Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 55 , Issue 10
Showing 1-50 articles out of 72 articles from the selected issue
  • Takao Yamamoto, Tsunenori Nozawa, Nagao Kobayashi, Masahiro Hatano
    1982 Volume 55 Issue 10 Pages 3059-3063
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Temperature variation experiments on near infrared magnetic circular dichroism spectra (700–2000 nm) have demonstrated that metmyoglobin (iron(III) myoglobin) cyanide and metmyoglobin fluoride derivatives which are typical low and high spin iron(III) heme complexes, respectively, exhibit the Faraday C term and the Faraday C and A terms, respectively. The results are consistent with theoretical predictions based on the assignment that the near infrared bands of the iron(III) heme complexes are attributable to the charge-transfer transitions from the occupied a1 and a2 π orbitals to the vacant iron dπ (dxz, dyz) orbitals in a C4v notation.
  • Goro Wada, Eiko Tamura, Mitsuko Okina, Mariko Nakamura
    1982 Volume 55 Issue 10 Pages 3064-3067
    Published: 1982
    Released: June 27, 2006
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    The ratios of the zwitterion form to the uncharged form of glycine, KD=[NH3+CH2COO]/[NH2CH2COOH], were determined in mixtures of water with methanol, ethanol, t-butyl alcohol, dimethyl sulfoxide, acetonitrile, 1,4-dioxane, N,N-dimethylformamide, and tetrahydrofuran. The value of In KD decreases and, therefore, ΔG298° increases, with the increase in the mole fractions of the organic solvents. The plots of ΔG° vs. reciprocal of the dielectric constants of the alcoholic mixtures are simply linear indifferent to the kind of alcohols, indicating that this relation obeys the Scatchard equation and that the free energy change of the process of the intramolecular protonation in glycine is controlled mainly by electrostatic interaction, especially by the entropy change associated with the preferential solvation around the charged amino and carboxyl groups.
  • Akio Okamoto, Katsumi Uchiyama, Itaru Mita
    1982 Volume 55 Issue 10 Pages 3068-3072
    Published: 1982
    Released: June 27, 2006
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    Rections of some fluorescent reagents with substrates, used widely in biochemistry for quantitative analysis of some functional groups in aqueous media, have been studied in organic solutions with a view that they may be used also in the area of synthetic polymer science. Reactions studied by fluorometry were (i) 5-dimethylamino-1-naphthalensulfonyl chloride with butylamine, (ii) 2-naphthalenesulfonyl chloride with butylamine, and (iii) N-(1-naphthyl)maleimide with 1-pentanethiol. In polar solvents all the fluorescent probes studied are too labile and converted spontaneously into fluorescent compounds. In less polar solvents, however, such side reactions do not take place and the reaction of fluorescent reagents with substrates proceeds quantitatively with a simple second-order kinetics. The second-order rate constants for the three reactions are of the order of 10−3 to 10−1 M−1 s−1 in the range of about 30 to 50 °C, and they increase with the solvent polarity.
  • Toshiki Wakabayashi, Katsuko Takaizumi
    1982 Volume 55 Issue 10 Pages 3073-3078
    Published: 1982
    Released: June 27, 2006
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    The shifts (ΔT) in the temperature of maximum density (tmd) of water produced by electrolytes have been revised. It was found that the temperature dependences of Sv and/or by bv coefficients in the Redlich-Meyer equation should be taken into account, to obtain exactly the Despretz constants (KD) or the standard partial molal expansibility (\barE°) from tmd data. The KD’s for 1 : 1 electrolytes were divided into the ionic components (KD,i), by applying the value for \barEi° (H+, 4 °C). Of the familiar monovalent ions, the KD,i values are negative (ΔT>0) only for H+ and Li+ ions and are positive for all the anions examined, including F ion. A further attempt was made to extract from KD,i’s for organic ions the structural part Kst,i’s, based on a model. The Kst,i’s seem to reflect the structure-influencing ability of organic ions, but may not always be the case.
  • Yuji Yoneyama, Keizo Ogino
    1982 Volume 55 Issue 10 Pages 3079-3084
    Published: 1982
    Released: June 27, 2006
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    The behavior of carbon black (CB) in a detergent (sodium dodecyl sulfate (SDS): 20%, zeolite: 20%, sodium silicate: 5%, sodium carbonate: 3%, sodium (carboxylatomethyl)cellulose (CMC): 1%, sodium sulfate: 51%) solution is discussed in terms of the ζ-potential and potential energy of interaction. The ζ-potential of CB in each solution of SDS, various builders, and the detergent was measured by microelectrophoresis. The potential energies between CB and fabrics (nylon and cellulose), between CB and clay, and between CB and zeolite were calculated by the use of the theory of heterocoagulation. The potential energy between one CB particle and another CB particle was calculated by the use of D-L-V-O theory. The ζ-potential was increased by the addition of builders, except sodium sulfate. The high negative ζ-potential of CB in the detergent solution resulted from the effect of builders. From the potential energies, it became evident that 1) CB in the detergent solution deposits with difficulty onto fabrics; 2) The CB coagulates with zeolite only with difficulty; 3) The CB coagulates with clay or CB.
  • Nagamune Nishikido, Tomoyuki Takahara, Hideki Kobayashi, Mitsuru Tanak ...
    1982 Volume 55 Issue 10 Pages 3085-3088
    Published: 1982
    Released: June 27, 2006
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    The surface tensions of the systems of hexa(oxyethylene) dodecyl ether (C12E6) vs. lysozyme (Lyz) or bovine serum albumin (BSA) were measured for constructing the binding isotherms, since the surface tension method is more convenient for the systems of nonionic detergents and proteins than is equilibrium dialysis. The obtained binding isotherms depend on the protein concentration; this effect is much more remarkable for Lyz–C12E6 systems than for BSA–C12E6 ones. The binding isotherms of BSA–C12E6 systems obey the Scatchard equation, and the maximum number and estimated free energy for C12E6 binding to BSA are comparable to those for the system of Triton X-100 and BSA determined by equilibrium dialysis. The agreement suggests that the surface tension method is sound and has advantages over equilibrium dialysis for the estimation of the number of detergent molecules bound to protein. In the systems of Lyz–C12E6, the binding isotherms follow the Freundlich-type equation rather than the Scatchard equation. The remarkable protein concentration dependence of the binding isotherms and this result suggest the occurrence of protein aggregation.
  • Susumu Tsuchiya, Takatoshi Misumi, Noriyuki Ohuye, Hayao Imamura
    1982 Volume 55 Issue 10 Pages 3089-3092
    Published: 1982
    Released: June 27, 2006
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    The isomerization of butenes over KC8 has been investigated. The double-bond-migration and the cis-trans isomerization took place over KC8, but the skeletal isomerization could not be observed. From the rates of reactions and the selectivity ratios, all six of the relative rate constants and the activation energies of reaction were determined. The reaction paths on the triangular graph calculated from the rates constants show the cis-convex-type profile, which suggests one of the catalytic characteristics of KC8.
  • Nobuaki Kanamaru
    1982 Volume 55 Issue 10 Pages 3093-3096
    Published: 1982
    Released: June 27, 2006
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    Radiationless transitions in aromatic molecules in condensed phase are examined for the case where sparse intermediate levels are involved. Effects of surrounding mediums on radiationless transitions are also discussed in which the random fluctuation of the vibrational manifolds in the solvent cages is shown to be important to meet the resonance conditions in the transitions. The theory is applied to explain the “unusually” fast S1-T2-T1 intersystem crossing in the system such as anthracene derivatives.
  • Hitoshi Kuno, Kazuo Kasatani, Masahiro Kawasaki, Hiroyasu Sato
    1982 Volume 55 Issue 10 Pages 3097-3100
    Published: 1982
    Released: June 27, 2006
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    The two-photon fluorescence excitation spectra of 1-azabicyclo[2.2.2]octane (ABCO) and trimethylamine were measured in the excitation wavelength range of 410–520 nm. The effect of the polarization (linear or circular) indicates that the symmetries of the upper states are \ ildeA1A1, \ ildeB1A1, and \ ildeC1E for ABCO while \ ildeA1A1 and \ ildeB1E for trimethylamine in C3v point group approximation. Rotational envelopes for the sequence structures are calculated forcircularly and linearly polarized light excitation and are in good agreement with experiment.
  • Koichiro Miyajima, Masahiro Sawada, Masayuki Nakagaki
    1982 Volume 55 Issue 10 Pages 3101-3103
    Published: 1982
    Released: June 27, 2006
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    Viscosities of aqueous solutions of sodium salts of formic acid, acetic acid, propionic acid, and butyric acid were measured in the concentration range 0.01–0.1 mol dm−3 at 15, 25, and 35°C For formate ion, values of Bst, the increment of viscosity B-coefficient arising from structural change of water, and of (dBiondT), the temperature dependence of ionic B-coefficient, are both nearly zero, indicating that formate ion is neither a structure maker nor a structure breaker. For the alkanoate ions the signs of Bst and (dBiondT) are positive and negative, respectively. From these facts, alkanoate ions may be concluded to be hydrophobic structure making ions.
  • Kumao Hamanoue, Satoshi Hirayama, Masayuki Amano, Kazuo Nakajima, Tosh ...
    1982 Volume 55 Issue 10 Pages 3104-3108
    Published: 1982
    Released: June 27, 2006
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    The acid-base equilibrium of the title compound (BAOH) was studied in various media containing 4% triethylamine (TEA) by volume as a base. As the polarity of solvents increases, the equilibrium shifts toward the base form (BAO) and 100% yield of BAO is achieved in solvents with dielectric constant (ε) greater than 20. The equilibrium is also affected by temperature, favoring the base form at lower temperatures. The associated enthalpy change is estimated to be −14.6 kJ mol−1. Of particular interest is the dominant existence of BAO in poly(methyl methacrylate) (PMMA), since the acid form (BAOH) dominates in a monomeric solvent (MMA). The microscopic effective dielectric constant of PMMA is estimated to correspond to that of a solvent with ε=22–30 by comparing spectral data in PMMA with those in various solvents. No base form is formed in polystyrene, indicating that not only rigidity but also polar groups in PMMA may be responsible for the anomalously large dielectric constant of PMMA.
  • Tsunetaka Sasaki, Takashi Kud\={o}, Ikuko Machida, Satoshi Ishiwata
    1982 Volume 55 Issue 10 Pages 3109-3112
    Published: 1982
    Released: June 27, 2006
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    Macromolecular ion flotation of Fe3+, Cu2+, and Ni2+ ions was studied using macromolecular ions such as sodium metasilicate, sodium polyacrylate, sodium carboxymethylcellulose, sodium alginate, and sodium cyclo-hexaphosphate (SCHP) together with hexadecyltrimethylammonium chloride (HTAC). Diagrams of floatability vs. composition of macromolecular ion and HTAC, and floatability vs. pH at fixed composition of macromolecular ions and HTAC were constructed. Regions of optimum composition and pH for the flotation were determined and tabulated. Maximum floatabilities greater than 95%, some attaining nearly 100%, in the alkaline region were obtained for most of the systems, except for the system Fe3+–SCHP–HTAC which showed its maximum floatability, 91.7%, in the acid region. Metallic ions are considered to be combined as hydroxides with macromolecules which are then floated.
  • Kohsuke Fukushima, Gohsuke Sugihara, Yoshio Murata, Mitsuru Tanaka
    1982 Volume 55 Issue 10 Pages 3113-3115
    Published: 1982
    Released: June 27, 2006
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    The binding isotherms of sodium perfluorooctanoate (SPFO) to lysozyme have been investigated as a function of added NaCl by a potentiometric method utilizing a perfluorooctanoate ion selective electrode. The general feature of the binding of SPFO to lysozyme resembled that of sodium dodecyl sulfate. Although the lysozyme–SPFO system is different in detail from that of lysozyme–sodium dodecyl sulfate system, resulting from the mutual phobicity and the difference in hydrophobicity, the binding mechanism proposed for lysozyme–sodium dodecyl sulfate system can be true also for the binding of SPFO to lysozyme.
  • Hiroyuki Ishida, Ryuichi Ikeda, Daiyu Nakamura
    1982 Volume 55 Issue 10 Pages 3116-3118
    Published: 1982
    Released: June 27, 2006
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    The proton spin-lattice relaxation time T1 at 20 MHz and the second moment of 1H NMR absorptions at 40 MHz were determined at various temperatures between 77 and 300 K for CH3NH3NO3 and CH3NH3SCN, and their partially deuterated analogs, CH3ND3NO3 and CH3ND3SCN. A phase transition was located at 242 K for CH3NH3SCN. The fully protonated compounds yielded two T1 minima, the low- and high-temperature one of which could be attributed to the reorientation of the CH3 and NH3+ groups, respectively, of the cation about the C–N bond axis. The activation energy was evaluated for these motional modes.
  • Masao Nanba, Yasumichi Oishi, Hajimu Wakabayashi
    1982 Volume 55 Issue 10 Pages 3119-3122
    Published: 1982
    Released: June 27, 2006
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    Concentration distributions after interdiffusion at 1200 °C were analysed for the diffusion couple of average composition 16Na2O·12CaO·72SiO2 (wt%) in terms of self-diffusion coefficients of constituent elements. Theoretical calculation was conducted using a multiatomic ion model assuming that Si migrates with oxygens as a silicate ion. The composition of the silicate ion was estimated by determining the parameters in the diffusion equation so as to provide the best fit of the theoretical calculations to the experimental concentration profiles.
  • Akiko Ikekawa, Sohachiro Hayakawa
    1982 Volume 55 Issue 10 Pages 3123-3128
    Published: 1982
    Released: June 27, 2006
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    Amobarbital was ball-milled with methylcellulose (MC), microcrystalline cellulose, or dextran. The analysis of the IR spectra indicated that hydrogen bonds were formed between the C=O groups of amobarbital and the OH groups of the diluents upon ball-milling. It was also shown that formation of the bonds was more predominant with MC than with dextran. After suspensions of various kinds of samples in distilled water had been set aside for a week after the time of preparation, the solid state of the amobarbital remaining undissolved in the suspension was compared with the state before dissolution. There are three kinds of polymorphs for amobarbital: Crystals I, II, and III. Crystal I is given by heating Crystal II (at 150 °C), which has been recrystallized from a 25 v/v% aqueous ethanol solution. Crystal III is given by freeze-drying an aqueous solution. The above comparison suggests that Crystal III and the amorphous part are transformed into Crystal I in the absence of any diluent. It seems that the presence of dextran ball-milled with amobarbital prevents Crystal III from being transformed into Crystal I. The presence of MC ball-milled with amobarbital also seems to prevent both the amorphous part from crystallization and Crystal III from transformation into Crystal I. The solubility of amobarbital in distilled water increased remarkably upon ball-milling with diluents; this was attributed to the stabilization of the amorphous state by the interaction with diluents.
  • Hiroatsu Matsuura, Hiromu Murata
    1982 Volume 55 Issue 10 Pages 3129-3134
    Published: 1982
    Released: June 27, 2006
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    The vibration-rotation infrared spectrum of the Coriolis-interacting band system ν6 and ν3 was measured with a resolution of 0.08 cm−1. The analysis of the spectrum gave values, more precise than before, of the parameters for these bands along with the interaction parameters. A close examination of the observed spectrum revealed a weak Fermi resonance between ν6 and ν48. The parameters determined, in cm−1, include: (ν0)6 1046.659, α6A 0.01550, α6B−0.000443, (ν0)3 1110.46, α3A−0.0078, and α3B 0.00092, where α6B of and α3B af do not involve the contribution of the Coriolis interaction between ν6 and ν3.
  • Yasuhiko Yukawa, Yoshie Inomata, Toshio Takeuchi, Mamoru Shimoi, Akira ...
    1982 Volume 55 Issue 10 Pages 3135-3137
    Published: 1982
    Released: June 27, 2006
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    An X-ray diffraction study of the title complex has been carried out. The crystal is monoclinic, with the space group P21; Z=2; a=8.196(4), b=7.275(3), c=7.740(4) Å, β=103.73(4)° Full-matrix least-squares refinements have led to the final R value of 0.030. The structure consists of one-dimensional polymers bridged by chlorine atoms and a carboxyl group. Four chlorine atoms coordinate to a cadmium atom and form a square plane. The planes extend in the direction of the b axis like an infinite folding screen, sharing opposite edges. From the trough positions in the zigzag structure, the carboxyl oxygen atoms of 4-hydroxy-L-proline coordinate forkedly to two cadmium atoms. The ligand is a zwitter ion in the complex.
  • Yonezo Maeda, Miyako Yamashita, Hiroki Ohshio, Naoto Tsutsumi, Yoshima ...
    1982 Volume 55 Issue 10 Pages 3138-3143
    Published: 1982
    Released: June 27, 2006
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    New intercalated compounds of FeOCl and aniline derivatives were synthesized by soaking FeOCl in ethanol solution containing Lewis base intercalants. Only those Lewis base intercalants whose acid-dissociation constant is greater than 5 intercalate into the lattice of FeOCl. The acid-strength of the solvent is important for the formation of an intercalation compound. The intercalates of iron(III) chloride oxide FeOCl(G)1⁄n have been characterized by elemental analysis, powder pattern of X-ray diffraction, Fe-57 Mössbauer and infrared spectroscopies. The research on expansion of the b-axis of the unit cell and IR data confirm the location of the “guest” molecule within the van der Waals layer or the FeOCl lattice. Effective vibrating mass and lattice temperature derived from the Mossbauer spectra are affected by chemical bonding in the first coordination sphere of the iron atom.
  • Masanobu Saeki, Mitsuko Onoda
    1982 Volume 55 Issue 10 Pages 3144-3146
    Published: 1982
    Released: June 27, 2006
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    The phase relation of the titanium–sulfur system was studied in the range from TiS1.38 through TiS1.96 at 900 °C by the use of the thermobalance method under controlled sulfur pressure. It was found that four phases, (a) Ti2S3 (4H) with a short-range ordering of titanium vacancies, (b) the superstructure of Ti2S3 (4H) due to the ordering of titanium vacancies, (c) Ti2S3 (4H), and (d) TiS2 (2H), exist in this composition range. The Ti5S8 phase of the 12R type reported previously was not detected for any composition.
  • Kunihiro Watanabe, Yoshitaka Imaeda, Ky\={o}z\={o} Kawagaki
    1982 Volume 55 Issue 10 Pages 3147-3150
    Published: 1982
    Released: June 27, 2006
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    The solvent extraction-spectrophotometric determination of lead(II) with bismuthiol II was conducted in the presence of 1,10-phenanthroline(phen). Lead(II) was quantitatively extracted as ternary complexes into the chloroform phase over the pH range of 3.0–7.0. The composition of the extracted ternary complexes were confirmed to be Pb: bismuthiol II: phen= 1 : 2 : 2 or 1 : 2 : 1, depending on the concentration of bismuthiol II added to the aqueous solution. The absorption maximum of the ternary complex (1 : 2 : 2) in chloroform was found to be at 342 nm, with a molar extinction coefficient of 3.5×104 dm3 mol−1 cm−1. Under optimum conditions, the absorbance follows Beer’s law up to 300 μg of lead in 10 ml of chloroform. The coefficient of the variation was 1.3% for 30 μg of lead. Many elements interfered with the determination of lead(II). However, the interfering ions, with the exception of the indium and bismuth ions, were masked with a potassium cyanide solution. The proposed method was then applied to the determination of lead in standard zinc metals. A good agreement was observed between the results obtained by the proposed method and the standard values of the samples.
  • Etsu Yamada, Eiichiro Nakayama, Tooru Kuwamoto, Taitiro Fujinaga
    1982 Volume 55 Issue 10 Pages 3151-3154
    Published: 1982
    Released: June 27, 2006
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    The extraction behavior of zinc and cadmium with diphenylcarbazone(DPC) into benzene and chloroform were studied in both the absence and presence of neutral bases(S). In the case of chloroform, all of the neutral bases gave rise to adduct complexes with the formula of M(DPC)2S. On the other hand, in the case of benzene, the adduct complexes can be represented as M(DPC)2S for all neutral bases except for 1,10-phenanthroline(phen), in which the adduct complexes can be expressed as M(DPC)2(phen)2. The stability of the adduct complexes is related not only to the basicity of the bases, but also to the steric effect attributable to substitution. Furthermore, the adduct-formation constant increase in the following order against the normalized values of basicity: pyridine bases<2,2′-bipyridyl<1,10-phenanthroline derivatives. This order agrees with the increasing order of the coordinated ability as ligands. The basicity of the bases has a larger effect on the adduct-formation constants for Cd than on those for Zn. This may be attributed to the fact that Zn chelates have greater stability than the Cd chelates, as a result, the “residual Lewis acidity” of Zn is smaller than that of Cd, and therefore zinc chelates form less stable adducts.
  • Etsu Yamada, Eiichiro Nakayama, Tooru Kuwamoto, Taitiro Fujinaga
    1982 Volume 55 Issue 10 Pages 3155-3159
    Published: 1982
    Released: June 27, 2006
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    The extraction of zinc and cadmium using chloroform and benzene solutions constaining diphenylcarbazone (DPC=Hdpc), either alone or combined with pyridine(py) or 1,10-phenanthroline(phen), was studied thermodynamically. The formation constants were measured as functions of the temperature in order to ascertain the free energy, enthalpy, and entropy changes. The thermodynamic parameters support a proposed mechanism for the synergism of zinc in which the coordination number of the zinc ion expands with formation of Zn(dpc)2S, where S is pyridine or 1,10-phenanthroline. On the other hand, the thermodynamic values for the synergistic reaction of cadmium support a mechanism in which pyridine or 1,10-phenanthroline replaces the residual waters of hydration in the first coordination sphere of cadmium.
  • Mitsuyoshi Ichihashi, Hisanobu Wakita, Takeharu Mibuchi, Isao Masuda
    1982 Volume 55 Issue 10 Pages 3160-3164
    Published: 1982
    Released: June 27, 2006
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    The solute structure of concentrated aqueous copper(II) bromide solutions was determined by the analysis of the radial distribution curves of X-ray diffraction measured on the solutions with varying concentrations, 4.364–1.016 mol dm−3. The mixed-ligand aquabromocopper(II) complexes were found to be present in these solutions, and to have a distorted octahedral geometry. The Cu2+ ion was coordinated with Br ions at the equatorial sites whose bond lengths were shorter than the axial sites. The interatomic distances of the equatorial Cu–Br and Cu–OH2 bonds were, respectively, 2.42–2.46 and 1.96–1.99 Å, and that of the axial Cu–OH2 bond, 2.37–2.51 Å. The average coordination number of Br ions in the nearest neighbor of the Cu2+ ion increased from 0.33 to 1.31 as the concentration of CuBr2 increased from 1.016 to 4.364 mol dm−3. Even in the 4.364 mol dm−3 solution, which was nearly saturated, the coordination of the Br ion at the axial site was not evidenced. In the 1.474 mol dm−3 CuBr2 solution dissolved in an aqueous 6.923 mol dm−3 HBr solution, the tetrabromocopper(II) complex species was proposed to exist in a flattened tetrahedral form, wherein the Cu–Br distance was 2.41 Å.
  • Naohide Matsumoto, Kenichiro Wakizaka, Akira Ohyoshi
    1982 Volume 55 Issue 10 Pages 3165-3169
    Published: 1982
    Released: June 27, 2006
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    The (tetraazacycloalkadienato)nickel(II) complexes [Ni(Me2[Z]dienatoN4)]+ (Z=13, 14), which have an unsaturated chelate ring containing nucleophilic center, react with electrophilic reagents such as benzoyl chloride. p-methylbenzoyl chloride, and p-nitrobenzoyl chloride to give the substituted derivatives [Ni(Me2E[Z]dienatiN4)PF6. These complexes have been characterized by elemental analyses, 1H NMR, infrared, and electronic spectra. One of the parent complexes [Ni(Me2[14]dienatoN4)]Br·H2O has been subjected to the single-crystal X-ray diffraction technique and its structural data indicated that the average Ni–N bond distance is longer than that of the corresponding thirteen membered complex.
  • Naohide Matsumoto, Masahiko Imaizumi, Akira Ohyoshi
    1982 Volume 55 Issue 10 Pages 3170-3174
    Published: 1982
    Released: June 27, 2006
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    (Tetraazacyclotetradecatetraenato)copper(II) complexes with the general formula [Cu(Me2E2[14]tetraenatoN4)], where E denotes the substituent group of acetyl, propionyl, isobutyryl, benzoyl, p-methylbenzoyl, or p-nitrobenzoyl, have been prepared via electrophilic substitution of the parent complex [cu(Me2[14]tetraenatoN4)] with acid chlorides, and characterized by elemental analyses and infrared spectra. For the p-substituted benzoyl derivatives, both the position of d-d electronic band maxima and reduction potential assignable to Cu2+e→Cu+ vary linearly with the Hammett substituent constants. The crystal structure of one of the complexes [Cu(Me2Acyl2[14]tetraenato)4]·H2O has been determined by the single-crystal X-ray diffraction method. The copper atom assumes a square planar coordination geometry and the overall conformation of the complex assumes a chair-like shape, where the seat and the rests are formed by the coordination plane (CuN4) and the two conjugated six-membered chelate rings respectively.
  • Masao Sugawara, Toyoaki Uchida, Tomihito Kambara
    1982 Volume 55 Issue 10 Pages 3175-3178
    Published: 1982
    Released: June 27, 2006
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    The reduction behavior of cobalt(II) in ammonium citrate and tartrate solutions containing 1-nitroso-2-naphthol was investigated by means of d.c, a.c, normal and differential pulse polarography (n. p. p. and d. p. p.). When cobalt(II) is added to the supporting electrolyte of citrate or tartrate in the presence of the nitrosonaphthol, the reduction potential of 1-nitroso-2-naphthol shifts to a more negative value, the well-defined a. c. and d. p. p. peaks appearing. The drop time-potential curve indicated that adsorption of nitrosonaphthol as well as its reduction product at the mercury surface occurs. The analytical potentiality of the use of nitrosonaphthol for the microdetermination of cobalt(II) is also described.
  • Masamichi Atoh, Isamu Kinoshita, Kazuo Kashiwabara, Junnosuke Fujita
    1982 Volume 55 Issue 10 Pages 3179-3186
    Published: 1982
    Released: June 27, 2006
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    New complexes of the [Co(O–O)(edpp)2]- and [Co(O–O)(en)(dppe)]- type were prepared from trans(Cl, Cl)[CoCl2(edpp)2]ClO4 and trans-[CoCl2(en)(dppe)]ClO4·H2O, respectively, where O–O is an acetylacetonate, malonate, oxalate, or carbonate ion, and en, edpp, and dppe denote ethylenediamine, (2-aminoethyl)diphenylphosphine, and 1,2-bis(diphenylphosphino)ethane, respectively. All the complexes of the former type gave two geometrical isomers of trans(P, P) and trans(P, N) configurations, which were assigned on the basis of the 1H and 3C NMR, and electronic absorption spectra. No trans(N, N) isomers were formed. The yields of the trans(P, N) isomers were always larger than those of the corresponding trans(P, P) isomers. With the decreasing ring members of the O–O chelates, the yield of the trans(P,P) isomer decreases, the trans(P,P)-carbonato complex being formed in trace amounts. The first absorption bands of the trans(P,P) isomers have very strong intensity as compared with those of the corresponding trans(P,N) and the dppe complexes. All the complexes except for [Co(O–O)(en)(dppe)]+ (O–O=malonate and oxalate ions) were resolved by the chemical or SP-Sephadex C-25 column chromatographic method, and the circular dichroism spectra were recorded and compared with those of related complexes.
  • Yoshio Shijo, Tokuo Shimizu, Kaoru Sakai
    1982 Volume 55 Issue 10 Pages 3187-3189
    Published: 1982
    Released: June 27, 2006
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    The extraction equilibria and the fundamental conditions for extracting the titanium(IV)–Pyrocatechol Volet complex anion in a form of an ionic associate with tridodecylethylammonium bromide into carbon tetrachloride is described. The absorption maxima of the extracted complex occurs at 586 nm, the molar absorptivity and the distribution ratio being 5.17×104 dm3 mol−1 cm−1 and 2.82×102. The optimum pH range for the extraction is 5.1–6.4. The composition of the complex is estimated to be Ti(PV)2(R3R′N)2. The extraction constant would be:
    Kex=\frac[Ti(PV)2(R3R′N)2]0[Ti(PV)22−][R3R′N+]2,
    logKex obtained is 13.5. The interference of foreign ions is discussed.
  • Kazuaki Ito, Etsuro Iwamoto, Yuroku Yamamoto
    1982 Volume 55 Issue 10 Pages 3190-3192
    Published: 1982
    Released: June 27, 2006
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    The conductometric study of bis(2,4-pentanedionato)(diamine) cobalt(III) bromides in nitrobenzene at 25 °C indicated that the ion association constant of the chelate salts increases in the order, [Co(acac)2(N,N,N′,N′-tmen)]Br<Bu4NBr<[Co(acac)2(N,N-dmen)]Br<[Co(acac)2(en)]Br<[Co(acac)2(N,N′-dmen)]Br (acac=2,4-pentanedione anion, diamine: en=ethylenediamine, N,N-dmen= N,N-dimethylethylenediamine, N,N′-dmen=N,N′-dimethylethylenediamine, N,N,N′,N′-tmen=N,N,N′,N′-tetramethylethylenediamine). The results were discussed from the view points of hydrogen bonds through the N–H protons of the chelate cations to the bromide anion and cation-solvent interactions.
  • Yuzo Saeki, Ryoko Matsuzaki, Akimasa Yajima, Masayo Akiyama
    1982 Volume 55 Issue 10 Pages 3193-3196
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The reaction products of gaseous TiCl4 with ammonia were TiCl4·5NH3 at 200 °C, TiCl4·5NH3, TiClN, and NH4Cl at 250–400 °C, TiCl4·5NH3, TiClN, TiNx, and NH4Cl at 450–650 °C, TiNx and NH4Cl at 700–1000 °C, and TiNx, NH4Cl, and HCl at 1100–1400 °C. The N/Ti atomic ratio, x, of the TiNx formed was 1.21 at 700 °C, 1.16 at 800 °C, 1.13 at 900 °C, and 1.10 above 1000 °C. The lattice constants of the TiNx formed are shown. The reaction process can be represented as follows: The reaction of gaseous TiCl4 with ammonia occurs first to form TiCl4·5NH3. Above ca. 220 °C, the TiCl4·5NH3 decomposes to TiClN. Above ca. 430 °C, the TiClN reacts with ammonia to form TiNx. Above ca. 1100 °C, in addition to these reactions, the reaction of TiCl2, formed by the reduction of TiCl4 with hydrogen resulting from the thermal dissociation of ammonia, with ammonia occurs to form TiNx. On heating the TiNx, formed by the vapor-phase reaction, at temperatures higher than 500 °C in an argon atmosphere, the value of x decreased and became close to that of the stoichiometric nitride, being 1.02 at 900–1100 °C.
  • Nobuatsu Watanabe, Yoshinori Ashida, Tsuyoshi Nakajima
    1982 Volume 55 Issue 10 Pages 3197-3199
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Graphite fluoride containing more than 60% poly(dicarbon monofluoride) (C2F)n was prepared from petroleum coke heat-treated at 2700 °C at a temperature between 337 and 460 °C. The interlayer spacings and F/C ratios of these graphite fluorides were in the ranges of 0.8–0.74 nm and 0.58–0.68, respectively. The (C2F)n content in graphite fluoride also increased with increasing fluorine pressure.
  • Ryoki Nomura, Masahiro Kimura, Satoshi Teshima, Akira Ninagawa, Haruo ...
    1982 Volume 55 Issue 10 Pages 3200-3203
    Published: 1982
    Released: June 27, 2006
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    In the cycloaddition of carbon dioxide to oxiranes to form cyclic carbonates in the presence of organometallic halides of group IVA, VA, and VIA, catalytic activities of organometallic halides are in the order Sb>Te>Sn>>Bi, Ge, and Si. An improvement of their catalytic activities is achieved by addition of an equimolar amount of Lewis base. In binary catalyst systems, the order of catalytic activities is in the order Sn>Te>Sb>>Bi, Ge, and Si. Organotin halide–base systems show the highest catalytic activity.
  • Hiroto Kidokoro, Masaru Sato, Seiji Ebine
    1982 Volume 55 Issue 10 Pages 3204-3207
    Published: 1982
    Released: June 27, 2006
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    Bromination of 2-methoxybiphenylene derivatives did not give biphenyl derivatives but benzocyclooctene derivatives. 1-Methoxybiphenylene, on the other hand, was brominated to give the benzobicyclo[4.2.0]octadienone derivatives.
  • Ken-ichi Watanabe, Atsushi Imazawa
    1982 Volume 55 Issue 10 Pages 3208-3211
    Published: 1982
    Released: June 27, 2006
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    The cross aldol condensations of aldehydes and ketones catalyzed by Co(II) complexes of pyridine-containing copolymers proceed under neutral conditions in DMF or DMSO to afford α,β-unsaturated ketones without any byproduct. The solid complex catalysts are capable of repeated use. The reactions of aromatic aldehydes and ketones give good results but not those of aliphatic compounds. Effects of substituent groups in chalcone formation are observed. The catalytic reaction features with the polymer-complex catalysts are compared with that with Co(II)–pyridine complex. The polymer-complex-catalyzed aldol condensations are discussed briefly in relation to the enzymatic reaction of Class II aldolase (metalloenzyme).
  • Ken-ichi Watanabe, Ken-ichi Miyazu, Kazuo Irie
    1982 Volume 55 Issue 10 Pages 3212-3215
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Michael-addition reactions have been found to proceed in the presence of the Ni(OAc)2 or Co(OAc)2-2,2′-bipyridine complex in DMF under neutral conditions at room temperature without any by-product. The reactions of chalcone and its derivatives with nitromethane generally gave good results. The effects of metal(II) ions, ligands, counter ions, and solvents on the catalysis were examined, and the features of the metal-complex-catalyzed Michael reactions were studied, with some considerations also being given to the catalysis mechanism.
  • Sanji Hagishita, Kaoru Kuriyama
    1982 Volume 55 Issue 10 Pages 3216-3224
    Published: 1982
    Released: June 27, 2006
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    1,2,3,4,4a,9,9a,10-Octahydroanthracene and tetralin derivatives with known absolute configurations were synthesized to estimate the contribution of a methyl substituent at the third sphere to the Cotton effect induced in the benzenoid transitions. The contributions were estimated from the CD spectra obtained based on the conformation of the skeleton deduced by Force Field Theory and the assumption that the contributions are additive. A large contribution was observed for the 1-quasiequatorial-methyl group in the 1Lb benzenoid transition and for the 2-axial-methyl group in the 1La benzenoid transition. The sign agreed well with the rule proposed by Snatzke except for the contribution of ring B in the 1La benzenoid transition.
  • Eiji Watanabe, Naohiro Imai, Katsuhiko Inomata, Hideki Kinoshita, Hiro ...
    1982 Volume 55 Issue 10 Pages 3225-3228
    Published: 1982
    Released: June 27, 2006
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    It was found that 3-(phenylthio)propanal dimethyl acetal is a very useful starting material for the preparation of 3-acylfuranoterpenes. Syntheses of two naturally-occurring furans, isoegomaketone and ipomeanine were described.
  • Tatsuro Ouchi, Masaya Inaba, Minoru Imoto
    1982 Volume 55 Issue 10 Pages 3229-3231
    Published: 1982
    Released: June 27, 2006
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    We have proposed a concept of hard and soft hydrophobic areas (HA) and monomers. In order to verify such a concept, two series of experiments were carried out. Poly(styrene-alt-disodium maleate) (1) and poly(styrene-altsodium methyl maleate) (2) were used as initiating macromolecules for the copolymerizations of styrene/methyl methacrylate (MMA) and acrylonitrile/MMA. When 1 was used, MMA was more easily polymerized than styrene. Inversely, when 2 was used, styrene was more easily polymerized than MMA. Poly(styrene-co-sodium acrylate) (3) substances with various compositions were used as intiators for the copolymerizations. The produced copolymers of MMA and styrene were found to have a larger content of MMA as the mole ratio of acrylate in 3 became higher. Inversely, the produced copolymers of MMA and acrylonitrile had a larger content of acrylonitrile as the mole ratio of acrylate became higher. Those results could be reasonably explained by the concept of hard and soft hydrophobic areas and monomers.
  • Kiichiro Nakajima, Hitomi Oda, Kenji Okawa
    1982 Volume 55 Issue 10 Pages 3232-3236
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Peptides containing 1-(α-aminoacyl)-2-aziridinecarboxylic acid were isomerized into the corresponding dehydroamino acid peptides by treatment with the tertiary amines, triethylamine or 1,4-diazabicyclo[2.2.2]octane (Dabco). Dehydrohydantoin derivatives were also prepared by treatment of benzyloxycarbonyl-2-aziridinecarboxylic acid derivatives with tertiary amines.
  • Kiichiro Nakajima, Takumi Tanaka, Masahiro Neya, Kenji Okawa
    1982 Volume 55 Issue 10 Pages 3237-3241
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Direct synthesis of peptides containing 1-benzyloxycarbonyl-2-aziridinecarboxylic acid were carried out by the reaction of β-hydroxy-α-amino acid peptides with DEAD–TPP reagents, and key O-peptide intermediates of actinomycin D synthesis were prepared via a ring-opening reaction of the aziridine with N-protected dipeptide. Peptide lactone was prepared by the DCC–HOBt method, and the subsequent debenzyl procedure and oxydation procedure gave the title compounds in good yields.
  • Kimiaki Imafuku, Kyoko Inoue
    1982 Volume 55 Issue 10 Pages 3242-3244
    Published: 1982
    Released: June 27, 2006
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    3-(1-Cyclopentenyl)-, 3-(1-cyclohexenyl)-, and 3-(1-cycloheptenyl)tropolones (3a, 3b, and 3c) were prepared by the hydrolysis of cycloadducts of dichloroketene to cyclopentylidene-, cyclohexylidene-, and cycloheptylidenecyclopentadiene, respectively. Compound 3a was oxidized with performic acid to give 1,2,3,5-tetrahydrocyclohepta[b]cyclopenta[d]furan-5-one and 3-(2-oxocyclopentyl)tropolone. Oxidation of 3b and 3c gave 1,2,3,4-tetrahydro-6H-cyclohepta[b]benzofuran-6-one (4b) and 5,7,8,9,10,11-hexahydrodicyclohepta[b,d]furan-5-one, respectively. Dehydrogenation of 4b with palladium catalyst gave 6H-cyclohepta[b]benzofuran-6-one.
  • Takeo Katsushima, Ryohei Yamaguchi, Mituyosi Kawanisi
    1982 Volume 55 Issue 10 Pages 3245-3247
    Published: 1982
    Released: June 27, 2006
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    Heating a mixture endo, exo- and endo, endo-2,4-dibromohomoadamantanes at 180 °C in hexamethylphosphoric triamide (HMPT) brings about a novel skeletal rearrangement with concomitant dehydrobromination to give tricyclo[5.3.1.04,9]undeca-2,5-diene (5) in 88% yield. Direct photoexcitation of 5 in diethyl ether induces an intramolecular [2+2] cycloaddition to produce 3,5-dehydronoriceane (2). The bicyclo[2.1.0]pentane moiety constrained in the cage structure of 2 shows almost the same 13C–H coupling constants as those of bicyclo[2.1.0]pentane itself. Finally hydrogenation of 2 over PtO2 easily proceeds to afford noriceane, which is named after the structure of iceane.
  • Kuniaki Tatsuta, Yoshiya Amemiya, Yoshinobu Kanemura, Mitsuhiro Kinosh ...
    1982 Volume 55 Issue 10 Pages 3248-3253
    Published: 1982
    Released: June 27, 2006
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    Total synthesis and antibacterial activities of a macrocyclic lactone antibiotic A26771B (1) and all its isomers (2, 3, and 4) are discussed. The starting 8,9,10,12-tetra-O-benzyl-2,3,4,5,11-pentadeoxy-aldehydo-D-xylo-(E)-6-dcdecenose derived from D-glucose reacted with racemic Wittig reagent, (3-hydroxybutyl)triphenylphosphonium iodide to give 1,3,4,5-tetra-O-benzyl-2,8,9,10,11,14,16-heptadeoxy-DL-glycero-L-xylo-hexadeca-6,12-dienitol, which was in turn converted into methyl 15-O-acetyl-6,7,8,9,10,11,12,13,14,16 -decadeoxy-4,5-O-isopropylidene-DL-glycero-L-threo-(E)-2-hexadecenonate (13) through effective oxidation and β-elimination. Saponification followed by Yamaguchi’s lactonization of 13 afforded two diastereomeric 16-membered-ring lactones which were converted into (5S, 15R)-A26771B (1) and its (5S, 15S-diastereomer (2) by successive deacetonation, selective succinylation and oxidation. The other starting 2,3,4,6-tetra-O-benzyl-5-deoxy-aldehydo-D-lyxo-hexose, which was prepared from 2-deoxy-D-glucose, reacted with a Wittig reagent to give 8,9,10,12-tetra-O-benzyl-2,3,4,5,11-pentadeoxy-aldehydo-D-lyxo-6-dodecenose (20) followed by hydrol ysis. Similar reaction sequence from 20 with the aforesaid series for 1 and 2 afforded the (5R, 15R)-isomer (3) and (5R, 15S)-isomer (4).
  • Kuniaki Tatsuta, Satoru Miyashita, Kohji Akimoto, Mitsuhiro Kinoshita
    1982 Volume 55 Issue 10 Pages 3254-3256
    Published: 1982
    Released: June 27, 2006
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    Methyl 2-amino-2N,3O-(o-benzenedisulfonyl)-2-deoxy-α-D-glucopyranoside, which was prepared from methyl 2-amino-2-deoxy-α-D-glucopyranoside and o-benzenedisulfonyl dichloride, was treated with sodium methoxide to afford exclusively a branched-chain amino sugar, methyl 2,3-dideoxy-3-C-formyl-2-(o-sulfobenzenesulfonyl)amino-α-D-xylofuranoside-3′R,5-hemiacetal sodium salt (6). Some derivatives were synthesized from 6.
  • Koichi Komatsu, Ken’ichi Takeuchi, Makoto Arima, Yoshinori Waki, ...
    1982 Volume 55 Issue 10 Pages 3257-3261
    Published: 1982
    Released: June 27, 2006
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    The polysubstituted tropylium ions having cyclopropyl or t-butyl groups at the ring positions with the least steric hindrance, i.e. 1,3- and 1,4-dicyclopropyltropylium, 1,3- and 1,4-di-t-butyltropylium, 1,3,-5-tricyclopropyl- and 1,3,5-tri-t-butyltropylium and 1,2,4,6-tetracyclopropyltropylium ions (4), were synthesized, and their properties were compared with the known monosubstituted and unsubstituted cations. The 1H and 13C NMR spectra for the cyclopropyl derivatives and the 13C NMR spectra for the t-butyl derivatives exhibited a gradual upfield shift for the seven-membered ring signals upon consecutive substitution. Accordingly, for the t-butyl derivatives, the pKR+ values were found to linearly increase upon introduction of each substuent; for the cyclopropyl derivatives, a larger extent of the pKR+ increase was observed with each substitution, and the pKR+ of the tetrasubstituted derivative 4 amounted to 9.10 (50% aq MeCN, 25 °C), the highest value presently known for the hydrocarbon cations having the tropylium unit, although the cumulative substituent effect deviated from the linear additivity correlation as the substituent number increased. The substituent effects upon the reduction potential and the CT transition energy (pyrene as a donor) were also examined and shown to have the same tendency in general.
  • Yoshito Tobe, Tetsuo Yonezawa, Kiyomi Kakiuchi, Yoshinobu Odaira
    1982 Volume 55 Issue 10 Pages 3262-3266
    Published: 1982
    Released: June 27, 2006
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    The acetolysis rates and products of [4.2.2]propellan-7-ylmethyl tosylates were determined in order to clarify the effect of the central and external cyclobutane bonds on the modes of the ring expansion of the cyclobutylmethyl moiety. Since the products obtained from the endo tosylate were the olefin and the acetate having 1,7-tetramethylenenorbornane skeleton, it is deduced that the ring expansion occurs selectively to afford [4.3.2]propellan-7-yl cation which is stabilized by the external cyclobutane bond. In contrast, the exo tosylate gave the products derived from both [4.3.2]propellan-7-yl and -8-yl cations which are subject to the participation of the external and central cyclobutane bonds, respectively.
  • Ryo Saito, Michinori Oki
    1982 Volume 55 Issue 10 Pages 3267-3272
    Published: 1982
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Rotational barrier (apsp) in 9-(2-formyl-1-naphthyl)fluorene was determined: ΔH\ eweq24.0 kcal/mol and ΔS\ eweq−7.9 e.u. Oxidation of the aldehyde with chromium(VI) oxide was extremely slow in the ap form, whereas it proceeded smoothly in the sp form. As models of the 2 steps involved in the aldehyde oxidation, oxime formation of the aldehyde and oxidation of related alcohols were carried out to conclude that the second elimination step in the aldehyde oxidation is slow in the ap form because of the steric effect. Dehydration of the oxime of the aldehyde exhibited a large ksp/kap value as well. Sodium tetrahydridoborate reduction and Grignard additions of the aldehyde were also carried out to show that the former gave a large ksp/kap value whereas the latter exhibited rather a small ksp/kap. The implication of the results is discussed.
  • Ryo Saito, Michinori Oki
    1982 Volume 55 Issue 10 Pages 3273-3276
    Published: 1982
    Released: June 27, 2006
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    Rotational isomers (sp and ap) of several 9-[2-(substituted carbonyl)-1-naphthyl]fluorenes where the substituent is methyl, phenyl, hydroxyl, methoxyl, 1-imidazolyl, or others have been obtained as stable entities. Barriers to rotation in these compounds were ca. 26.5 kcal for the process spap but those for the reverse (apsp) were dependent on the substituent, ranging from 23.8 to 25.3 kcal/mol at 55 °C. The difference is reflected in the populations of rotamers: if the substituent is a hydroxyl, the sp/ap value becomes as large as ca. 20. The relative instability of the ap form was attributed to twisting of the carbonyl plane from that of naphthalene. Infrared spectra support the twisting. Addition reactions to the carbonyl occur smoothly in the sp conformation but they do not occur to a detectable extent in the ap conformation, if the substituent on the carbonyl is larger than hydrogen. The results are attributed to the steric effect of the fluorene ring.
  • Keisuke Suzuki, Akihiko Ikegawa, Teruaki Mukaiyama
    1982 Volume 55 Issue 10 Pages 3277-3282
    Published: 1982
    Released: June 27, 2006
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    Catalytic asymmetric addition of thiols to 2-cycloalkenone was studied by using the chiral amino alcohols, derived from L-hydroxyproline or (S)-proline, as base catalysts. Detailed investigation was carried out on the effects of the structure of the catalyst, the reaction medium, the temperature, and the concentration on the enantioselectivity. Good optical yields (47–88%) were achieved by the reaction of arenethiols and 2-cyclohexen-1-one in toluene at −5 °C, by using the catalyst (2S, 4S)-2-anilinomethyl-1-ethyl-4-hydroxypyrrolidine.
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