Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 10
Showing 1-50 articles out of 94 articles from the selected issue
  • Ryo Hirohashi, Yasushi Hishiki, Masahiro Haruta
    1971 Volume 44 Issue 10 Pages 2573-2577
    Published: 1971
    Released: March 27, 2006
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    Eight polystyrylpyrimidines were synthesized from p-xylylpyrimidine with p-phenylene diisothiocyanate (DIT), terephthaloylchloride (TPC), p-xylylenedibromide (XDB), p-phenylenediamine (PDA), 4,4′-diaminodiphenyl (BD), 4,4’-diamino diphenylsulfone (DPS), hexamethylene diamine (HMD), and 4,4′-diaminodiphenylmethane (DPM). These polymer films have a fairly large photoconductive character; using a surface-type photoconductive cell, the logarithmic relation of the photo-current (Ip) to the applied potential was found to be linear. Further, it was found that the slopes (n) obtained from the logarithmic relation (Ip=kLn) of the photo-current to the light intensity (L) have values from 1.0 to 2.4. The peaks of the spectral response of the photo-current of the eight samples exit around 500–600 mμ and/or near the ultraviolet wavelength region. The photoconduction of these polymers was enhanced by the bridging groups attached to xylylpyrimidine; the enhancement is in the following order;
    (Remark: Graphics omitted.)
  • Toshio Akimoto, Masamichi Tsuboi, Masatsune Kainosho, Fumihide Tamura, ...
    1971 Volume 44 Issue 10 Pages 2577-2582
    Published: 1971
    Released: March 27, 2006
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    Raman spectrum of α-aminobutyric acid has been observed in its 15% aqueous solution (neutral). By comparing it with the Raman and infrared spectra of crystal A (in which 40% of the total molecules are the T-form molecules, 36% Ga-, and 24% Gb-form molecules), crystal B (which consists only of T-form molecules), and a complex crystal of this amino acid with calcium chloride (in which 85% are the Ga-form molecules), it has been shown that the Ga-form molecules are predominant in the aqueous solution. Here, T-, Ga-, and Gb-forms have respectively the amino group, the hydrogen atom, and the carboxy group in the position trans to the methyl group in the internal rotation around the Cα-Cβ bond. Proton magnetic resonance spectrum was observed of a Cγ-deuterated product (CD3CH2CH NH3+COO) in its aqueous solution at several temperatures in the −1.5 to 91°C range. It has been indicated that the Ca-form is more stable by about 300 cal/mole than the other two forms.
  • Takashi Moriyoshi
    1971 Volume 44 Issue 10 Pages 2582-2587
    Published: 1971
    Released: March 27, 2006
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    An apparatus capable of following reaction rates under pressure without sampling has been designed and constructed. The pressure change due to the progress of a reaction in a closed system could be accurately measured to about 0.08 atm by means of a “fixed bridge” combined with a manganin pressure gauge, in which the unbalanced e.m.f. generated at a constant bridge current was potentiometrically determined to 0.1 μV. The rates of the acid-catalyzed inversion of sucrose and the base-catalyzed decomposition of diacetone alcohol, with the expansion in volume and the contraction respectively, were measured in order to verify the applicability of this apparatus. The agreement between the results obtained by this method and those obtained by the analytical method was satisfactory. From these results, it has been confirmed that the method is sufficiently applicable to the measurement of reaction rates under pressure.
  • Hiroshi Kato, Kazuhiro A. Ishida, Hiroshi Nakatsuji, Teijiro Yonezawa
    1971 Volume 44 Issue 10 Pages 2587-2590
    Published: 1971
    Released: March 27, 2006
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    A correlation formula between the chemical shifts of inner-shell electrons and molecular-charge distributions is derived by an MO scheme with CNDO-type approximations. Errors imposed in these schemes are discussed. Reorganization energy terms are briefly discussed in the same level of approximations.
  • Kenji Ishida
    1971 Volume 44 Issue 10 Pages 2591-2595
    Published: 1971
    Released: March 27, 2006
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    Entropy production, originated from an ideal gas second-order reaction taking place in a closed system, has been stochastically formulated by defining the entropy in a form similar to the conditional entropy used in the theory of information. The entropy is introduced in the natural way as a result of the partial factorization of joint probability for reaction states devised for the approximate solution of the stochastic process of the second-order reaction. The entropy production has also been discussed in comparison with the usual one.
  • Isao Mochida, Tetsuji Jitsumatsu, Akio Kato, Tetsuro Seiyama
    1971 Volume 44 Issue 10 Pages 2595-2600
    Published: 1971
    Released: March 27, 2006
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    The oxidative dehydrogenation of cyclohexane over molecular sieves ion-exchanged with cupric ion (Cu(II)–Y) was investigated by means of an ordinary flow reactor with a reactant gas composed of 1.0% cyclohexane, 50% oxygen, and 49% nitrogen. The reaction was studied at temperatures between 210–350°C; here, carbon dioxide and benzene were the main products. The Cu(II)–Y was found to be a very active catalyst for the oxidation of cyclohexane as well as for that of olefins, in comparison with an ordinary cupric oxide catalyst supported on silica gel; the selectivity for benzene formation was as high as 80% below 10% conversion. Both products were found to be formed in competitive reactions. The catalytic activities were also studied on molecular sieves ion-exchanged with other transition metal ions, such as palladium (II), silver (I), and zinc (II). The relations between the catalytic activities and the heats of formation of the corresponding metal oxides per g-atom oxygen were examined; volcano-shaped correlations were observed for both benzene and carbon-dioxide formations for these catalysts. The most active catalyst was Cu(II)–Y for benzene formation, whereas it was Pd (II)–Y for the carbon dioxide formation. The meaning of the correlations was discussed according to Balandin’s explanation, based on thermochemistry, although no satisfying explanation was found. The compensation effects were observed between the activation energies and the frequency factors in these oxidations.
  • D. L. Mathur, G. V. Bakore
    1971 Volume 44 Issue 10 Pages 2600-2602
    Published: 1971
    Released: March 27, 2006
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    The oxidation of s-butyl alcohol by Ce(IV) in dilute nitric acid medium has been studied. The reaction is of first order with respect to Ce(IV)but of fractional order with respect to s-butyl alcohol. A plot of inverse of alcohol concentration against inverse of observed first order rate constant gave a straight line which did not pass through the origin. This suggests an intermediate Ce(IV)-alcohol complex formation. By repeating this procedure at different temperatures the formation constants of the complex and the thermodynamic parameters for the complex formation process have been evaluated. Hydrogen, nitrate, and sulphate ions decrease the rate of oxidation. The results have been explained on the basis of equilibrium Ce4++H2O\oversetKh\ ightleftarrows Ce(OH)3++H+ and assuming Ce(OH)3+ as the reactive species of Ce(IV). From the slope-intercept of straight line obtained between inverse of observed rate constant and [H+], value of Kh=6.19 at 35°C has been evaluated in dilute nitric acid at μ=2.55 M. A mechanism in which the first step is the rapid reversible formation of a complex between Ce(IV) and Substrate followed byα–C–H bond rupture in the rate determining step has been suggested.
  • Takayoshi Kobayashi, Keitaro Yoshihara, Saburo Nagakura
    1971 Volume 44 Issue 10 Pages 2603-2610
    Published: 1971
    Released: March 27, 2006
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    Fluorescence lifetimes and quantum yields were measured for some tetracyanobenzene complexes with benzene and its methyl derivatives, and the radiative and nonradiative rate constants were determined under various conditions. The results show that the low fluorescence intensities of the complexes in nonpolar fluid media are due to small radiative rate constants and that nonradiative processes become important for the complexes in polar fluid media. From the theoretical consideration of the observed radiative transition probability, it is found that the geometry and the charge distribution in the excited equilibrium state are greatly different from those in the excited Franck-Condon state for the complexes in fluid media at room temperature and that the degree of the charge-transfer in the former state amounts to 96–100%, while it is only 12–45% in the latter state. The stabilization energy due to the reorientation was obtained from the temperature dependence of the fluorescence spectrum.
  • Hideo Yamazaki, Kyoji Shinsaka
    1971 Volume 44 Issue 10 Pages 2611-2615
    Published: 1971
    Released: March 27, 2006
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    A mathematical treatment of the electron recombination process is presented on the basis of the extended Smoluchowski equation, which includes the effects of several positive ions as ion cores in a spur and of a scavenger. The equation is reduced to the usual Smoluchowski equation for the geminate recombination in a special case. The time dependence of the electron concentration is obtained using a successive approximation. The results of numerical calculations for various reaction parameters are presented.
  • Hiroshi Hosaka, Takao Fujiwara, Kenjiro Meguro
    1971 Volume 44 Issue 10 Pages 2616-2619
    Published: 1971
    Released: March 27, 2006
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    The electron-donor properties of metal oxides (magnesia, alumina, silica, titania, zinc oxide, and nickel oxide) were investigated by means of TCNQ adsorption. When TCNQ was adsorbed on the surfaces of the metal oxides from its acetonitrile solution, the surfaces of the metal oxides acquired the colorations characteristic of each oxide. The coloration was caused by the formation of TCNQ anion radicals on the metal oxide surfaces. The presence of the TCNQ anion radicals on the colored metal oxide surfaces was confirmed by studying the ESR absorption and electronic spectra. The radicals were formed as a result of electron transfer to TCNQ from the metal oxide surfaces. The order of the radical-forming activity, determined by ESR, was as follows: magnesia>zinc oxide>alumina>titania>silica>nickel oxide. The electron-donor property of the metal oxide surfaces might be dependent on the natures of the semiconductor and the surface hydroxyl ion.
  • Terunobu Wakayama, Tetsuo Miyazaki, Kenji Fueki, Zen-ichiro Kuri
    1971 Volume 44 Issue 10 Pages 2619-2626
    Published: 1971
    Released: March 27, 2006
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    The effect of phase on the hot-hydrogen-atom abstraction reaction with isobutane at 77°K has been studied by electron spin resonance spectroscopy in the photolysis and the radiolysis of solid isobutane containing hydrogen iodide. While only the isobutyl radical is formed by the UV-illumination of isobutane–hydrogen iodide systems in the polycrystalline state, the tertiary butyl radical, accompanied with a small amount of isobutyl radicals, is produced from isobutane-methylcyclohexane-hydrogen iodide systems in the glassy state. The hot hydrogen atom produced by dissociative electron attachment to hydrogen iodide abstracts the tertiary hydrogen atom from isobutane at 77°K, independent of whether the matrix is polycrystalline or glassy. It appears that the H-abstraction reaction from isobutane by hot hydrogen atoms depends upon the energy of the hot hydrogen atoms.
  • Teikichi Sasaki, Shin-ichi Ohno
    1971 Volume 44 Issue 10 Pages 2626-2630
    Published: 1971
    Released: March 27, 2006
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    The yield of trapped electrons produced in ethylene glycol-water glass at 77°K increased linearly with the gamma dose up to 1.5×1020 eV/g, and the G value was estimated to be 2.8±0.2. The relative reaction rates of mobile electrons with various inorganic ions at 77°K were determined by competition kinetics. The observed relative reaction rates with simple inorganic ions corresponded to those of hydrated electrons obtained at room temperature. For complex ions, however, the reactivities of the mobile electrons were larger than those of hydrated electrons. The reaction products, such as bromine dioxide, Cr(V) species, and the pentacyano Co(II) ion, all of which are unstable at room temperature, could be detected by optical and ESR spectroscopies at 77°K.
  • Hitoshi Suzuki, Tsunetaka Sasaki
    1971 Volume 44 Issue 10 Pages 2630-2634
    Published: 1971
    Released: March 27, 2006
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    Gel filtration of an aqueous solution of sodium dodecylsulfate (SDS) was carried out using Sephadex G-50 as a gel column, and the overall elution rate (Rf) of SDS was measured. The value of Rf was found to be independent of the concentration C of SDS below a certain point, above which it increased with increasing C. A sharp break point observed coincided with the critical micelle concentration (CMC) of SDS. The intermicellar concentration of SDS was estimated from the shape of the elution curve for the solutions beyond CMC, and shown independent of the total concentration C. The value of Rf for the micelle was further determined by direct measurement. The value was found to increase slightly with C above CMC, becoming practically constant above about 1.4×10−2 mol/l. It was concluded from the results that the size of the micelle also increase with the concentration above CMC. Theoretical equations were derived for the relation between Rf and C below and above CMC. Observed Rf vs. C relation fitted the equations satisfactorily, from which CMC was calculated. A rapid equilibrium between micelles and monomer ions and the independence of intermicellar concentration on C were also confirmed.
  • Jiro Higuchi
    1971 Volume 44 Issue 10 Pages 2634-2638
    Published: 1971
    Released: March 27, 2006
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    The effect of deviation from the planar structure in electron spin-spin interaction has been semiempirically investigated for spin multiplet ground state of radicals with methylene bonds. If these bonds are not coplanar, a significant influence occasionally appears on the values of D and E, while the influence is very small if the relative orientation among the methylene bonds still does not change.
  • Takeo Oyamada, Takao Iijima, Masao Kimura
    1971 Volume 44 Issue 10 Pages 2638-2642
    Published: 1971
    Released: March 27, 2006
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    The molecular structure of tetramethyllead has been determined by the sector-microphotometer method of gas-phase electron diffraction. The structure parameters determined by a least-squares analysis on molecular intensities are, with estimated limits of error, as follows; rg(Pb–C)=2.238±0.009 Å, rg(Pb–H)=2.72±0.06 Å, rg(C···C)=3.66±0.07 Å, and rg(C–H)=1.08±0.02 Å. The experimental cut-off point was nearly 37 in q value for the 42.0 keV electrons; this was not in sufficient agreement with the theoretical value as calculated from the Thomas-Fermi-Dirac potential for Pb and from the Hartree-Fock potential for C. Moreover, the experimental background showed a significant deviation from its theoretical counterpart in the region of small q values. This discrepancy has not been accounted for even by the use of scattering factors based on a relativistic SCF calculation, or by the correction for the polarization effect available at present.
  • Hideji Fujii, Masao Kimura
    1971 Volume 44 Issue 10 Pages 2643-2647
    Published: 1971
    Released: March 27, 2006
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    The molecular structure of dimethyltin dichloride was determined by the sector-microphotometer method of electron diffraction to be as follows: rg(Sn–Cl)=2.327±0.003 Å, rg(Sn–C)=2.108±0.007 Å, and rg(C–H)=1.113±0.020 Å, and all the valency angles were near 109.5°. In comparison with the Sn–Cl distances in the series of Sn(CH3)4−nCln, as determined previously by the same method, a regular bond contraction in going from Sn(CH3)3Cl to SnCl4, as pointed out previously by Skinner and Sutton, was ascertained.
  • Ryuichiro Ohnishi, Kozo Tanabe
    1971 Volume 44 Issue 10 Pages 2647-2649
    Published: 1971
    Released: March 27, 2006
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    A method of determining the solubility of a solute with a considerable rate of hydrolysis and small solubility in water was devised. The method consists of measurements of the hydrolysis rate below or at saturation solubility, the rate constants and order of reaction, and analysis of kinetic data. The solubility of benzyl chloride in water was found to be 33.1 mg/100 ml at 4.5°C, 49.3 at 20°C, and 55.5 at 30°C. Solubility of benzal chloride and benzotrichloride was calculated to be 25 mg/100 ml at 30°C and 5.3 at 5°C, respectively, by utilizing the kinetic data given in literature
  • Toyoaki Kimura, Kenji Fueki, Zen-ichiro Kuri
    1971 Volume 44 Issue 10 Pages 2650-2652
    Published: 1971
    Released: March 27, 2006
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    The yield of scavengeable electrons produced by γ-irradiation in mixtures of cyclopentane and methylcyclohexane at −196°C has been determined by electron-scavenging experiments with bromobenzene. It has been found that the maximum yield of scavengeable electrons in these mixture glasses increases with an increase in the cyclopentane concentration and that it reaches the total ionization yield in a liquid hydrocarbon. The implication of these results for the yield of radiation-induced ionization in condensed systems is discussed.
  • Yoshiharu Nawata, Yoichi Iitaka
    1971 Volume 44 Issue 10 Pages 2652-2660
    Published: 1971
    Released: March 27, 2006
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    The structure of ascochlorin, C23H29O4Cl, has been determined by the three-dimensional X-ray crystal structure analysis of ascochlorin p-bromobenzenesulfonate. The crystal is orthorhombic, space group P212123, with four molecules in a unit cell of dimensions, a=13.86, b=30.04, and c=6.82 Å. The structure was solved by the heavy atom method and refined by the method of block-matrix least-squares. The final R value was 0.102 for 1627 independent reflexions. Ascochlorin consists of (3-chloro) orcylic aldehyde and (2,3,4-trimethyl) cyclohexanone moieties which are connected with each other through a zigzag chain of trans-(3-methyl)penta(2,4)diene. The cyclohexanone ring takes a typical chair form, and the intramolecular hydrogen bond exists in the orcylic aldehyde residue. The absolute configuration was determined by the anomalous dispersion method.
  • Kenji Mori, Naoto Yamamoto, Hiroshi Tsubomura
    1971 Volume 44 Issue 10 Pages 2661-2665
    Published: 1971
    Released: March 27, 2006
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    Electrochemiluminescence (ECL) of aromatics was studied in dimethylformamide. The solutions were electrolyzed with square-wave voltage at various frequencies. For anthracene, emission from species produced by electrochemical reaction was observed together with anthracene fluorescence. These emissions were quenched when water was added to the solution. For rubrene and perylene, fluorescence from the molecules was observed. For phenanthrene, emission differing from phenanthrene fluorescence was observed at 515 mμ.
  • Yoji Tokuma, Hiroshi Nojima, Yukiyoshi Morimoto
    1971 Volume 44 Issue 10 Pages 2665-2670
    Published: 1971
    Released: March 27, 2006
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    The crystal structure of 3-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)-1-ethyl-2-methllpyrrolidine hydrobromide, C22H26NBr, has been determined. The crystal is monoclinic with space group P21a; the unit-cell dimensions are: a=30.16, b=18.78, c=7.048 Å, β=90.53°. The asymmetric unit contains two molecules. The intensities were estimated visually from the multiple-film equi-inclination Weissenberg photographs. The structure was solved by the heavy atom method. The atomic parameters were refined by the blockdiagonal least-squares method, and final R index was reduced to 0.147. It is concluded that the overall geometry of the two independent molecules is similar in every detail The pyrrolidine ring is puckered. The 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene part consists of three planes. The dihedral angles between the planes are 63° for the benzene planes I and II, 59° for the benzene plane I and the ylidene plane, and 76° for the benzene plane II and the ylidene plane.
  • Yuji Ogata, Kinichi Obi, Hajime Akimoto, Ikuzo Tanaka
    1971 Volume 44 Issue 10 Pages 2671-2676
    Published: 1971
    Released: March 27, 2006
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    The decomposition and the collisional deactivation of energized ethylene formed in the photolyses of ethane, propane, n-butane, and cyclobutane at 1470 Å have been studied from the change in ethylene and acetylene yields with varying pressures of alkane or nitrogen added as a deactivator. The rate constants of the collisional deactivation and decomposition of energized ethylene were determined from the experimental data. The unimolecular decomposition theory has been applied to energized ethylene, and the results compared with the experimental rate constants.
  • Hideaki Chihara, Nobuo Nakamura
    1971 Volume 44 Issue 10 Pages 2676-2681
    Published: 1971
    Released: March 27, 2006
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    35Cl nuclear quadrupole resonance frequencies were measured in electron donor-acceptor complexes between chloranil (tetrachloro-p-benzoquinone) and such donors as aromatic hydrocarbons, polyaromatics and amines. Some correlations between the resonance frequencies and infrared spectra were found and discussed in a qualitative way in terms of the π-electron transfer between donors and the chloranil molecule as acceptor. A Zeeman effect experiment was carried out on a single crystal of the 1:2 chloranil-8-hydroxyquinoline complex. The direction of one of the two non-equivalent C-Cl bonds obtained slightly differs from that determined by an X-ray diffraction study. Possible effects of the charge transfer on the resonance frequency and the asymmetry parameter are discussed according to the Mulliken theory of ’weak’ charge-transfer complex. No simple relations could be found between the experimental resonance frequencies and the ionization potential of the donor. This suggests that crystal field effects are rather large in comparison with the effect of charge transfer interaction.
  • Hideaki Chihara, Yoshikata Koga
    1971 Volume 44 Issue 10 Pages 2681-2684
    Published: 1971
    Released: March 27, 2006
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    A linear retationship was found between the transition temperature of plastic crystals and potential energy barrier hindering molecular rotation determined below or above the transition point, with the slope of the line 7.5 R and 4.1 R, respectively, where R is the gas constant. Consideration of the distribution of molecules between the librational and the rotational states showed that the transition starts to occur cooperatively when the fraction of the rotating molecules reaches a value of 1/60 and concludes with a value of 1/3. The model gives the entropies of transition which reasonably agree with the observed values.
  • Shozo Kubota, Masamoto Iwaizumi, Taro Isobe
    1971 Volume 44 Issue 10 Pages 2684-2688
    Published: 1971
    Released: March 27, 2006
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    The methyl radicals produced on silica-gel surfaces by the photolysis of methyl iodide or methane have been investigated by ESR. When the silica gel is preheated at high temperatures (above ca. 300°C), two methyl radicals which have abnormally small hfs constants are trapped on the surfaces. In the case of the photolysis of methyl iodide, these two radicals disappear by continuing uv-irradiation, and instead an ordinary type of methyl radical is produced. The former two radicals have nearly isotropic g-values, and these values are approximately equal to that of a free electron and are considered to have a non-planar structure. The adsorption sites for these radicals were estimated to be siloxane groups. On the other hand, when the silica gel is preheated at low temperatures (below ca. 300°C) the methyl radicals produced have hfs constants of the same magnitude as that of the ordinary type of methyl radical, but each proton line of the radicals is accompanied by four satellite lines. The outer satellite lines have been confirmed by measurements of the X- and K-band spectra to be a concurrent spin-flip transition of an odd electron and a nearby proton of the silica-gel surface. The models of the adsorption state of the radicals are considered.
  • Kei Utsunomiya
    1971 Volume 44 Issue 10 Pages 2688-2693
    Published: 1971
    Released: March 27, 2006
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    The gas-chromatographic behavior of aluminum(III), gallium(III), and indium(III) chelates with various β-diketones was investigated. The β-diketones studied were acetylacetone and 8 synthesized, alkyl-substituted acetylacetones, benzoylacetone, dibenzoylmethane, trifluoroacetylacetone and its 5 synthesized alkyl derivatives, hexafluoroacetylacetone, benzoyltrifluoroacetone, furoyltrifluoroacetone, and thenoyltrifluoroacetone. The trifluoromethyl group increases the volatility of the chelates, while the aromatic group tends to decrease the volatility. In the alkyl-substituted acetylacetone series, the retention time of the chelates increases with an increase in the molecular weight, but it does not depend upon the volatility. On the other hand, the retention of the chelates containing the trifluoromethyl group is almost inversely correlated with the volatility.
  • Michio Mashima, Kazuo Maruyama
    1971 Volume 44 Issue 10 Pages 2693-2697
    Published: 1971
    Released: March 27, 2006
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    The separation of Al from Fe was attempted as a first step in the chromatographic application of the zone-melting method to metal complexes. N,N′-ethylenedianthranilic acid and benzoic acid complexes, and various organic solid solvents were prepared. The experiment was carried out with a zone speed of 6 cm/hr and a moltenzone length of 0.6–1.0 cm at 75°C. When stearic acid was used as the solvent, the recovery percentage of Al was about 75% with the benzoic acid complex and about 99% with the NN′-ethylenedianthranilic acid complex. Furthermore, the effective distribution coefficient and phase diagram supported due idea of the behavior of the complexes.
  • Kazuo Horikawa, Shinroku Masuyama
    1971 Volume 44 Issue 10 Pages 2697-2702
    Published: 1971
    Released: March 27, 2006
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    The dissociation constants of erythro- and threo-2-methyltartaric and meso- and threo-2,3-dimethyltartaric acids were determined by the potentiometric titration method at the ionic strength of μ=0.1 and at 22°C. The values of the dissociation constants were pK1=3.54 and pK2=5.03 for erythro-2-methyltartaric acid, and pK1=3.28 and pK2=4.70 for the threo-form. For meso-2,3-dimethyltartaric acid, the corresponding values were 3.52 and 4.98, while the threo-form had values of 3.04 and 5.30. The complex formation of copper(II) with these acids has been investigated using Job’s method of continuous variations at the ionic strength of μ=0.2 and at 22°C. Copper-(II) and erythro-2-methyltartaric acid react in a 1 : 1 ratio at pH 2.40 and in a 3 : 2 ratio at pH 5.00. On the other hand, the threo-form does not combine with copper(II) at pH 2.40, though it does react at pH 5.00 in a 1 : 1 ratio. As for meso-2,3-dimethyltartaric acid, the complex formation in a 3 : 2 ratio was observed at pH 5.00. However, the threo-form and copper(II) react in a 1 : 2 ratio at pH 5.00. The equilibrium constants (apparent stability constants) were calculated by the method of Turner and Anderson. The values of the equilibrium constant were log K=9.71 (pH 5.00) and log K=2.02 (pH 2.40) for erythro-2-methyltartaric acid, log K=3.78 (pH 5.00) for the threo-form, log K=9.70 (pH 5.00) for meso-2,3-dimethyltartaric acid, and log K=5.19 (pH 5.00) for the threo- form. On the basis of these data, the structures of these complexes are discussed.
  • Yasutaka Takahashi, Hiroyuki Akahori, Shizuyoshi Sakai, Yoshio Ishii
    1971 Volume 44 Issue 10 Pages 2703-2705
    Published: 1971
    Released: March 27, 2006
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    The substituent constants of the 2- and 1-positions of the π-allylic group of acetylacetonato (a) and cyclopentadienyl (b) derivatives of π-[2-(p-substituted phenyl)allyl]-(I) and π-(p-substituted cinnamyl)-palladium complexes(II) were estimated from their NMR spectra. The differences in the chemical shift (Δν, Hz) between the p-phenylene ring protons H1 and H2 of the complexes was found to be dependent upon the ligand and the substituent X. The plot of Δν against the substituent constant σp+, of X gave a fairly good linear relationship, and from the intercept of the straight line at Δν=0, the substituent constants of the 1-and 2-positions of the π-allylic group in the IIa or IIb complex and the Ia or Ib complex were estimated: σp: at the 1-position, 0.27 (IIa) or 0.24 (IIb), and at the 2-position, 0.21 (Ia) or 0.03 (Ib).
  • Iwao Tsukahara
    1971 Volume 44 Issue 10 Pages 2706-2709
    Published: 1971
    Released: March 27, 2006
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    Using the following solid oxide-electrolyte galvanic cells, Pt/air//ZrO2 (+CaO) O//(in Cu–Ni alloy)/Mo and Pt/air//ZrO2 (+CaO) O//(in Cu–Ag alloy)/Mo, the electromotive forces of the cells have been measured as a function of the oxygen concentration in copper-nickel or -silver alloys at oxygen concentrations ranging from several ppm to 1000 ppm, at 1210°C for copper-nickel alloys and at 1100°C or 1200°C for copper-silver alloys respectively. The activity coefficient of oxygen has been determined from the electromotive force for the alloy systems investigated. In the case of copper-nickel, the activity coefficient of oxygen decreases with an increase in the nickel concentration and also with a decrease in the oxygen concentration. The solubility of oxygen in the copper-nickel alloy has also been measured at 1210°C by the use of the following galvanic cell, Pt/air//ZrO2(+CaO)//O(in Cu–Ni alloy), NiO/Mo.
  • Kenyu Kina, Haruo Miyata, Kyoji Tôei
    1971 Volume 44 Issue 10 Pages 2710-2712
    Published: 1971
    Released: March 27, 2006
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    A new chelating agent, o-phosphonophenylazo-2-hydroxynaphthalene-3,6-disulfonic acid, has been synthesized. The acid dissociation constants of this ligand and the chelate stability constants with alkaline earth metals have been measured by the pH titration method at an ionic strengh of 0.10 and at 25.0±0.1°C. This ligand forms the acido complex, MHL, in the pH 5–7 region. The stability constants of the acido complex decrease in this order: log KSrHL≈logKCaHL>log KMgHL; whereas the decreasing order of the stability constants, logKML, is as follows: log KMgL>log KCaL>log KSrL.
  • Takeshi Katayama, Haruo Miyata, Kyoji Tôei
    1971 Volume 44 Issue 10 Pages 2712-2716
    Published: 1971
    Released: March 27, 2006
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    The acid dissociation constants of phenylazochromotropic acid and its o-substituted derivatives with -CH3, -OCH3, -COCH3, -COOH, -CH2COOH, -COCOOH, -OCH2COOH, and -CH(OH)COOH in the ortho position to the azo group, and the stability constants of their 1 : 1 metal chelates with alkaline earth metals have been measured by potentiometric titation. The measurements have been carried out at 25°C and at μ=0.10 with KNO3. The effects of these substituents on the acid dissociation constants of the reagents and on the stability constants of these chelates were discussed. The pKa value for the naphtholic proton of the o-substituted reagents was larger than that of phenylazochromotropic acid, and the stability constants of these chelates with alkaline earth metals decreased as follows: Mg>Ca>Sr>Ba, while for the chelates of the o-OCH2COOH reagent the order was Ca>Mg>Sr>Ba, and for the o-CH(OH)COOH reagent it was Mg≈Ca>Sr>Ba. The plots of the stability constants, log K1 against the sum of the acid dissociation constants, pKA(=pKa1+pKa2), were approximately linear except for the above two reagents with calcium, strontium, and barium. From the results obtained, the o-OCH2COOH reagent that behaves as a quadridentate ligand forms a more stable chelate with calcium, strontium, and barium, and the effect of the -OCH2COOH group, especially that of the coordination of the -O- atom, is remarkable in its calcium chelate.
  • Osamu Yamaughi, Hiroko Miyata, Akitsugu Nakahara
    1971 Volume 44 Issue 10 Pages 2716-2721
    Published: 1971
    Released: March 27, 2006
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    The aqueous solution equilibria of the systems containing copper(II) ion and glycinamide, β-alaninamide, glycine-N,N-diethylamide, or β-alanine-N,N-diethylamide have been investigated by potentiometric titration at 25°C (μ=0.1 (KNO3)). The stability constants K1 and K2 and the constants of the deprotonation reactions K1H, Kc1, and Kc2, for the glycinamide-copper(II) systems, and K1 and K2 for the other ligand-copper(II) systerrs were calculated by the method of non-linear least-squares with the aid of a computer. The K1 values were found to be in the order, glycine-N,N-diethylamide (6.17)>β-alanine-N,N-diethylamide (5.5)>glycinamide (5.30)>β-alaninamide (5.1). The sequence reveals that the five-membered chelates are more stable than the six-membered ones. The K1 and Kc1 values for glycylglycine and β-alanylglycine have been determined anew, and the structures of the chelates formed in acid solution have been discussed from comparative studies of the equilibrium constants, which suggest a tridentate nature of the dipeptides in the chelates of the type Cu(HL)+ where HL denotes free dipeptide.
  • Keiji Matsumoto, Shun’ichiro Ooi, Hisao Kuroya
    1971 Volume 44 Issue 10 Pages 2721-2724
    Published: 1971
    Released: March 27, 2006
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    The crystal structure of (+)589-[Co(CN)2en2]Cl·H2O has been determined from three-dimensional X-ray photographic data. The crystals are monoclinic, with the lattice constants of a=8.15(1), b=11.69(2), c=6.61(1) Å, and β=107.1(2)°, and with the space group of P21 containing two formula units in the cell. The structure was solved by a conventional Fourier technique and was refined by the least-squares method to an R factor of 0.114. The absolute configuration of the complex ion can be denoted as Λ(λλ); this is in accordance with the assignment made by Mason et al. The complex ion has an approximately two-fold axis, and both of the ethylenediamine chelate rings are of the ob-conformation.
  • Tsunao Araki, Daiyo Terunuma, Tamio Sato, Norio Nagai, Mitsuharu Furui ...
    1971 Volume 44 Issue 10 Pages 2725-2729
    Published: 1971
    Released: March 27, 2006
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    The polymerization of 1,1,3-trimethyl-1-silacyclopentene-3 (I), 1-methyl-, 1-allyl-1,1-diallyl-1-silacyclopentenes and -pentanes with aluminum chloride was carried out. By means of an IR spectroscopic analysis of the resulting polymers, it was established that not only ring opening but also vinyl polymerization due to the C–C double bond occur in this polymerization. Attempts to polymerize I with other catalysts, such as BF3·OEt2, AIBN, KOH, and a Ziegler catalyst, were unsuccessful.
  • Akira Takeda, Satosi Wada, Yasuo Murakami
    1971 Volume 44 Issue 10 Pages 2729-2732
    Published: 1971
    Released: March 27, 2006
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    Electrolysis of 2,2-dichloro-3-phenylcyclopropanecarboxylic acid (1a) in hydroxylic solvents such as methanol and acetic acid, or in aqueous methanol with acetic acid in excess, was carried out with a platinum anode. Solvolysis rather than coupling was found to occur yielding 3,3-dichloro-1-phenylallyl methyl ether (4a) or 3,3-dichloro-1-phenylallyl acetate (5a), or both, depending on the solvent. Electrolysis of 2,2-dichloro-3-methyl-3-phenylcyclopropanecarboxylic acid (1b) in aqueous methanol gave ether 4b. Structural characterization of the products was also discussed.
  • Yoshio Hirabayashi, Nobukatsu Kato, Masateru Mizuta, Hideharu Ishihara
    1971 Volume 44 Issue 10 Pages 2733-2736
    Published: 1971
    Released: March 27, 2006
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    Studies were made of the infrared absorption spectra of methyl esters of oleic, elaidic, linoleic, linoelaidic, trans-10, cis-12-octadecadienoic, α-eleostearic, stearolic, stearic, 9,10-dideutero-oleic, and 9,10-dideutero-elaidic acids in the C–H stretching region. It was further confirmed that the prominent absorption bands at 3020 cm−1 occurring in the infrared absorption spectra of methyl esters of unsaturated higher fatty acids are assignable to the =C–H stretching vibrations of a cis-ethylenic double bond. The =C–D stretching vibrations of deuteroethylenic double bonds (–CD=CD–) in methyl 9,10-dideutero-oleate and -elaidate occurred at 2250 and 2225 cm−1 respectively.
  • Yasuhisa Senda, Sekio Mitsui, Ryuko Ono, Shizuo Hosokawa
    1971 Volume 44 Issue 10 Pages 2737-2741
    Published: 1971
    Released: March 27, 2006
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    Five different 2-substituted cyclopentanones have been reduced by complex aluminum hydrides in various solvents. In the lithium aluminum hydride reduction, the proportion of cis 2-substituted cyclopentanols tends to increase with the steric bulkiness of the substituent. The fact that the composition of the products changes with the sort of solvent is discussed in terms of the difference in the coordinating abilities of the solvents. More cis 2-substituted cyclopentanols are obtained by lithium trimethoxyaluminum hydride than by the other complex aluminum hydrides used in the present study. Lithium tri-t-butoxyaluminum hydride and lithium aluminum hydride-aluminum chloride reduction are also investigated.
  • Kyu-Jang Chong, Tsujiaki Hata
    1971 Volume 44 Issue 10 Pages 2741-2744
    Published: 1971
    Released: March 27, 2006
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    Phosphorylation of alcohols by means of P1,P2-di-p-nitrophenyl pyrophosphate and p-nitrophenyl phosphate was investigated. Alcohols were phosphorylated in almost quantitative yields by use of P1,P2-di-p-nitrophenyl pyrophosphate. It was found that p-nitrophenyl phosphate acts as an effective phosphorylating reagent for alcohols in dry pyridine to give the corresponding alkyl phosphate.
  • Yasuo Abe, Takeshige Nakabayashi, Jitsuo Tsurugi
    1971 Volume 44 Issue 10 Pages 2744-2749
    Published: 1971
    Released: March 27, 2006
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    Pyridinium alkane- and arenethiolsulfonates were allowed to react with arenesulfenyl chlorides, CISAr′, to yield sulfonyl disulfides in which R is n-dodecyl, benzyl, phenyl, or p-tolyl group, and Ar′ o-nitrophenyl or o-nitro-p-chlorophenyl. p-Toluenesulfonyl p-nitrophenyl disulfide was also prepared by this method. IR and UV spectra of these compounds were determined and compared with those of the corresponding thiolsulfonates. Decomposition of 35S-labeled p-toluenesulfonyl p-nitrophenyl disulfide, p-CH3C6H4SO2S35SC6H4NO2-p, gave 35S-labeled p-nitrophenyl p-toluenethiolsulfonate, p-CH3C6H4SO235SC6H4NO2-p. Triphenylphosphine was found to attack two oxygen atoms and a sulfur atom of p-toluenesulfonyl o-nitrophenyl disulfide at the same rate. The reaction of triphenylphosphine with 35S-labeled p-toluenesulfonyl o- and p-nitrophenyl disulfides revealed that the central sulfur atom of these sulfonyl disulfides was desulfurated. This result coincides with that of the decomposition mentioned above. The susceptibility of sulfonyl disulfides containing p-nitrophenyl group to the decomposition and the desulfuration of the central sulfur atom of sulfonyl disulfides in general are also discussed.
  • Otohiko Tsuge, Sumio Iwanami
    1971 Volume 44 Issue 10 Pages 2750-2755
    Published: 1971
    Released: March 27, 2006
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    The reaction of benzoylmethanesulfonyl chloride with cinnamylideneamines in the presence of triethylamine has been investigated; the products were identified, by spectral studies as well as by chemical transformations, as the corresponding Diels-Alder adducts of benzoylsulfene as a dienophile to the α,β-unsaturated anils, 2-substituted 5H, 6H-6-benzoyl-5-phenyl-1,2-thiazine 1,1-dioxides, in which the phenyl and benzoyl groups are quasi-equatorial and quasi-axial respectively. The cycloadducts underwent inversion, on treatment with sodium methoxide in methanol or with silica gel in chloroform, to the corresponding epimers, in which both the phenyl and benzoyl groups are quasi-equatorial.
  • Kazuhiro Maruyama, Heisaburo Shindo, Tetsuo Otsuki, Tetsuo Maruyama
    1971 Volume 44 Issue 10 Pages 2756-2760
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Strongly-enhanced NMR signals were observed in the photo-induced hydrogen abstraction reaction of phenanthraquinone with several hydrogen donors in benzene. Chemically-induced dynamic nuclear polarization was kinetically treated in the photochemical reaction during the course of irradiation by visible light and shut-off. It was found that the relaxation time of the nuclear-spin system under the irradiation is shorter by a factor of 2 to 4 than that in the black-out stage and that the enhancement factor for the methine proton of the 1,2-adduct of phenanthraquinone was evaluated as 1000–2000.
  • Yoshinori Asakawa
    1971 Volume 44 Issue 10 Pages 2761-2766
    Published: 1971
    Released: March 27, 2006
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    Four new flavonoids with an unsubstituted B-ring, alnusin, alnetin, alnustin, and alnustinol, isolated from Alnus sieboldiana were established to be 3,5,7-trihydroxy-6-methoxyflavone (1), 5-hydroxy-6,7,8-trimethoxyflavone (2), 5-hydroxy-3,6,7-trimethoxyflavone (3), and 3,5,7-trihydroxy-6-methoxyflavanone (15) respectively. Some previously-known flavonoids, chrysin (4), izalpinin (5), tectochrysin (6), pinocembrin (16), pinobanksin (17), strobopinin (19) and naringenin (20), and some stilbenes, pinosylvin (24), pinosylvin monomethyl ether (25), and pinosylvin dimethyl ether (26), were identified along with the above new flavonoids.
  • Takashi Matsumoto, Yakudo Tachibana, Junji Uchida, Kenji Fukui
    1971 Volume 44 Issue 10 Pages 2766-2770
    Published: 1971
    Released: March 27, 2006
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    A total synthesis of (±)-taxodione (I) has been achieved. The Friedel and Crafts reaction of 1,2-dimethoxy-3-isopropylbenzene (IV) with succinic anhydride gave β-(4-hydroxy-3-isopropyl-5-methoxybenzoyl)propionic acid (V), which was then converted to γ-(4,5-dimethoxy-3-isopropylphenyl)butyric acid (IX). Since the cyclization of IX gave 6,7-dimethoxy-8-isopropyl-1-tetralone (X), the acid (IX) was subjected to bromination, cyclization, and then debromination. Subsequently, 7,8-dimethoxy-6-isopropyl-1-tetralone (XIII) was converted to (±)-7,8-dimethoxy-6-isopropyl-1-methyl-2-tetralone (XV). The condensation of (±)-XV with the methyl vinyl ketone gave a (±)-hexahydro-2-oxo-phenanthrene derivative (XVI), which was then further converted to (±)-11,12-dimethoxyabieta-5,8,11,13-tetraene (XIX). The introduction of a carbonyl group at the 6 position was achieved by the hydroboration of (±)-XIX, followed by the oxidation of the resulting 6-hydroxyl derivative. Finally, (±)-11,12-dimethoxyabieta-8,11,13-trien-6-one (XXI) was converted to (±)-I, whose IR, UV, and NMR spectra were identical in every respect with those of natural taxodione.
  • Toshikazu Nagai, Yukio Horikawa, Hon Son Ryang, Niichiro Tokura
    1971 Volume 44 Issue 10 Pages 2771-2776
    Published: 1971
    Released: March 27, 2006
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    The chlorinations of propionic acid with chlorine were carried out at 70°C in various solvent mixtures with photo-irradiation or with initiation by benzoyl peroxide. Benzene - CCl4, naphthalene - CCl4, and anthracene -CCl4 mixtures, and sulfur dioxide - CCl4 were used as the solvents. In the benzene - CCl4 mixtures, the relative reactivity, β/α, of the a and the α positions of propionic acid changed from 1.68 (CCl4) to 1.11 (benzene), the ratio being inversely proportional to the electron-donor properties of the solvents. In the naphthalene -CCl4 mixtures, the plot of the relative reactivity, β/α, versus the naphthalene content showed a minimun at ca. 0.1 mol/l of naphthalene; however, the total yield of the chlorinated acids decreased as the content of the naphthalene increased. No chlorinated acids were obtained in the anthracene - CCl4 system. In the presence of sulfur dioxide, the α-position was more readily substituted than the β-position, the β/α ratio decreasing as the molar ratios of C12/SO2 were decreased, from 1.3 (Cl2/SO2=0.286/0.036) to 0.49 (0.286/0.858), by the initiation of benzoyl peroxide. However, dilution with CCl4 or photo-irradiated chlorination cause no change in the selectivity in spite of the presence of sulfur dioxide. A mechanism to account for such a selectivity has been suggested.
  • Tsuneo Imamoto, Seung-Geon Kim, Yuho Tsuno, Yasuhide Yukawa
    1971 Volume 44 Issue 10 Pages 2776-2779
    Published: 1971
    Released: March 27, 2006
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    Kinetic isotope effects in the Hofmann rearrangement of phenyl-1-14C and carbonyl-14C labeled N-chlorobenzamides were measured in a sodium hydroxide solution at 15°C. The observed isotope effect on the phenyl-1-carbon is
    k12k14=1.0456±0.0012
    and that on carbonyl-carbon is
    k12k14=1.0447±0.0006
    These results strongly support a concerted mechanism for this rearrangement. Attempts have been made to correlate the isotope effect on phenyl-1-carbon to the r-value of the linear aromatic substituent-reactivity relationship in related 1,2-rearrangements.
  • Tetsuya Ichikawa, Sadao Maeda, Toshiro Okamoto, Younosuke Araki, Yoshi ...
    1971 Volume 44 Issue 10 Pages 2779-2786
    Published: 1971
    Released: March 27, 2006
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    An investigation of the mechanism of the reaction which involves the base-catalyzed condensation of bis(glycinato)copper(II) with aldehydes was carried out with the purpose of improving it so that it can proceed even with lower molar equivalent ratios of aldehydes to the complex and under milder conditions. On the basis of the results reported in the literature and those of this investigation, the reaction has been carried out as expected and has been newly shown to be applicable to p-tolualdehyde and p-chlorobenzaldehyde, and, moreover, to such aldehydo sugar derivatives as 2,3-O-isopropylidene-D-glyceraldehyde by the use of N-pyruvylideneglycinatocopper(II) complexes in the reaction in place of bis(glycinato)copper(II). An attempt at further improvement will also be described in the present communication.
  • Yasuo Ariyoshi, Naotake Sato
    1971 Volume 44 Issue 10 Pages 2787-2789
    Published: 1971
    Released: March 27, 2006
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    It was found that DL-allothreonine forms scarcely any soluble compounds with 5-nitronaphthalene-1-sulfonic acid, α-naphthylphosphoric acid, chlorendic acid, and tetrachlorophthalic acid in water. DL-Threonine formed soluble or unstable compounds in water with these acids. The synthetic threonine mixture was successfully separated into DL-threonine and DL-allothreonine.
  • Heisaburo Shindo, Kazuhiro Maruyama, Tetsuo Otsuki, Tetsuo Maruyama
    1971 Volume 44 Issue 10 Pages 2789-2794
    Published: 1971
    Released: March 27, 2006
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    Polarized quartet NMR signals due to methylene protons were observed in the hydrogen-abstraction reactions of phenanthraquinone with o-substituted toluenes under the irradiation of light. The relative intensities of these signals could be predicted only by the general treatment of the CKO theory, taking account of the electronic singlettriplet interactions (ST0 and ST1) of the radical pair. The scalar electronic-coupling constants, Je, were evaluated approximately by comparing the theory with the experimental results and were found to be in the order of 7×109 sec−1. The rather large value of Je was discussed in relation to the nature of the reaction system; consequently, the existance of electronic π–π interaction was suggested for the radical-pair intermediate of the reaction.
  • Kazuyoshi Nishiyama, Yuzo Inouye
    1971 Volume 44 Issue 10 Pages 2795-2797
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The solvent polarity-dependence of asymmetric stereochemistry was unambiguously corroborated in the Michael type cyclopropane formation in a system designed so as to proceed through the transition state conformations of an equal dipole moment not involving any geometrical isomerism: the NaH-catalyzed condensation of (−)-menthyl methacrylate with ethyl chloromalonate in solvent media of varying polarity resulted in the formation of (−)-1-methylcyclopropane-1,2,2-tricarboxylic acid having the same sign of rotation in all cases. The fit of the stereochemistry to the Kirkwood equation was borne out by the linearity found for the plots of logRS against the Kirkwood-Onsager parameter. The R-configuration of (−)-1-methylcyclopropane-1,2,2-tricarboxylic acid was established by the correlation to (+)-2,2-diphenyl-1-methylcyclopropanecarboxylic acid of the well-defined (R)-configuration.
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