Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 53 , Issue 11
Showing 1-50 articles out of 77 articles from the selected issue
  • Shozo Furuyama, Osamu Murashita, Yuko Yukumoto, Tetsuo Morimoto
    1980 Volume 53 Issue 11 Pages 3039-3043
    Published: 1980
    Released: April 19, 2006
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    Three kinds of silica–alumina catalysts were prepared by hydrothermal treatment (heating a sample in hot water) over the range of 25–250 °C for various periods. It was found that the hydrothermal treatment significantly increased its catalytic activity for butene isomerization. The dependencies of various surface properties (the production ratio of 2-butene isomers, the surface acidity, the surface area, the pore-size distribution, and the shape and size of the catalyst particle) on the hydrothermal conditions and the kind of starting catalyst sample were systematically investigated, too. It was concluded that the increase in the catalytic activity might be due to the progress of the Si/Al isomorphic substitution in the tetrahedral surface silica network. Hot water might serve as a solvent for the cations and facilitate their movements. Since the hydrothermal treatment can erase the effects of the blending method on the catalytic activity and other surface properties almost completely, this treatment can be used to prepare a standard sample.
  • Kenji Ichimura, Yasunobu Inoue, Iwao Yasumori
    1980 Volume 53 Issue 11 Pages 3044-3049
    Published: 1980
    Released: April 19, 2006
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    Catalysis by a mixed oxide with a perovskite structure, LaCoO3, was studied for the hydrogenolysis of ethylene and ethane at temperatures 300–600 K using the hydrogen-excess mixtures. The high and stable activity was obtained by evacuating LaCoO3 at 600 K. Ethylene hydrogenolysis above 420 K proceeded consecutively via the intermediate, ethane, to produce methane, whereas only the hydrogenation to form ethane occurred below 420 K. Different temperature dependence of the rate was observed, i.e., the activation energy of −19.3 kJ·mol−1 in the range 420–600 K and 33.6 kJ·mol−1 in the range 300–420 K. The mechanistic analysis and tracer study using D2 showed that the slow step of the hydrogenation shifts, with increasing temperature, from the adsorption of hydrogen to the surface reaction between hydrogen atom and ethyl radical. The hydrogenolysis of ethane produced only methane and no ethylene was observed in gas phase; the reaction orders with respect to hydrogen and ethane pressures were, respectively, −0.5 and 1.0. In the reaction with D2, methane [D4] was the main product and an equilibrium among the formed H2, HD, and D2 was quickly established. The adsorption of ethane to undergo the rupture of the carbon-carbon bond and to form monocarbon species was proposed to be a slow step. The catalytic activities of the component oxides, La2O3 and Co2O3, were also examined for a comparison. The structure and electronic states of LaCoO3 were investigated by means of X-ray diffraction and X-ray photoelectron spectroscopy in connection with the catalytic activity. It was proposed that the hydrogenation proceeded mainly on a pair of La3+ and O2− ions, whereas the hydrogenolysis was accelerated by the Co3+ ion; the (110) plane is suggested to be the most favorable for the catalysis.
  • Hisao Yamashita, Yoshihiro Ozawa, Fumito Nakajima, Toshifumi Murata
    1980 Volume 53 Issue 11 Pages 3050-3053
    Published: 1980
    Released: April 19, 2006
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    The adsorption of uranium from sea water with hydrous titanium(IV) oxide(HTO) was studied. HTO was prepared by mixing titanium(IV) chloride and aqueous ammonia at different pHs and temperatures. The fundamental property of HTO was investigated for apparent crystal size, specific surface area, and pore size. The uranium uptake of HTO was found to depend more strongly on the temperature than on the pH in the preparation. HTO prepared at higher temperatures exhibited larger pores and a higher uranium uptake. A kinetic study of the uranium adsorption revealed that the rate of adsorption was controlled by the particle diffusion. The diffusion coefficients were calculated.
  • Haruka Yamada, Keiji Fukumura, Bun-ichi Tamamushi
    1980 Volume 53 Issue 11 Pages 3054-3058
    Published: 1980
    Released: April 19, 2006
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    The Raman spectra of thin films of nematic liquid crystals, MBBA and NP-5A, have been measured for samples sandwiched between two glass (or quartz) plates, which had been pretreated in several ways. The intensities of the fundamental bands of the molecules and the polarization components of each band depend on the molecular orientation structures, such as the homogeneous and homeotropic alignments. The intensity ratio provides a semi-quantitative measure for the molecular orientation, and the Raman results are compared with those from polarizing microscopic observations and infrared spectra. The molecular orientation of the liquid crystals varies with the concentrations of surface-active agents as well as the materials used for the pretreatment of the plates. The molecular interactions, which give rise to the orientation structures, are briefly discussed.
  • Yoshio Sakaguchi, Hisaharu Hayashi, Saburo Nagakura
    1980 Volume 53 Issue 11 Pages 3059-3063
    Published: 1980
    Released: April 19, 2006
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    2,2′-, 2,3′-, and 3,3′-Dimethylbiphenyls were found in the photodecomposition reaction of dibenzoyl peroxide using toluene as solvent. We carried out the experiments to study the external magnetic field, oxygen scavenging, and excitation light intensity effects on their yields. It is concluded that they are produced through the dimerization of (benzoyloxy)methylcyclohexadienyl radicals. This is a new case of the assisted reaction by benzoyloxyl radical. The yields of dimethylbiphenyls were found to be affected remarkably by the small variation of the concentration of benzoyloxyl radical through the three experiments.
  • Akira Kaito, Masahiro Hatano
    1980 Volume 53 Issue 11 Pages 3064-3068
    Published: 1980
    Released: April 19, 2006
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    Calculations of the magnetic circular dichroism(MCD) of methylpurines and methyladenines were carried out not only by the CNDO/S-CI procedure, but also by the INDO/S-CI procedure. The CNDO/S-CI procedure correctly predicted the signs and magnitudes of the MCD spectra of 1-, 3-, and 7-methylpurines and of 9-methyladenine which cannot be improved by the parameter adjustment. On the other hand, the signs of the MCD spectra and transition energies of all these purine derivatives were clearly explained by the INDO/S-CI procedure.
  • Akira Kaito, Masahiro Hatano
    1980 Volume 53 Issue 11 Pages 3069-3072
    Published: 1980
    Released: April 19, 2006
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    The magnetic circular dichroism(MCD) spectra of pyridinols (pyridinones) and pyrimidinols (pyrimidinones) were measured in the wavenumber region of 27000–50000 cm−1. The transition energies, the oscillator strengths, and the Faraday B terms were calculated within the framework of the INDO/S-CI approximation. The calculated results for the π*←π transitions were in good agreement with the experimental results. The lactim-lactam tautomerism of 3-pyridinol(3(1H)-pyridinone) and 2-pyrimidinol (2-pyrimidinone) was discussed.
  • Akita Kaito, Masahiro Hatano, Toru Ueda, Susumu Shibuya
    1980 Volume 53 Issue 11 Pages 3073-3078
    Published: 1980
    Released: April 19, 2006
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    The MCD and absorption spectra of cytosine and isocytosine and their N-substituted derivatives were measured in the wave-number region of 30000–50000 cm−1. On the basis of the experimental results, the tautomerism of cytosine and isocytosine was discussed. The transition energies, the oscillator strengths, and the Faraday B terms of the tautomeric forms of cytosine and isocytosine were calculated within the framework of the intermediate neglect of the differential overlap(INDO) approximation. The calculated results are in good agreement with the experimental data.
  • Kotaro Araya, Yoshio Matsunaga
    1980 Volume 53 Issue 11 Pages 3079-3084
    Published: 1980
    Released: April 19, 2006
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    The formation of solid molecular complexes and the induction of nematic and smectic phases have been demonstrated with a number of binary mixtures of potentially-mesomorphic electron donors and acceptors of the type N-(p-X-benzylidene)-p-Y-aniline. One of the components contains a dimethylamino group as X or Y, and the other a nitro group as X or Y. The remaining substituents are methoxyl, ethoxyl, or propoxyl groups. The maximum temperature of the nematic phase induced in these electron donor-acceptor systems is higher by 23 to 45 °C than the straight line joining the latent transition temperatures of the two components. The tendency to form a solid complex and that to induce a nematic phase are both shown to a large extent by the propoxy derivatives, to a lesser extent by the methoxy derivatives, and least by the ethoxy derivatives. All the solid molecular complexes are reddish brown and exhibit an additional electronic absorption band located at about 500 nm. The mesophases are similarly colored. The enhanced thermal stability of the nematic and smectic phases in these binary mixtures is ascribed to the complex formation by an electron donor-acceptor interaction.
  • Yoshio Matsunaga, Reiko Usui
    1980 Volume 53 Issue 11 Pages 3085-3088
    Published: 1980
    Released: April 19, 2006
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    The combination of o-aminobenzoic acid and picric acid was found to yield four kinds of adducts. These were a stable yellow (1:1) salt, formed by the proton transfer from the picric acid to the o-aminobenzoic acid molecule, two red (1:1) molecular complexes of markedly different stability, and a red (2:1) complex consisting of the o-aminobenzoic acid molecule, its protonated ion, and the picrate ion. The enthalpy change and the activation energy for the isomerization from the salt to the charge-transfer complex by a solid-solid transformation were shown to decrease during storage. The 1,3,5-trinitrobenzene complexes with o-(methylamino)benzoic acid, o-, m-, and p-(dimethylamino)benzoic acids, and their sodium and potassium salts were prepared. Their electronic spectra were measured, along with those of the complexes with o- and p-aminobenzoic acids and their salts presented in the work of Sudborough and Beard. The displacement of the charge-transfer absorption maxima to the lower wavenumber side by the salt formation is 2×103 cm−1 on the average and seems to be consistent with our proposition that the picrate ion acts as an electron acceptor in aromatic amine-picric acid (2:1) complexes.
  • Yoshiyuki Nakamura, Ken-ichi Maruya, Tsutomu Mizoroki
    1980 Volume 53 Issue 11 Pages 3089-3092
    Published: 1980
    Released: April 19, 2006
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    The amine substitution of bromo(o-tolyl)bis(triphenylphosphine)nickel(II) was investigated by the use of 31P- and 13C-NMR. The triphenylphosphine ligands are readily replaced by sterically less crowded amines, such as primary amines, secondary amines, pyridine, and γ-picoline, at room temperature in chlorobenzene, while no replacement at all takes place with tertiary amines. The equilibrium constants with γ-picoline, pyridine, or dibutylamine, as defined by Eq. 2, show that the entropy change contributes predominantly to the constant. The substitution with pyrrolidine, as monitored by means of 13C-NMR, indicates that the amine coordinates to the nickel(II) atom.
  • Nobuatsu Watanabe, Satoshi Koyama
    1980 Volume 53 Issue 11 Pages 3093-3099
    Published: 1980
    Released: April 19, 2006
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    The rate of thermal decomposition of (CF)n prepared under several reaction conditions was measured in a vacuum. The rate was expressed by Avrami-Erofeyev’s equation of second-order for highly oriented sample and of first-order for disordered one. The apparent activation energies of the decomposition reaction were about 50 kcal/mol (1 cal=4.184 J) for the former, and about 14 kcal/mol in higher temperature region and about 100 kcal/mol in lower temperature region for the latter. Thermal decomposition of (CF)n proceeds two-dimensionally around a nucleus of carbon which is formed at the initial stage of decomposition. The rate of thermal decomposition of various samples is dependent on the number of the nucleus forming sites. The nucleation of carbon takes place on a grain boundary between two small crystallites of (CF)n. The rate of the growth of the nucleus is fast along the grain boundary but slow in other directions. The activation energy was estimated to be about 100 kcal/mol for the former and almost 0 kcal/mol for the latter.
  • Nobuatsu Watanabe, Toshihiko Kawamura, Satoshi Koyama
    1980 Volume 53 Issue 11 Pages 3100-3103
    Published: 1980
    Released: April 19, 2006
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    Thermal decomposition of (CF)n was carried out under an oxygen atmosphere. The decomposition temperature was found to be a decisive factor to control the decomposition mechanism and the structure of residual substances. The decomposition reaction proceeded faster in oxygen than in a vacuum at temperatures higher than 588 °C. However, it was reversed below 588 °C. The decomposition mechanism in high temperature region was similar to that in a vacuum. The ESCA spectra of residual substances prepared above 588 °C indicated the presence of carbon atoms which were not bonded with fluorine, namely the nuclei comprised of carbon still remained even in oxygen. The rate of the weight decrease was larger in oxygen than in a vacuum because of the reaction of carbon nuclei, which was formed by thermal decomposition, with oxygen. On the other hand, it considerably decreased below 588 °C, where no nuclei was found for any sample.
  • Noriaki Hirayama, Kunikatsu Shirahata, Yuji Ohashi, Yoshio Sasada
    1980 Volume 53 Issue 11 Pages 3104-3108
    Published: 1980
    Released: April 19, 2006
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    Fortamine dihydrochloride, C8H18N2O4·2HCl, is obtained by the hydrolysis of fortimicin B with hydrochloric acid. The space group is C2 with a=16.109(2), b=10.047(1), c=8.603(1) Å, β=108.69(1)°, and Z=4. The structure was solved by the heavy atom method, and least-squares refinement using 1564 reflexions led to the final R value of 0.030. The ring conformation of fortamine dihydrochloride is an inversed chair form of fortamine. The chair form is significantly compressed to relax the non-bonded interactions between axial substituents.
  • Jiro Tanaka, Masashi Tanaka, Masuo Hayakawa
    1980 Volume 53 Issue 11 Pages 3109-3119
    Published: 1980
    Released: April 19, 2006
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    Reflection spectra of single crystals of 1,1′-diethyl-2,2′-cyanine iodide, bromide and chloride were measured in order to find the origin of the J band. The spectra were obtained by the Kramers-Kronig transformation of reflectivity. The positions of absorption peaks and the shapes of vibronic envelope for each crystalline faces are explained by a calculation of surface exciton splitting with a weak coupling model. The intensity of each bands is interpreted by the oriented gas model, however, a peculiar anomalous band shape characteristic of J band is explained by the charge resonance (CR) and the molecular exciton interaction. The J band is found along particular crystalline direction, in which the dye molecules are stacked face to face, showing importance of interplanar π electron interaction. The molecular exciton band shape is changed significantly to give a J band because the higher vibronic bands are blurred off by the enhanced relaxation mechanism of the CR interaction.
  • Shigetoshi Makio, Nobuaki Kanamaru, Jiro Tanaka
    1980 Volume 53 Issue 11 Pages 3120-3124
    Published: 1980
    Released: April 19, 2006
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    The aggregation of the title dye in a dilute alkaline aqueous solution is investigated at 283–303 K by measuring the electronic absorption spectra. The association number is estimated to be 8, the heat of formation and the entropy change for the association are found as ΔH=−91.5 kcal mol−1 (1 cal=4.184J) and ΔS=−139.3 cal K−1 mol−1, respectively. The structure of the octamer is discussed from a view of spectral shift, intermolecular force and the crystalline structural data. The lifetimes, quantum yields and polarization of fluorescence are investigated on the monomeric and the J-aggregate state of the dye. The energy transfer between several J-aggregate units is indicated in the excited state.
  • Yoshio Fukuda, Toshiro Fukushima
    1980 Volume 53 Issue 11 Pages 3125-3130
    Published: 1980
    Released: April 19, 2006
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    The incorporation of sulfate into anodic film formed on aluminium in an H2SO4–MgSO4 solution was investigated by infrared spectroanalysis using the compensation method. The sulfate content of the film was very small at the initial stage of anodizing, but increased with time to a nearly constant value. This result is explained in terms of the variation of strength of electric field and the mobility of each anion in the barrier layer. The distribution of sulfate across the cell wall also was examined. The sulfate content was relatively small near the wall/solution interface, but increased with the distance across the wall from the surface, reached a maximum value on the intermediate layer between the wall/solution interface and the cell boundary, and decreased gradually. Such distribution is considered to be similar to that across the barrier layer. The SO4 distribution and the transfer of anions from the barrier layer to the porous layer are explained.
  • Masao Itabashi, Koichi Itoh
    1980 Volume 53 Issue 11 Pages 3131-3137
    Published: 1980
    Released: April 19, 2006
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    The pH and pD dependences of the Raman spectra of Cu(II)–L-histidine (1:2) and Cu(II)–L-histidine-d3−5 (1:2) were analyzed based on the pH titration data. Several ring vibrations of the imidazolyl group with cationic, neutral and anionic forms, the out-of-plane bending vibration of the bound carboxylate, and the Cu(II)–N stretching vibrations of the bound amino groups are used to study the chelation structures of the species taken by the solutions. From the results it was concluded that MHA2+, the major species below pH 3, assumes a glycine-like chelation structure with an unbound imidazolium cation. The results also indicate that the species MHA2+, which is prominent in the pH region 4.0–4.5, takes a mixed-type structure, in which one histidine molecule coordinates to Cu(II) as a terdentate ligand and another binds as a substituted glycine. MA2, the major species around pH 7, is determined to have the chelation structure in which two nitrogen atoms of the amino groups and two nitrogen atoms of the imidazole rings are bound to the Cu(II) ion in the square-planar trans position and at least one carboxyl group in the axial position.
  • Hiroshi Terada, Kazuhiko Watanabe, Fujio Kametani
    1980 Volume 53 Issue 11 Pages 3138-3142
    Published: 1980
    Released: April 19, 2006
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    Studies with the probe dye 2-(4-hydroxyphenylazo)benzoic acid, which can detect small conformational differences in serum albumin, showed that the conformation of “heat-resistant” serum albumin (form N′) was not constant, but depended on the heating temperature, becoming similar to that of the denatured monomer as the heating temperature was increased from 55 °C to 70 °C in buffer of pH 7.0. Denatured albumin was suggested to protect native serum albumin from full denaturation. In the presence of denatured albumin, native albumin was found to undergo only a slight conformational change to give the N′ form. This protective effect may explain why a constant amount of serum albumin remains as “heat-resistant” serum albumin even after prolonged heating.
  • Akiko Okumura, Mie Kitani, Yuiko Toyomi, Nobukazu Okazaki
    1980 Volume 53 Issue 11 Pages 3143-3148
    Published: 1980
    Released: April 19, 2006
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    The oxygen-exchange reaction between chromate ions and water has been studied under the following conditions: 25 °C, pH=7–12, [Cr(VI)]=0.075 mol dm−3, I=0.2 and 1 mol dm−3. The rate law of the exchange reaction has been found to be:
    R=k_1[CrO_4^2-]+k_2[HCrO_4^-]+k_3[H^+][HCrO_4^-]+k_4[HCrO_4^-][CrO_4^2-]+k_5[HCrO_4^-]^2.
    The exchange rate has been analyzed in terms of this rate law to obtain the values of k1k5. The presence of the third-order rate term in [Cr(VI)] has been suggested. The activation energy of the overall exchange reaction (I=1 mol dm−3) is (25.5±0.7) kJ/mol at pH 7.4 and (98.9±1.0) kJ/mol at pH 11.0. The salt effect is negative at pH<10.5 and absent at pH>10.5.
  • Osamu Kikuchi
    1980 Volume 53 Issue 11 Pages 3149-3153
    Published: 1980
    Released: April 19, 2006
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    Open-shell restricted SCF and MC-SCF methods with the semi-empirical MINDO/3 approximation have been applied to the Σ and II states of the formyloxyl and formylaminyl radicals. In the MC-SCF formalism, the π→π* singly- and doubly-excited configurations are included. The optimized molecular structures and spin distributions predicted by the SCF and MC-SCF methods are compared. For the II state of formyloxyl, the restricted SCF method gives a distorted Cs structure as the most stable II structure, while the MC-SCF gives a symmetric C2V structure. The use of the MC wavefunctions is recommended for the evaluation of the molecular and electronic structures of these radicals, in which a doublet instability of the restricted SCF solution is expected to occur.
  • Yuriko Nitta, Toshinobu Imanaka, Shiichiro Teranishi
    1980 Volume 53 Issue 11 Pages 3154-3158
    Published: 1980
    Released: April 19, 2006
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    Co–B catalyst has higher selectivity than Ni–B catalyst for the formation of α,β-unsaturated alcohols from α,β-unsaturated aldehydes and lower selectivity for the formation of olefins from acetylenes. The differences between the two catalysts can be ascribed to the differences in the adsorption strength of reactants on Co and Ni metals. The hydrogenation activities of the Co–Ni–B catalysts vary through a maximum, but the selectivities vary monotonously with nickel content. These features are explained in terms of the surface composition measured by XPS and of the surface area of the catalysts. The enrichment of nickel on the surface and the increase of the surface area are observed for the Co–Ni–B catalysts. Co–B catalysts modified by a small amount of metal salts (Fe, Cr, Cu, etc.) are more effective for the selective hydrogenation of α,β-unsaturated aldehydes than co-precipitated binary boride catalysts.
  • Ko-ichi Sugawara, Yo-ichi Ishikawa, Shin Sato
    1980 Volume 53 Issue 11 Pages 3159-3164
    Published: 1980
    Released: April 19, 2006
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    The pulse-radiolysis technique was used for the measurement of the quenching rates of the metastable nitrogen atoms, 2D and 2P, both in nitrogen and in helium. The rate constants obtained for N(2D) were (1.3±0.2)×10−14 cm3 molecule−1 s−1 (1 cm3 molecule−1 s−1=6.022×1017 m3 mol−1 s−1) in nitrogen and (4.6±0.4)×10−17 in helium; these values were larger than those for the higher energy metastable nitrogen atoms, N(2P), (3.3±0.3)×10−17 in nitrogen and (4.2±1.3)×10−18 in helium. The room temperature rate constants of the reactions of these atoms with nitrogen monoxide and with ethylene were also measured. All of these rate constants were found to be of the order of 3×10−11 cm3 molecule−1 s−1. The rate constants of the reactions, N(4S)+NO→N2+O(3P) and O(3P)+NO+M→NO2+M, were also measured and compared with literature values.
  • Kiwamu Yamaoka, Mineo Takatsuki, Kinya Nakata
    1980 Volume 53 Issue 11 Pages 3165-3170
    Published: 1980
    Released: April 19, 2006
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    Visible and UV absorption spectra of two dyes, 9-aminoacridinium (AA) and 10-methylacridinium (MeA) cations, were measured at 25 °C in the presence of three different polyelectrolytes—sodium salts of poly(p-styrenesulfonate) (NaPSS), polyphosphate (NaPP), and polyacrylate (NaPA)—for polymer residue-to-dye ratios from zero to near unity. The optical titration curves of AA-polyanion systems showed a slightly sigmoidal curvature. The method of extended principal component analysis was applied to the experimental spectra of the AA–NaPSS, –NaPP, –NaPA and MeA–NaPSS systems. Only two absorbing component dyes, i.e., bound and unbound, were verified to exist in each system. The equilibrium constant of the binding between dye and polyanion, the pure spectrum of bound dye, and the adjustable parameter α, by which the sigmoidal titration curve is characterized, were determined. In each of the above systems, the bound-dye spectrum behaves in opposition to the common notion of “metachromasy,” showing a bathochromic shift without any new band. The spectra of MeA changed only moderately by the addition of NaPSS. The ultrafiltration of the MeA–NaPP and –NaPA solutions confirmed that most of the MeA cations remain unbound.
  • Hiroyuki Shinohara, Masahiro Kotani
    1980 Volume 53 Issue 11 Pages 3171-3175
    Published: 1980
    Released: April 19, 2006
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    The transfer of singlet energy in p-terphenyl crystal was measured as a function of the dopant (tetracene) concentration and the temperature. The simple hopping model yields a value of 3×10−14 s. This value is believed to be correct within a factor of 5. In the low temperature phase of the crystal, the energy transfer is temperature dependent with an activation energy of 66 cm−1 in undeuterated p-terphenyl and 90 cm−1 in perdeuterated p-terphenyl. It seems probable that in the low temperature phase the freedom of the conformational change of the molecule plays an important role in the energy migration.
  • Yoshihisa Yamamoto, Hideo Sugimoto
    1980 Volume 53 Issue 11 Pages 3176-3179
    Published: 1980
    Released: April 19, 2006
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    Ylide-IIb-group metal (Zn, Cd, Hg) complexes, bis(triphenylphosphonium alkylide)metal dichloride, (Remark: Graphics omitted.) (M: Zn, Cd, Hg), and chloro(triphenylphosphonium isobutylide)metal dichloride, (Remark: Graphics omitted.) (M: Zn, Cd), have been obtained from alkylidenetriphenylphosphoranes, (C6H5)3P=CH–R (R: H, CH3 CH(CH3)2), and ZnCl2, CdCl2, or HgCl2. In these organometallic complexes, the alkylidenetriphenylphosphoranes are attached to the IIb-group metals atom through the carbanionic donor atom. They are thermally stable.
  • Sei’ichiro Iijima, Izumi Motoyama, Hirotoshi Sano
    1980 Volume 53 Issue 11 Pages 3180-3183
    Published: 1980
    Released: April 19, 2006
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    The temperature dependence first observed in the Mössbauer spectrum for mono-oxidized trans-μ-(as-indacene)bis(cyclopentadienyliron) was interpreted in terms of the increase in the rate of intervalence-electron transfer between two irons with an increase in the temperature. The cyclic voltammetric study of trans-μ-(as-indacene)bis(cyclopentadienyliron) indicates that the metal-metal interaction in the monocation of the compound is greater than that in the monocation of biferrocene at room temperature.
  • Akira Nomura, Yazaemon Morita, Yukitoshi Kogure
    1980 Volume 53 Issue 11 Pages 3184-3188
    Published: 1980
    Released: April 19, 2006
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    Pyrolysis of nitrogen compounds with use of steam and FeCl3–Al2O3 catalyst was investigated in detail in order to develop a new method for nitrogen determination. The catalyst was prepared by mixing an aqueous FeCl3 solution and porous active Al2O3 for column chromatography and drying the mixture. A sample solution containing nitrogen was added to the catalyst in a boat and was then covered with an additional catalyst after removal of the solvent, leaving the sample adsorbed on the catalyst. The boat was then inserted into a pyrolysis tube, the sample being pyrolyzed in the presence of steam also used as carrier gas. The nitrogen in the sample converted into ammonia by the pyrolysis reaction was determined by titration after steam distillation under alkaline conditions. The nitrogen compounds except for N–O and N–N bonded compounds were converted quantitatively into ammonia by the pyrolysis under optimum conditions. The reaction was applied to the determination of nitrogen in various compounds.
  • Mamoru Shimoi, Yoshinari Orita, Takashi Uehiro, Itsuro Kita, Toschitak ...
    1980 Volume 53 Issue 11 Pages 3189-3194
    Published: 1980
    Released: April 19, 2006
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    The crystal and molecular structure of the title complex has been determined by X-ray diffraction using 1882 reflections. The crystal was orthorhombic, with the space group Pbn21; a=10.98(2), b=18.496(4), c=7.341(9), Z=4, Dx=1.99, Dm=1.98(2) g cm−3,μ(Mo Kα)=19.3 cm−1, and the final R value was 0.036. A distorted ψ-pentagonal bipyramid is formed around the central antimony(III) atom by two nitrogen and two oxygen atoms, together with a lone electron pair at the equatorial positions and two oxygen atoms at the axial positions. One of the Sb–O distances, 2.78 Å, is longer than the others (2.20(2) Å on the average), and it is determined that the carbonyl oxygen is essentially of the free-acid type and that its carbonyl oxygen is weakly coordinated. The splitting of the νas(COO) band of its infrared and Raman spectra shows the existence of both free and coordinated carboxyl groups. The 1H- and 13C-NMR results show that the antimony(III)–edta complex does not exchange with the free ligand in an aqueous solution at pH 1.5–3.5.
  • Hiroshi Tanigaki, Hitoshi Obata, Tai Tokuyama
    1980 Volume 53 Issue 11 Pages 3195-3197
    Published: 1980
    Released: April 19, 2006
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    A kinetic method of the determination of kojic acid with 2,6-dichlorophenolindophenol(DCIP) is described. The oxidized form of DCIP, reacting with kojic acid, changes to the colorless reduced form of DCIP. By spectrophotometrically measuring the rate of discoloration, the apparent first-order rate constant, kapp, and the second-order rate constant, k, were obtained. The determination of kojic acid in the fermentation medium is possible by using k the constant, even in the presence of various organic substances.
  • Makoto Kimura, Teiichi Suzuki, Yoshiro Ogata
    1980 Volume 53 Issue 11 Pages 3198-3201
    Published: 1980
    Released: April 19, 2006
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    The hypochlorite oxidation of ammonia giving rise to nitrogen evolution was carried out in the dark or under irradiation in order to study the reaction mechanism and application to waste water treatment. UV-irradiation accelerates remarkably the rate of decomposition of unfavorable chloramines. The acceleration covers the pH region 2–12, where corresponding dark reactions are slow. The irradiation also affects the formation of byproducts such as NO2 and NO3, the effect being a slight increase in NO2 formation in the pH range 2–12. These results suggest an effective industrial application to avoid eutrophication in seas and lakes. The irradiation effect is discussed in relation to reaction mechanism, in which the irradiation possibly facilitates the N–N bond formation after chloramine formation.
  • Yutaka Hosokawa, Yoichi Shimura
    1980 Volume 53 Issue 11 Pages 3202-3207
    Published: 1980
    Released: April 19, 2006
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    Penta- and hexa-nuclear condensates of mono(diamine)cobalt(III) complexes and tellurates have been prepared and some of the optically active isomers separated. They are [{Co(TeO6H4)(diamine)}(Te2O10){Co(TeO6H4)(diamine)}]6− (brown complexes) and [{Co(TeO6H4)(diamine)}(TeO6){Co(TeO6H4)(diamine)}]4− (blue complexes), where diamine=ethylenediamine, (R)-(−)-propylenediamine, and (R,R)-(−)-1,2-cyclohexanediamine. The structures have been determined from the visible and ultraviolet absorption and circular dichroism spectra; the electrostatic repulsion between cobalt(III) and tellurium (VI) atoms is considered in detail.
  • Hiroshi Kawaguchi, Makoto Kanekiyo, Tomoharu Ama, Takaji Yasui
    1980 Volume 53 Issue 11 Pages 3208-3213
    Published: 1980
    Released: April 19, 2006
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    The mixed-ligand complexes, Ba[Co(mida)(dipept)]2 (where mida is N-methyliminodiacetate and dipept denotes dianions of glycyl-L-alanine, L-alanylglycine, glycyl-L-leucine, L-leucylglycine, glycyl-β-alanine, β-alanyl-glycine, L-alanyl-β-alanine, and β-alanyl-L-alanine) have been prepared. The structure and properties of these complexes have been characterized by their electronic absorption, CD, and NMR spectral data.
  • Hiro Kuma, Kyoji Motobe, Wasuke Mori, Shoichiro Yamada
    1980 Volume 53 Issue 11 Pages 3214-3217
    Published: 1980
    Released: April 19, 2006
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    Cobalt(II), nickel(II), and copper(II) complexes with 2-furancarbaldehyde oxime have been prepared and characterized mainly on the basis of electronic spectra and magnetic data. The cobalt(II) and nickel(II) complexes of the formula MX2(oxime)4 (X=Cl, Br) have been isolated. They are all six-coordinated, the oxime being coordinated as a unidentate through the nitrogen atom. Copper(II) forms complexes of the formula CuX2(oxime)2 (X=Cl, Br). Possible structures for these complexes are discussed.
  • Hiro Kuma, Shoichiro Yamada
    1980 Volume 53 Issue 11 Pages 3218-3220
    Published: 1980
    Released: April 19, 2006
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    Cobalt(II), nickel(II), cobalt(III), manganese(III), and iron(III) complexes have been synthesized with Schiff bases (abbreviated as X-sal-prpi) derived from N,N′-bis(3-aminopropyl)piperazine and salicylaldehyde derivatives. On the basis of electronic spectra, infrared spectra, and magnetic data, the structures of the metal complexes are discussed. Complexes of the type CoII(X-sal-prpi) are five-coordinated, and MIII(X-sal-prpi)ClO4 consist of six-coordinated [M(X-sal-prpi)]+ and free ClO4 ions, the ligands X-sal-prpi being quinquidentate in the former and sexadentate in the latter.
  • Shigeharu Onozuka, Masayoshi Kojima, Kenjiro Hattori, Fujio Toda
    1980 Volume 53 Issue 11 Pages 3221-3224
    Published: 1980
    Released: April 19, 2006
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    α- and β-Cyclodextrins were tosylated with tosyl chloride in an alkaline solution. The products were confirmed to be monotosylated compounds, and the tosyl group was introduced at the C-3 position of one glucose unit of the cyclodextrin molecule. The 1:1 complex formation of cyclodextrin with tosyl chloride was observed spectrometrically.
  • Hiroshi Suginome, Tsutomu Uchida
    1980 Volume 53 Issue 11 Pages 3225-3231
    Published: 1980
    Released: April 19, 2006
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    Irradiation of hydrazones of benzophenone, 4-methylbenzophenone and 4-methoxybenzophenone in carbon tetrachloride with monochromatic light in the presence of oxygen afforded the corresponding azine, resulting from N–N bond cleavage, as the major product together with the hydrazone hydrochloride. In contrast to the hydrazones, benzophenone acetylhydrazone in carbon tetrachloride in the presence of oxygen afforded an unstable hydroperoxide as the only product, on photolysis with monochromatic light (288±8 nm); this product was transformed spontaneously into benzophenone on evaporation of the solvent at room temperature. 4-Methylbenzophenone acetylhyd razone and 4-methoxybenzophenone acetylhydrazone reacted in a manner similar to benzophenone acetylhydrazone. Irradiation of benzophenone diacetylhydrazone with 266±8 nm light under conditions analogous to the photo-reactions of hydrazones and acetylhydrazones resulted in loss of an acetyl group, resulting in N–CO bond cleavage to afford acetylhydrazone. The mechanism of the photooxygenation of benzophenone acetylhydrazones is interpreted in terms of chlorine radical-induced autoxidation.
  • Masaru Kimura, Kyosuke Satake, Shigeaki Yonemori, Shiro Morosawa
    1980 Volume 53 Issue 11 Pages 3232-3239
    Published: 1980
    Released: April 19, 2006
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    4-Ethoxyindeno[1,2-d]azepine(18) and 10-bromo-4-ethoxyindeno[1,2-d]azepine were prepared by O-ethylation of indeno[1,2-d]azepin-4-ol(12ab) and 10-bromoindeno[1,2-d]azepin-4-ol(13ab) with Et3OBF4 in 62 and 69% yields, respectively. 12ab was obtained by bromination of 1,2,3,4,5,10-hexahydro-4-indeno[1,2-d]azepine(3) or 1,2,3,4-tetrahydroindeno[1,2-d]azepin-4-one with NBS, and subsequent dehydrobromination of the corresponding bromide formed in situ on basic alumina in 10% yield. When the bromination time was over 20 h, only 13ab was isolated in 20% yield. Direct dehydrogenation of 3 with DDQ gave 10-chloroindeno[1,2-d]azepin-4-ol in 27% yield. The NMR and electronic spectra of 18 indicated the presence of a fully conjugated 14-pi ring system in it. We also investigated the possibility for dehydrogenation of 3-ethoxycarbonyl-1,2,3,4,5,5a,10,10a-octahydroindeno [1,2-d] azepin-10-one.
  • Tadatoshi Ota, Seizo Masuda, Masaru Kido
    1980 Volume 53 Issue 11 Pages 3240-3243
    Published: 1980
    Released: April 19, 2006
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    The thermal oligomerization of methacrylaldehyde oxime leads preferentially to two 2,4,7-trimethylperhydroisoxazolo[2,3-a]pyridine-2,7-dicarbaldehyde dioximes, which are comformationally isomeric with each other. The crystal structure of the α-form has been determined by means of X-ray diffraction. It is monoclinic, with the space group P21/a. The cell dimensions are a=7.858(3), b=13.186(6), c=17.259(6) Å, β=130.38(3)°, and Z=4. The molecules are linked by OH···O and OH···N intermolecular hydrogen bonds, with the O···O and O···N distances of 2.794(6) and 2.760(5) Å respectively. Since attempts of the crystallization of the β-form have been unsuccessful, the determination of its chemical structure was attempted by means of 13C-NMR spectroscopy and gas chromatography-mass spectrometry. The β-form is, at any rate, different from the α-form.
  • Atsuyoshi Ohno, Shinro Yasui, Shinzaburo Oka
    1980 Volume 53 Issue 11 Pages 3244-3247
    Published: 1980
    Released: April 19, 2006
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    Reduction of 1-phenyl-2-(2-pyridyl)-1,2-ethanedione with 1-benzyl-1,4-dihydronicotinamide in acetonitrile in the presence of zinc perchlorate has been studied. The α-diketone coordinates onto zinc ion through its pyridine-ring nitrogen and benzene-side carbonyl oxygen, whereas the reduction takes place on pyridine-side carbonyl group. It is concluded that an effective ligand to a metal ion is not necessarily a facile substrate of the reduction.
  • Mikio Nakamura, Michinori Oki
    1980 Volume 53 Issue 11 Pages 3248-3251
    Published: 1980
    Released: April 19, 2006
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    9-(2-Hydroxy-1-naphthyl)fluorene, 9-(2-hydroxy-4,6-dimethylphenyl)fluorene, and their methyl ethers have been prepared. They give stable rotamers, sp and ap, at room temperature, ap forms of the hydroxylic compounds are favored over the sp and contrary is true for the methyl ethers. These results are attributed to the stabilization of the ap form of the hydroxylic compounds due to intramolecular OH···π interaction. Barriers to rotation are ca. 105 kJ mol−1.
  • Masaya Nakata, Yutaka Ikeyama, Hideaki Takao, Mitsuhiro Kinoshita
    1980 Volume 53 Issue 11 Pages 3252-3258
    Published: 1980
    Released: April 19, 2006
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    3,6-Dideoxy-3-C-methyl-2-O-methyl-D-galactopyranose(12) was prepared in 10 steps from methyl 4,6-O-benzylidene-3-deoxy-3-C-methyl-α-D-altropyranoside. 12 was converted into 4,5-di-O-acetyl-3,6-dideoxy-3-C-methyl-2-O-methyl-D-galactose, which was then condenced in ether with (methoxymethylene)triphenylphosphorane (generated from the phosphonium salt with the dimethylsulfinylmethanide anion in ether) to produce 5,6-di-O-acetyl-2,4,7-trideoxy-4-C-methyl-1,3-di-O-methyl-D-galacto-1-enoheptitol (16). The treatment of 16 with NBS in methanol, followed by the debromination of the resulting 2-bromo aldehyde dimethyl acetal with tributylstannane, deacetylation, and mild methanolysis afforded methyl 2,4,7-trideoxy-4-C-methyl-3-O-methyl-β-D-galacto-heptopyranoside(19), which then provided the title compound 20 upon Jones oxidation. The potential intermediates, the 1-lithio-1-(methyl 2,4-dideoxy-4-C-methyl-3-O-methyl-α-L-arabino-pentopyranos-5-yl)ethene and (E)-2-(methyl 2,4-dideoxy-4-C-methyl-3-O-methyl-α-L-arabino-pentopyranos-5-yl)propenylcopper intermediates, were prepared from 20 via the corresponding alkenyl iodide and (methyl 2,4-dideoxy-4-C-methyl-3-O-methyl-α-L-arabino-pentopyranos-5-yl)ethyne and were demonstrated to condense with benzaldehyde and ethylene oxide respectively.
  • Sumio Umezawa, Akihiko Harayama, Yoshio Nishimura
    1980 Volume 53 Issue 11 Pages 3259-3262
    Published: 1980
    Released: April 19, 2006
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    The total synthesis of the pseudo-tetrasaccharides antibiotic neomycin C is described, involving condensation of 6,3′,4′,5″-tetra-O-acetyl-1,3,2′,6′-tetra-N-(benzyloxycarbonyl)ribostamycin with 3,4-di-O-acetyl-2-deoxy-2-(p-methoxybenzylideneamino)-6-O-tosyl-α-D-glucopyranosyl bromide by a modified Koenigs-Knorr reaction.
  • Akira Sugimori, Masaru Matsui, Takeo Akiyama, Masatsugu Kajitani
    1980 Volume 53 Issue 11 Pages 3263-3265
    Published: 1980
    Released: April 19, 2006
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    Similar to ferrocene the UV-irradiation of ruthenocene–polychloromethane–ethanol systems brings about substitution (ethoxycarbonylation for CCl4, formylation for CHCl3, and ethoxymethylation for CH2Cl2) and oxidation. When CHCl3 and CH2Cl2 are used, substitution is dominant. In the irradiation of ruthenocene–CCl4–ethanol system, [Ru(C5H5)2]+[RuCl4] and cyclopentenes substituted by chlorine and trichloromethyl are obtained. The excitation of the CT-complex between ruthenocene and polychloromethane initiates the reaction.
  • Makoto Komiyama, Shohei Inoue
    1980 Volume 53 Issue 11 Pages 3266-3269
    Published: 1980
    Released: April 19, 2006
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    The cleavage of p-nitrophenyl 1-adamantaneacetate was accelerated by β- and γ-cyclodextrins, which was in contrast with their deceleration of the cleavage of a sterically analogous substrate, p-nitrophenyl 1-adamantanecarboxylate. The presence and absence of a methylene group in these substrates absolutely governed the directions of the rate effects of the cyclodextrins. The specificity, explicitly showing that cyclodextrins are quite good models of enzymes, was attributed to the difference of the structures of the inclusion complexes of cyclodextrins with these substrates.
  • Teiji Chihara, Kazunori Tanaka
    1980 Volume 53 Issue 11 Pages 3270-3272
    Published: 1980
    Released: April 19, 2006
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    The rates of hydrogenation of cyclohexanone and its 2-alkyl derivatives have been measured using decalin as the solvent in a temperature range of −5 to 68 °C over Ru/Al2O3, Rh/Al2O3, and Pt/Al2O3 catalysts. As predicted previously, 2-methyl-, 2-ethyl-, and 2-propylcyclohexanone have exhibited nearly identical temperature dependencies in adsorption and hydrogenation, while cyclohexanone and 2-isopropylcyclohexanone had quite different dependencies.
  • Akio Ohsawa, Yoshihito Abe, Hiroshi Igeta
    1980 Volume 53 Issue 11 Pages 3273-3275
    Published: 1980
    Released: April 19, 2006
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    3-(Dialkylamino)indolizines were synthesized in one step by the reaction of 2-bromopyridine, propargyl alcohol, and secondary amines in the presence of Pd(PPh3)2Cl2–CuI as a catalyst. 3-(2-Pyridyl)-2-propyn-1-ol and 3-(2-pyridyl)acrylaldehyde were suggested to be intermediates of the reaction. 3-Dialkylamino derivatives of pyrrolo[1,2-a]quinoline, pyrrolo[2,1-a]isoquinoline, and pyrrolo[1,2-b]pyridazine were obtained from the corresponding α-haloazaaromatics in a similar way.
  • Motoyasu Saito, Tadayoshi Morita, Kahei Takase
    1980 Volume 53 Issue 11 Pages 3276-3278
    Published: 1980
    Released: April 19, 2006
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    The reaction of 2-methylazulene derivatives, such as dimethyl 2-methylazulene-1,3-dicarboxylate, methyl 3-cyano-2-methylazulene-1-carboxylate, and 1-cyano- and 1-carbamoyl-2-methylazulenes, with benzaldehyde in the presence of alkoxide resulted in condensation to give 2-styrylazulene derivatives. 2-Styrylazulene, a parent hydrocarbon, and its p-nitro and p-dimethylamino derivatives were also synthesized.
  • Akira Kawamoto, Hisashi Uda, Nobuyuki Harada
    1980 Volume 53 Issue 11 Pages 3279-3283
    Published: 1980
    Released: April 19, 2006
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    It is shown that acid-catalyzed decomposition of the 1,2-dioxetane derivative, 3,3-dimethyl-7,7-diphenyl-1-2-dioxaspiro[3.5]nona-5,8-diene, obtained from 1-isopropylidene-4,4-diphenyl-2,5-cyclohexadiene, gives 1-methyl-1-(o-terphenyl-4′-yl)ethyl hydroperoxide, bis[1-methyl-1-(o-terphenyl-4′-yl)ethyl] peroxide, 1-(1-hydroperoxy-1-methylethyl)-4,4-diphenylcyclohexa-2,5-dien-1-ol, and o-terphenyl-4′-ol, along with the usual dioxetane-scission product, 4,4-diphenyl-2,5-cyclohexadienone. The distribution and yield of these products depend on acidic agents and/or conditions employed.
  • Takumi Oshima, Toshikazu Nagai
    1980 Volume 53 Issue 11 Pages 3284-3288
    Published: 1980
    Released: April 19, 2006
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    The kinetics and products of the reactions of fifteen meta- and para-substituted diphenyldiazomethanes with chloranil were investigated in tetrahydrofuran. The second-order rate constants, k, increased with the electron-donating ability of the substituents, and the values could be correlated with the Yukawa-Tsuno equation: logkk0=−1.67(σ0+0.66Δ\barσR+)+0.009, (r=0.996). The ρ value, −1.67, indicates the large development of a positive charge at the diazo carbon in the transition state, while the R value, 0.66, confirms the considerable stabilization of the positive charge by the π-electronic contribution of the para substituents. The products of these reactions were the corresponding 2,3,5,6-tetrachlorohydroquinone poly(benzhydryl)ethers, but these polyethers were easily hydrolyzed into the corresponding benzophenones and tetrachlorohydroquinone(HQ). On the other hand, the initial presence of water or methanol as an additive changed the reaction features to give benzophenone or α,α-dimethoxydiphenylmethane, together with HQ. Reaction mechanisms which account for the results are discussed.
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