∠H–N–C(carbonyl)=110±5°. In comparison with the molecular structure in the crystal, the N–C(carbonyl) bond is about 0.10 Å longer, whereas the C–C and C=O bonds are about 0.02 and 0.01 Å shorter, respectively. The two methyl groups are in the trans conformation about the N–C (carbonyl) bond, no other conformer being observed.
  • Tatsuya Sekine, Yoshihiro Takahashi, Naohiko Ihara
    1973 Volume 46 Issue 2 Pages 388-391
    Published: 1973
    Released: March 27, 2006
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    Aqueous solutions containing sodium hydroxide and sodium perchlorate at various mixing ratios, 1 M Na-(OH, ClO4), were equilibrated with several organic solvents containing 2-thenoyltrifluoroacetone (TTA) at 25°. From the measurements of the hydrogen-ion concentration of the aqueous phase, the (KD+l)Ka−1 values, where KD is the distribution constant and Ka is the acid dissociation constant of TTA, were obtained; they were, 107.17(hexane), 107.74 (CCl4), 108.01 (C6H6) and 108.17 (CHCl3). From the values of KD obtained in another study, the value of Ka was determined to be 10−6.28. However, a much lower value than that expected was obtained for the MIBK system; this was due to the extraction of sodium (I) with TTA. The extraction was also confirmed by the distribution experiments of sodium (I). The extraction constant, Kex=[NaA]org/[Na+] [A] (where A is the TTA anion), was found from these results to be 100.86 in 1 M NaClO4 and 100.79 at an infinite dilution.
  • Katsumi Shimada, Sadao Okido, Osamu Tanimoto
    1973 Volume 46 Issue 2 Pages 392-397
    Published: 1973
    Released: March 27, 2006
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    Green’s function matrix method for the calculation of the orbital energies of π-electron systems, which has been discussed in previous papers, is applied to the allyl cation, butadiene, rectangular cyclobutadiene, and cyclic polyenes with various molecular lengths. The higher-order correction for the Hartree-Fock orbital energies are calculated, and in the case of butadiene the theoretical value of the ionization potential is discussed in comparison with the experimental data. The relation between the higher-order correction effect and the molecular length is illustrated in the cases of the cyclic polyenes. In particular, the breakdown of perturbation calculation based on the Hartree-Fock orbitals occurs in the case of the C30H30 molecule.
  • Tsuneo Okubo, Shou-Xyng Chen, Norio Ise
    1973 Volume 46 Issue 2 Pages 397-400
    Published: 1973
    Released: March 27, 2006
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    The solubility of alkyl bromides (alkyl : ethyl, n-propyl, n-butyl and n-amyl) in aqueous solutions of neutral polymers and polyelectrolytes was measured and discussed. The polymers used were polyacrylamide (PAAm), polyvinylalcohol(PVA), polyethyleneglycol (PEG), polyvinylpyrrolidone(PVP), polyethylenimine(PEI) and polyacrylic acid(PAA) and its salts. The solubility of alkyl bromide increased linearly with concentration of neutral polymer in the order PAAm>PVP∼PEI>PEG>PVA∼PAA. Sodium salt of PAA decreased the solubility of alkyl bromide, but organic salts of PAA such as tetraalkylammonium salts increased it. Using the equation In (SoS)=km2, the limiting Setchénow constant k was obtained for these systems. The results were accounted for in terms of the hydrophobic structural modifications of water and the direct dipole and/or hydrophobic interactions between solute and cosolute.
  • Hisashi Uedaira
    1973 Volume 46 Issue 2 Pages 401-404
    Published: 1973
    Released: March 27, 2006
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    The diffusion coefficients of sodium salts of m-benzene disulfonate, 1,5-naphthalenedisulfonate, 1,2-ethanedisulfonate, and 1,4-butanedisulfonate in aqueous solutions were measured at 25°. The concentration dependence of the diffusion coefficients for sulfonates decreased with increasing charge distance and was smaller than that of the corresponding ordinary 2 : 1 electrolytes. The concentration dependence of diffusion coefficient for sodium m-benzenedisulfonate was the largest. It is shown that bolaform electrolytes behave like normal 1 : 1 electrolytes in the concentration range where the ion atmosphere around each charged group is independent.
  • Shigehiro Konaka, Masao Kimura
    1973 Volume 46 Issue 2 Pages 404-407
    Published: 1973
    Released: March 27, 2006
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    The molecular structure and mean amplitudes of SbCl3 have been determined, by the sector-microphotometer method of gas-phase electron diffraction, to be as follows: rg(Sb–Cl)=2.333±0.003 Å, rg(Cl–Cl)=3.50±0.02 Å, θα=97.2°±0.9°, l(Sb–C1)=0.063±0.004 Å, and l(Cl–Cl)=0.147±0.014 Å. The zero-point average structure derived from the diffraction results by the use of the estimated potential constants is consistent with the rotational constants, Bz, derived from the Bo of microwave measurements. The joint use of the ED and MW data has given a value of 2.326±0.001 Å for rz(Sb–Cl).
  • Kuniaki Kashiwabara, Shigehiro Konaka, Takao Iijima, Masao Kimura
    1973 Volume 46 Issue 2 Pages 407-409
    Published: 1973
    Released: March 27, 2006
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    Electron scattering by dimethylmercury has been studied for 42 keV electrons. The theoretical scattering factors currently used have shown satisfactory conformity to the observed scattering intensity, with the following distance parameters: rg(Hg–C)=2.083±0.005 Å, rg(Hg…H)=2.71±0.02 Å, and rg(C–H)=1.106 Å (assumed). A comparison of the background functions has revealed that the scattering factors based on the relativistic Hartree-Fock-Slater potential are better than those based on the Thomas-Fermi-Dirac and Thomas-Fermi potentials. The zero-point average distance determined from the spectroscopic data has shown significant inconsistency with the diffraction result. The diffraction value is shorter than the spectroscopic one by 0.015 Å.
  • Kuniaki Kashiwabara, Shigehiro Konaka, Masao Kimura
    1973 Volume 46 Issue 2 Pages 410-413
    Published: 1973
    Released: March 27, 2006
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    The molecular structure of mercury (II) chloride has been determined by the sector-microphotometer method of gas-phase electron diffraction at accelerating voltages of 29 and 42 kV. The parameter values obtained are: rg(Hg–Cl), 2.252±0.005 Å; l(Hg–Cl), 0.052±0.005 Å; rg(Cl–Cl), 4.48±0.04 Å; and l(Cl–Cl), 0.09±0.04 Å. A linear structure has been confirmed within an error of 16°. The experimental mean amplitudes are consistent with the estimated values based on the spectroscopic data. No appreciable differences in the structure parameters have been found between the results of analysis carried out on the basis of the Thomas-Fermi-Dirac and the relativistic Hartree-Fock-Slater scattering factors.
  • Shigehiro Konaka, Masao Kimura
    1973 Volume 46 Issue 2 Pages 413-416
    Published: 1973
    Released: March 27, 2006
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    The molecular structure and mean amplitudes of SbBr3 at 102°C have been determined by the sector-microphotometer method of gas-phase electron diffraction to be as follows: rg(Sb-Br)=2.490±0.003 Å, rg(Br-Br)=3.76±0.01 Å, θα=98.2°±0.6°, l(Sb–Br)=0.060±0.003 Å and l(Br–Br)=0.15±0.01 Å. General quadratic force constants have been determined from the observed mean amplitudes and vibrational frequencies. The molecular structure supports the validity of the empirical rules between a bond length and the covalent radii and electronegativities of its constituent atoms. An empirical equation, θ(YXY)=92+8xX−3xY(+xZ), has been proposed for the bond angles of Vb-group halides, (Z)XY3, and the electronegativities, x.
  • Hiroshi Kashiwagi, Suehiro Iwata, Tsuguo Yamaoka, Saburo Nagakura
    1973 Volume 46 Issue 2 Pages 417-422
    Published: 1973
    Released: March 27, 2006
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    Electronic spectra were measured for azidobenzene, 1-azidopyrene, benzenediazonium ion, and 1-pyrenediazonium ion at room temperature, and also for nitrenobenzene and 1-nitrenopyrene at liquid nitrogen temperature. The π-electron structures of these compounds were calculated by the Pariser-Parr-Pople LCAO SCF MO CI method for the closed-shell systems and by the restricted open-shell SCF MO CI method for the open-shell systems. The calculated transition energies and oscillator strengths could satisfactorily explain the observed spectra. It was shown that the π-electron structures of azidobenzene and nitrenobenzene are similar to those of dimethylaniline and the benzyl or anilino radical, respectively.
  • Yôichi Iida
    1973 Volume 46 Issue 2 Pages 423-426
    Published: 1973
    Released: March 27, 2006
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    The infrared spectra of tetracyanoethylene (TCNE) and its anion radical in the rock-salt region were examined in order to observe any appreciable frequency differences between their corresponding bands. The vibrational assignments were made, and the basic Urey-Bradley force field was determined for the TCNE anion radical. By comparing them with those of the neutral TCNE, we discussed the difference in the electronic states between the neutral TCNE and its anion radical. The half-occupied molecular orbital of the TCNE anion radical was found to belong to the B2g irreducible representation.
  • Katsuhiko Miyoshi
    1973 Volume 46 Issue 2 Pages 426-430
    Published: 1973
    Released: March 27, 2006
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    Conductance equations derived by Fuoss-Onsager (1965), Fuoss-Hsia (1967) and Pitts (1953) were compared using the conductance data of bis(2,9-dimethyl-1,10-phenanthroline)Cu(I) perchlorate in acetonitrile, nitrobenzene and nitromethane at 25°C, which have relatively high dielectric constant. The chelate salt was found to be completely dissociated in these solvents. Though the Pitts equation was found to reproduce the data more satisfactorily than the Fuoss-Onsager (F–O) and the Fuoss-Hsia (F–H) equations, the derived distance of the closest approach a from the Pitts equation was unrealistically small for the bulky complex salt. It was shown that the F–H equation is preferable for the analysis of conductance data for both associated and unassociated electrolytes.
  • Yoshiharu Matsuda, Kazuo Kimura, Chiaki Iwakura, Hideo Tamura
    1973 Volume 46 Issue 2 Pages 430-434
    Published: 1973
    Released: March 27, 2006
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    The anodic oxidation of benzoic acid in acetonitrile and propionitrile was studied. Electrolysis was employed under a controlled potential or current. Benzoic acid was changed into an intermediate benzoyloxy radical through de-electronation in acetonitrile, and the resulting radical was reacted with acetonitrile to give N-acetylanthranilic acid in a 38% yield under constant potential electrolysis. In propionitrile, the anodic oxidation gave N-propionylanthranilic acid, N-propionylbenzamide, and dipropionylamine. No Kolbe-type reaction was observed.
  • Akio Furusaki, Nobuyuki Hamanaka, Takeshi Matsumoto
    1973 Volume 46 Issue 2 Pages 434-441
    Published: 1973
    Released: March 27, 2006
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    It has already been found that the Birch reduction of 1,1,4aα-trimethyl-2α-hydroxy-8-methoxy-1,2,3,4,4a,9-hexahydrophenanthrene affords a tetrahydro derivative, contrary to expectations. The present paper will describe the details of the molecular structure of the unexpected reduction product, as revealed by an X-ray crystal analysis of its p-bromobenzoate (racemate). The crystals are triclinic, with two molecules in a unit cell of the dimensions: a=11.155, b=18.123, c=5.912 Å, α=94°39′, β=111°35′, and y=90°42′. The space group is P\bar1. The intensity measurement was made on an automatic four-circle diffractometer with CuKα radiation. The structure was solved by the heavy-atom method, and was refined by the block-diagonal-matrix least-squares method, anisotropic thermal motions being assumed for all the non-hydrogen atoms. From a difference map, twenty-six of the thirty-one hydrogen atoms were also found. The final R factor was 6.5%. As a result of the present study, it has been found that the C ring of cyclohexene-type shows an unusual behavior. The length of the C–C single bond opposite to the double bond in this ring is found to be only about 1.34 Å. This remarkable shortening seems to be due to special vibrations of the two atoms concerned. The whole cyclohexene ring takes a considerably flattened, half-chair form.
  • Hiroshi Yokoi, Masaki Otagiri, Taro Isobe
    1973 Volume 46 Issue 2 Pages 442-447
    Published: 1973
    Released: March 27, 2006
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    ESR and spectrophotometric studies have been made of a number of 1 : 1 complexes of copper (II) with ethylenediamine, its analogues, and amino acids in aqueous-methanolic solutions. It has been shown that the complexes in the solutions are characteristic of copper(II) ions with a normal tetragonal environment and that their metal-ligand bondings are intermediate in the degree of covalency between those of hydrated cupric ions and the corresponding 1 : 2 complexes. The disproportionation constants and their temperature dependences, determined for the 1 : 1 complexes by the ESR and spectrophotometric methods, have been discussed, with particular empahsis on the fact that those values are in fair agreement with those derived from the step-by-step formation constants and the thermodynamic data obtained in aqueous solutions in the literature.
  • Hiroshi Yokoi, Taro Isobe
    1973 Volume 46 Issue 2 Pages 447-451
    Published: 1973
    Released: March 27, 2006
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    A study of the ESR spectra of several β-diketone chelate complexes of copper(II) in the frozen solution of toluene has revealed that triplet-state dimers are formed at high concentrations in the solution and that these dimers are in equilibrium with only the monomers. The approximate equilibrium constants have been determined by a careful analysis of the ESR spectra observed in various concentrations. Structures for the dimers have been suggested from magnetic parameters properly determined using a point dipole model.
  • Satohiro Tanaka
    1973 Volume 46 Issue 2 Pages 452-456
    Published: 1973
    Released: March 27, 2006
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    A Rocker-type DTA apparatus, with agitation by rocking, has been developed for use in the thermal analysis of various fluid mixture systems. The heater block, with its assembled cells, is continuously rocked at 20 r.p.m. with a rocking of 180° angle. The glass cell has a volume of about 8 ml and is sealed by means of a burner with a sample of about 5 ml. Distilled water is used as the inert reference in the reference holder. Two thermocouples are inserted in each cell, one to determine the temperature difference and the other for sample temperature measurements. The double thermocouple gives a constant transition temperature of the sample over a wide range of heating rates. The apparatus is applied to solid-liquid and starch-water systems. Variables affecting the DTA thermogram of the K2Cr2O7–H2O system are investigated, and a method is established to correlate the DTA curve with the solubility curve for the system.
  • Koichi Nakamura, Toshihiko Tsuchida, Akihiko Yamagishi, Masatoshi Fuji ...
    1973 Volume 46 Issue 2 Pages 456-459
    Published: 1973
    Released: March 27, 2006
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    The complex formation between Fe(III) and 10 kinds of phenols was investigated using a stopped-flow apparatus. It was confirmed that the reaction rate is acid-independent in the acid region 0.01–1.0 M. A mechanism for the aquation of the iron (III)-phenol complex is proposed in which a proton transfers intramolecularly from a co-ordinated water molecule to a phenolate ion, viz., Fe(OH2)5A2+→Fe(OH2)4(OH)·AH2+. From the observed isotope effects it was concluded that the state of a proton of HA in Fe(OH2)4(OH)·AH2+ differs from that in a free phenol.
  • Yoshihisa Matsui, Yoshio Date
    1973 Volume 46 Issue 2 Pages 460-463
    Published: 1973
    Released: March 27, 2006
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    Ethylamine at concentrations lower than 0.5 him in N,N-dimethylformamide gives a diffusion-controlled anodic wave due to the reversible oxidation of the mercury to a 1:2 complex of mercury(II) with the amine. At higher concentrations, another anodic wave appears at a potential less positive than the main wave; this has been attributed to the adsorption of the oxidation product on the mercury electrode. The adsorption prewave was analyzed on the basis of Brdicka’s theory, in which the Langmurian adsorption was assumed. It was shown that the nature of the prewave can be well interpreted on the additional assumption that the adsorption coefficient of the adsorbed complex decreases exponentially as the electrode potential becomes more positive.
  • Yoshihisa Matsui, Hitoshi Takaya, Yoshio Date
    1973 Volume 46 Issue 2 Pages 464-467
    Published: 1973
    Released: March 27, 2006
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    A solution of ammonia, methylamine, n-propylamine, isopropylamine, or n-butylamine in N,N′-dimethyl-formamide gives an anodic prewave due to the adsorption of the oxidation product, Hg(amine)22+, on the dropping mercury electrode. The shape of the prewave of each amine can be well interpreted by an equation derived on the basis of the assumptions that the adsorption follows the Langmuir isotherm and that the adsorption coefficient of the adsorbate complex decreases exponentially as the electrode potential becomes more positive. Some physicochemical properties of the mercury(II) complexes, such as the overall stability constants and the adsorption coefficients at 0.0 V vs. SCE, were determined by analyses of the polarographic waves.
  • Hidehiro Ishizuka, Takeo Yamamoto, Yoji Arata, Shizuo Fujiwara
    1973 Volume 46 Issue 2 Pages 468-471
    Published: 1973
    Released: March 27, 2006
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    NMR spectra of L-aspartic acid coordinated with Zn ions were measured in aqueous solution at various pH values. Three species of zinc-L-aspartic acid complexes were identified i.e., 1 : 1 zinc–L-aspartic acid(zwitter ionic form) complex (MAH), and 1 : 1 and 1 : 2 zinc–aspartic acid(anionic form) complexes (designated as MA and MA2, respectively). It is shown that, in MAH, the amino acid coordinates with Zn as a monodentate ligand, whereas in MA and MA2, approximately 65% of the molecules of amino acid coordinate as a tridentate ligand. From the chemical shift data, the equilibrium constants for these complexes are determined as follows: pKa-(MAH)=5.3±0.2 and logK2=4.5±0.2 where Ka(MAH)=[MA][H+]/[MAH] and K2=[MA2]/[MA][A].
  • Masaru Kimura, Toshiro Sato
    1973 Volume 46 Issue 2 Pages 471-474
    Published: 1973
    Released: March 27, 2006
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    The kinetics of the thermal decomposition of the trioxalatocobaltate(III) complex were studied in a sulfuric acid solution in the absence and in the presence of oxygen from 25 to 40°C. The decomposition of trioxalatocobaltate(III) was described by the equation: -d[Co(C2O4)33−]/dt=(k1+k2[H+])[Co(C2O4)33−]. The values of k1 and k2 were 6×10−6 sec−1 and 1.8×10−5 M−1 sec−1 respectively at 25°C. The values of the activation enthalpy change, ΔH1\ eweq and ΔH2\ eweq, were 29.7 and 30.0 kcal mol−1 respectively. The values of the activation entropy change, ΔS1\ eweq and ΔS2\ eweq, were 17.4 and 20.9 eu respectively at 40°C. Although hydrogen peroxide was formed in the presence of oxygen, and although a white precipitate of the polymerized products of acrylonitrile was found in the presence of acrylonitrile, neither oxygen nor acrylonitrile affected the kinetics of the decomposition of trioxalatocobaltate(III). The decomposition of peroxodisulfate was induced by the decompossition of trioxalatocobaltate(III). However, the rate of the decomposition of trioxalatocobaltate(III) was not affected by peroxodisulfate. On the other hand, both copper(II) and iron(III) ions were accelerators of the decompsition of trioxalatocobaltate(III). An anion radical of CO2 was predicted as an intermediate. The reaction mechanisms will be presented to account for these facts.
  • Ken-ichi Okamoto, Jinsai Hidaka, Yoichi Shimura
    1973 Volume 46 Issue 2 Pages 475-479
    Published: 1973
    Released: March 27, 2006
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    Four cobalt(III) complex anions, bis(L-prolinate-N-monopropionato)-, (L-prolinate-N-monoacetato)(imino-diacetato)-, (L-prolinate-N-monopropionato)(iminodiacetato)- and (L-prolinate-N-monoacetato)(L-prolinate-N-monopropionato)cobaltate(III) were synthesized. They were isolated as sodium or potassium salts by ion-exchange column chromatography. These complexes were characterized on the basis of their absorption and circular dichroism spectra in the visible and near ultraviolet regions. All the complexes obtained in solid state have trans(N)-RR or trans(N)-R. configuration. Two geometrical isomers were obtained for (L-prolinate-N-monopropionato)triamminecobalt(III) complexes.
  • Shigenobu Funahashi, Shoji Adachi, Motoharu Tanaka
    1973 Volume 46 Issue 2 Pages 479-483
    Published: 1973
    Released: March 27, 2006
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    Kinetics of the formation of monothiocyanato and mononitrilotriacetato complexes of iron(III) in aqueous solution have been studed by using a stopped-flow technique:
    Fe3++SGN\oversetk1\undersetk−1\ ightleftharpoonsFeNCS2+
    FeOH2++SCN\oversetk2\undersetk−2\ ightleftharpoonsFeNCS2++OH
    FeOH2++H2nta\oversetk→Fe(nta)+H+
    Rate constants at 25°C and μ=0.5 (NaClO4) are as follows: k=90 M−1 sec−1, k−1=1.6 sec−1, k2=5.1×103M−1sec−1, k−2=10×1013 M−1 sec−1, k=1.0×105 M−1 sec−1. Some discussions are made on the effect of hydroxide ion on the complex formation reactions.
  • Fumio Sagara, Hiroshi Kobayashi, Keihei Ueno
    1973 Volume 46 Issue 2 Pages 484-488
    Published: 1973
    Released: March 27, 2006
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    Divalent metal chelates of heptane-2,4,6-trione (H2daa) were synthesized and their structures were discussed. Nickel(II), cobalt(II) and palladium(II) ions gave Ni(Hdaa)2·2H2O, Ni2(daa)2·4H2O, Ni2(daa)2·4Py, Co(Hdaa)2·2H2O, Co2(daa)2·4H2O, Co2(daa)2·4Py, Pd(Hdaa)2 and Pd(Hdaa)2·2H2O respectively, while beryllium (II) ion unexpectedly gave bis (2-amino-2-heptene-4,6-dionato) beryllium (II) which resulted from an amino-derivative of the original ligand. Spectroscopic results suggested that the coordination structure of nickel(II) and cobalt(II) ions was octahedral hexacoordinate, that of palladium(II) ion square planar tetracoordinate and that of beryllium(II) ion tetrahedral tetracoordinate. NMR study of the palladium(II) chelate suggested partial enolization of an uncoordinated carbonyl group. It was also found that nickel, cobalt and platinum ions promoted catalytically the bimolecular-condensation of heptane-2,4,6-trione.
  • Genkichi Nakagawa, Hiroko Wada, Yoshio Fujita
    1973 Volume 46 Issue 2 Pages 489-493
    Published: 1973
    Released: March 27, 2006
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    The acid dissociation constants of Calmagite [1-(2-hydroxy-5-methylphenylazo)-2-naphthol-4-sulfonic acid] and the formation constants of zinc(II) chelates have been determined spectrophotometrically at 25°C and at the ionic strengths of 0.1 and 1.0. In an ammoniacal medium zinc forms mixed-ligand complexes with Calmagite (I3−) and ammonia (X); ZnIXn. The formation constants of the zinc(II)-Calmagite chelates are logKZnI=11.75, logKZnI2=7.82, logKZnIXx=2.09, and logKZnIX2x=1.70 (μ=1.0). Calmagite is recommended as an indicator for the titration of zinc(II) with EDTA. The color transition of Calmagite is clearer and sharper, and the aqueous solution of the indicator is more stable, than in the case of Eriochrome Black T.
  • Kosuke Izutsu, Sachiko Sakura, Taitiro Fujinaga
    1973 Volume 46 Issue 2 Pages 493-495
    Published: 1973
    Released: March 27, 2006
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    Polarographic reductions of barium, strontium and calcium ions in hexamethylphosphoramide (HMPA) have been investigated in the supporting electrolytes of various perchlorates. The reduction of these alkaline earth metal ions are strongly influenced by the cation of the supporting electrolyte. When the size of the cation of the supporting electrolyte is small and easily adsorbed on the negatively charged electrode surface as in the cases of Me4N+ and Et4N+ ions, the reduction of the metal ions does not occur until that of the supporting electrolyte. The reduction becomes easier with the increase of cationic size. Thus, in Hex4NClO4 or LiClO4, these metal ions are reduced almost reversibly. These effects of the cation of the supporting electrolyte can be explained as electrode surface phenomena as in the reduction of alkali metal ions.
  • Osamu Uyama, Yasuo Nakao, Akitsugu Nakahara
    1973 Volume 46 Issue 2 Pages 496-499
    Published: 1973
    Released: March 27, 2006
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    Nickel(II) and cobalt(III) chelates of the Schiff bases derived from salicylaldehyde and dipeptides such as glycylglycine, glycylalanine and alanylglycine have newly been prepared. The reactivity of methylene or methine groups in the dipeptide moieties of those Schiff base chelates has been investigated on the basis of their PMR spectra in D2O. It has been confirmed that the methylene or methine protons of the N-terminal amino acid residue are more easily activated than those of the C-terminal amino acid residue.
  • Tomihito Kambara, Masao Sugawara
    1973 Volume 46 Issue 2 Pages 500-502
    Published: 1973
    Released: March 27, 2006
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    The ternary complex composed of vanadium(V),8-hydroxyquinoline-5-sulphonic acid (H2QS), and zephiramine (Z+Cl) was extracted into chloroform. The absorption maxima of the ternary complex in the organic layer were 375 and 580 nm at pH 2.8 and 375 nm at pH 4.8. The optimum pH range for the extraction was 4.5–5.4. Beer’s law held for 1.29–35.6 μg of vanadium(V). The molar absorptivity of the complex was 0.99×104 cm−1 mol−1 l. The composition of the ternary complex was estimated to be [VO2+Z+(QS2−Z+)2]o and the extraction equilibrium was given by
    VO2++2[(HQSZ+)]o+Z++2OH\ ightleftharpoons[VO2+Z+(QS2−Z+)2]o+2H2O (1)
    The logarithm of the equilibrium constant K of this equation was found to be 32.57±0.49.
  • Shoji Harada, Tatsuya Yasunaga
    1973 Volume 46 Issue 2 Pages 502-506
    Published: 1973
    Released: March 27, 2006
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    Nickel maleate complex formation reaction in an aqueous solution, Ni2++Mal2−\oversetkf\undersetkd\ ightleftharpoons NiMal, where Mal2− represents the maleate ion, was studied by the pressure-jump method. The rate constants and the stability constant were obtained; kf=8.4×105 M−1s−1, kd=2.1×103 s1, and K=4×102M−1 at 25°C and at μ→0. The thermodynamic parameters of this reaction were obtained from studies at various temperatures between 10 and 30°C. The results indicate that the nickel maleate is stable as a monodentated complex rather than as a chelate complex. Moreover, the nickel dicarboxylate complex formation reactions and the rate equations were discussed.
  • Yozo Ohtsuka
    1973 Volume 46 Issue 2 Pages 506-509
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The condensation of several primary amines with 4-cyano-5-dialkoxymethylenaminooxazole gave 6-substituted 5-alkoxy-7(6H)-immooxazolo[5,4-d]pyrimidines. These compounds were converted into 3-substituted xanthines by treatment with aqueous alkali or by heating in formamide. The present reaction was compared with an analogous reaction, formation of 9-substituted hypoxantines via 7-aminooxazolo[5,4-d]pyridimine derivatives, and the difference in the reaction course was discussed in terms of the effect of substituents on the stability of oxazolopyrimidine intermediates.
  • Fumio Wada, Tsutomu Matsuda
    1973 Volume 46 Issue 2 Pages 510-514
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction of propargyl alcohol as well as its acetate and methyl ether with carbon monoxide and water in the presence of ironpentacarbonyl-amine catalyst under oxymethylation conditions proved to proceed at a much faster rate than that of 1-butyn-4-ol, 1-pentyn-5-ol and alkylacetylenes accompanied by elimination of the functional groups at C-3 to give dimethyl methylsuccinate. 3-Methyl-1-butyn-3-ol and 1-ethynylcyclohexanol reacted in a similar manner, but gave mixtures of unsaturated monoesters and diesters, saturated and unsaturated. The faster rate of reaction and the product obtained were interpreted by a scheme involving a concerted attack of hydroirontetracarbonyl anion, HFe(CO)4, at the terminal position to split off the group at C-3. The mononuclear hydrido anion was assumed to be an active catalytic species in the reaction on the basis of both the infrared spectra of the catalyst system under the reaction conditions and the efficiency of potassium hydroxide as a base component.
  • Tadashi Tanabe, Kazuo Okuda, Yoshiharu Izumi
    1973 Volume 46 Issue 2 Pages 514-517
    Published: 1973
    Released: March 27, 2006
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    In the asymmetric hydrogenation of methyl acetoacetate with modified Raney nickel catalysts, the effects of pH-adjusting reagents were studied using Ds-tartaric acid, Ls-2-hydroxyisovaleric acid, L-glutamic acid, and L-aspartic acid as the modifying reagents. The effects of various metal ions and ammonium ions were investigated at pH 5.0. The asymmetric activity of the catalyst modified with the 2-hydroxy monocarboxylic acid or 2-amino dicarboxylic acid was not affected by the pH-adjusting reagents. However, 2-hydroxy dicarboxylic acid was markedly influenced by the reagents. The univalent metal ion was more effective than divalent or ammonium ions. Sodium hydroxide was the best pH-adjusting reagent. The adsorption state of the modifying reagent was discussed on the basis of the effects of the pH-adjusting reagent.
  • Hiroo Inoue, Kenzo Kunikawa, Eiji Imoto
    1973 Volume 46 Issue 2 Pages 518-521
    Published: 1973
    Released: March 27, 2006
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    Disodium phthalocyanine (Pc–Na2) acts as a base for the aldol condensations of aldehydes, although it shows no effect upon those of ketones. In the aldol condensation of isobutyl aldehyde by Pc–Na2 in n-hexane, 2,6-diisopropyl-5,5-dimethyl-1,3-dioxane-4-ol (III) is produced through two processes with different rates; the reaction proceeds first by the slower rate, and then by a more rapid rate after a certain reaction period. The process is different from that of the catalysis by sodium ethoxide. During the reaction, Pc–Na2 is converted to sodium-free phthalocyanine (Pc–H2) via an intermediate. The formation of the intermediate results in the retardation of the aldol condensation with the product and phthalocyanine anions. Furthermore, the adsorption of water on Pc-Na2 brings about the retardation of the reaction.
  • Tetsuo Takano
    1973 Volume 46 Issue 2 Pages 522-523
    Published: 1973
    Released: March 27, 2006
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    The reactions of stannic chloride and bromide with triphenylphosphine, -arsine and -stibine tetracarbonyl iron(0) undergo oxidative-elimination reactions to afford new binuclear organometallic compounds in good yields; Fe(CO)4EPh3+SnX4→Fe(CO)3EPh3SnX4+CO (E=P, As, Sb; X=Cl, Br; Ph=C6H5), where one molecule of carbon monoxide is discharged. The complexes are characterized by elemental analysis, by infrared and Mössbauer spectroscopies, and by conductivity measurements; these data are used to predict their possible formulation as nonionic, hexa-co-ordinate iron derivatives of the Fe(CO)3(X)(EPh3)(SnX3) type containing a tin-to-iron metal-metal bond.
  • Akio Matsuda
    1973 Volume 46 Issue 2 Pages 524-530
    Published: 1973
    Released: March 27, 2006
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    The cobalt carbonyl-catalyzed hydromethoxycarbonylation of butadiene is studied. The reaction proceeds in the presence of a pyridine base to give methyl 3-pentenoate. Isoquinoline is found to be a better solvent for the production of methyl 3-pentenoate than pyridine, not only because the yield of the ester is somewhat higher in the presence of isoquinoline than in the presence of pyridine, but also because it is far less volatile than pyridine, so that the product can be easily separated from the solvent and the catalyst by distillation. Also, the hydromethoxycarbonylation of methyl 3-pentenoate under somewhat different conditions is found to give a good yield of dimethyl adipate. The hydroformylation of methyl 3-pentenoate is studied as well. The effect of such a solvent as THF, benzene, and acetonitrile in increasing the selectivity to methyl 5-formylpentanoate is found to increase in this order: acetonitrile<benzene<THF.
  • Yasukazu Yokoyama, Akira Tai
    1973 Volume 46 Issue 2 Pages 530-534
    Published: 1973
    Released: March 27, 2006
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    The reactions between amines and 1,4-bis(ethoxycarbonyl)-2,5-bis(alkyl- or arylamino)-1-4-cyclohexadiene(I) and its analogs are studied. The main products are N,N′-disubstituted urea(II) and 1,4-bis(alkyl- or arylamino)-1,4-cyclohexadiene(V) instead of the expected carboxamide. The presence of small amounts of ethyl N-substituted carbamate (III) in the products leads to the conclusion that the reaction proceeds through two successive steps: the nucleophilic attack by an amine upon a carbonyl carbon atom of the ethoxycarbonyl group, with a cleavage of a carbon-carbon bond to give III and V, and the amidation of III in situ, giving II. The rate of the second step is much faster than that of the first step. The formation of II occurs in the compounds with a β-amino α,β-unsaturated carbonyl group.
  • Shigeru Oae, Nobuko Tsujimoto, Akira Nakanishi
    1973 Volume 46 Issue 2 Pages 535-539
    Published: 1973
    Released: March 27, 2006
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    o-Nitroaniline was obtained when tri(o-nitrophenyl) triaziridine(I) was allowed to react with excess O,O-diethyl dithiophosphoric acid. It was found that azobenzene derivatives(IIa-e) are converted into the corresponding reduction products aniline derivatives (IVa-e) in the reaction with excess O,O-diethyl dithiophosphoric acid. Similarly, arylhydrazines (IIIa-c) were converted into the corresponding aniline derivatives (IVa,d,e) by the action of O,O-diethyl dithiophosphoric acid.
  • Tadashi Sasaki, Shoji Eguchi, Michio Sugimoto
    1973 Volume 46 Issue 2 Pages 540-543
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Ritter reaction of cyano- and chlorocyanoacetylene with appropriate substrates provided a facile one step synthesis of 4,4-dimethyl-2-ethynyloxazoline (5), 4,4,6-trimethyl-2-ethynyl (7) and -2-chloroethynyl-5,6-dihydro-1,3-oxazine (8), 5,5-dimethyl-3-isopropylidene-2-ethynyl- (10) and -2-chloroethynyl-1-pyrroline (11). On treatment with diazomethane, 7 gave 4,4,6-trimethyl-2-(4-1H-pyrazolyl)- (13) and -2-(3-1H-pyrazolyl)-5,6-dihydro-1,3-oxazine (14) in 42 and 40% yields respectively, while 8 afforded only 4,4,6-trimethyl-2-[3-(4-chloro-1-methyl)-pyrazolyl]-5,6-dihydro-1,3-oxazine (15) in 52% yield. On the other hand, 10 gave 5,5-dimethyl-3-isopropylidene-2-(3-1H-pyrazolyl)-1-pyrroline (16) in 64% yield and 11, 5,5-dimethyl-3-isopropylidene-2-[3-(4-chloro-1-methyl)-pyrazolyl]-1-pyrroline (17) in 16% yield.
  • Kimiaki Imafuku, Hisashi Matsumura
    1973 Volume 46 Issue 2 Pages 544-546
    Published: 1973
    Released: March 27, 2006
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    The dissociation constants of two series of 4- and 6-styryl-2-aminotropones were measured spectrophotometrically in 50% aqueous methanol at 20°C. It was found that Hammett’s free energy relationship is applied to the analysis of substituent effects, with ρ=0.59 and 0.40, respectively, and that there is a difference between the electronic effects of the two isomers.
  • Michio Kobayashi, Hiroshi Minato, Nobuko Watanabe
    1973 Volume 46 Issue 2 Pages 546-550
    Published: 1973
    Released: March 27, 2006
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    The effect of solvent on free radical phenylation of arenes was studied by using phenylazotriphenylmethane as the source of phenyl radical. Mixtures of two arenes were phenylated in a solvent (CCl4, CH3CN, DMSO, or cyclohexane), and isomer distributions of diaryls produced were determined. The effect of salts (NaNO2, KNO2, NaClO4) was also studied in DMSO. Both the solvent effect and salt effect suggest the contribution of polar structure in the transition states for the formation of phenylcyclohexadienyl radicals.
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