Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
46 巻 , 6 号
選択された号の論文の88件中1~50を表示しています
  • Kiyoshi Tamura
    1973 年 46 巻 6 号 p. 1581-1585
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    By a new method here proposed, an expression of the relaxation time has been obtained for the formation of the monocomplex of iron (III) with a univalent anionic ligand. The method enables us to express the rate equation in a manner analogous to the second-order reaction, and to calculate the relaxation time with less mathematical labor. The validity of the treatment has been confirmed by applying it to the analysis of the complex formation reaction of iron (III) with m-nitrophenol. The kinetic measurement was performed with the temperature-jump method in an acidic aqueous solution at 25°C and at an ionic strength of 0.10. Over the acidity range studied (0.005≤[H+]≤0.026 M), the complex formation occurs significantly via one path: FeOH2++m-NO2C6H4OH\ ightleftharpoonsm-NO2C6H4OFe2++H2O. The forward and backward rate constants obtained are 5.9×102 M−1s−1 and 1.8×102s−1 respectively. These results have been confirmed by examining the earlier kinetic data on similar reactions.
  • Harumi Endo
    1973 年 46 巻 6 号 p. 1586-1591
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    From the temperature dependency of the adiabatic compressibility in aqueous systems of nonelectrolytes, established by ultrasonic measurements, it is concluded that structural units to be termed “liquid clathrate hydrates” do exist for various systems, the concentration of the zero temperature coefficient of adiabatic compressibility representing the composition-mole-ratio, rcβ(water/solute), for these hydrates. Hydrates with rcβ=7.2⁄3 (for methanol, formamide, and urea) and 17 (for acetone and ethanol) correspond to the solid clathrate hydrates of Structures I and II respectively, while those with rcβ=24, 28, 32, etc, can be explained on the basis of appropriate assumptions.
  • Toshio Ichida
    1973 年 46 巻 6 号 p. 1591-1596
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The thermal decomposition products of SrFeO4 were studied by 57Fe-Mössbauer-effect and X-ray-diffraction measurements. Below 300°C in air, an amorphous Fe3+ product was formed. The Fe4+ or Fe5+ state was not observed in the process. A single-phase product with a perovskite structure was obtained in air at temperatures above 400°C. The products obtained between 400 and 650°C showed cubic symmetry, but above 700°C they showed tetragonal distortion. Two kinds of Fe3+-ion sites were detected in the tetragonal SrFeOx. compounds. All the products obtained under the oxygen pressures from 50 to 500 atm and at temperatures from 300 to 900°C showed cubic symmetry. The Fe3+/Fe4+ ratio in those products was determined from the relative intensities of the Mössbauer absorptions.
  • Masao Sakurai
    1973 年 46 巻 6 号 p. 1596-1602
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The apparent molal volumes, φv, of five series of homologous organic salts of the H(CH2)nCOONa (n=0–6), (CH2)n(COONa)2 (n=0,2,3,4,6,8), H(CH2)nNH3Cl (n=0,2,6), (CH2)n(NH3Cl)2 (n=2,3,6), and H(CH2)n-SO3Na (n=1,2) types in a dilute aqueous solution have been measured by means of a float method as a function of the concentration and the temperature. The coefficients of the deviation of φv from the Debye-Hückel limiting law, bv, are negative for most organic electrolytes. The large positive bv values observed for the sodium oxalate and sodium succinate solutions at 5°C have been attributed to ion-pair formation. The partial molal expansibility of organic ions has been evaluated and interpreted on the basis of the multilayer hydration model proposed by Frank and Wen. The estimation of volume increments per CH2 group suggests that the influences of ammonium ions on the hydrophobic hydration around CH2 groups differ significantly from those of carboxylate ions. The volume change accompanying the substitution of a terminal hydrogen atom with an ionic group has been calculated, and discussed in connection with the overlapping effect of electrostriction in bolaform electrolytes.
  • Takeshi Ohno, Shunji Kato
    1973 年 46 巻 6 号 p. 1602-1609
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Photoreactions of K3[CrIII(NCS)6] and NH4[CrIII(NCS)4(NH3)2] were investigated by means of a flash technique. At low temperature (−87°C), the lowest excited doublet states (2Eg) of the complexes were easily observed on d-d excitation in acetone, the yields decreasing rapidly with rising temperature. In methanol-ethyl–eneglycol-water, 2Eg states of both complexes were easily observed at dry-ice temperature, but not at −46°C. Thus, the lowest excited quartet state (4T2g), the precursor of 2Eg state, should rapidly undergo photolysis at room temperature before being converted into the 2Eg state. The rate of thermal degradation of 4T2g state including chemical reactions was calculated to be ca. 1010 s−1 at room temperature. The decay rate of 2Eg state was estimated to be ca. 105 s−1 at room temperature. In the presence of organic compounds having carbonyl group, a strong and sharp absorption band near the UV region was observed at room temperature. Irradiation of UV light produced (NGS)2− radical for both complexes.
  • Gunzi Saito, Yoshio Matsunaga
    1973 年 46 巻 6 号 p. 1609-1616
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The 3,3′,5,5′-tetranitrobiphenyl-4,4′-diol complexes with twenty-eight aromatic monoamines were prepared and characterized on the basis of their compositions and vibrational and electronic spectra. Many amines were found to form yellow-colored complexes with a 1 : 1 composition and orange- or red-colored complexes with a mole ratio of 2 : 1 or higher. The former complexes appeared to be salts formed by means of the proton-transfer from the diol to the amine molecule, while the latter appeared to be complexes of a new type where charge-transfer and proton-transfer interactions simultaneously operate. The deep coloration of the latter complexes was interpreted in terms of a charge-transfer interaction between the anion derived from the diol and the second monoamine molecule. Furthermore, the complexes with ten aromatic diamines were examined. The 1 : 1 o-dianisidine complex was of particular interest in that it is either of the charge-transfer type or of the proton-transfer type, depending upon the preparative conditions.
  • Yasuo Fukuda, Kozo Tanabe
    1973 年 46 巻 6 号 p. 1616-1619
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The infrared absorption spectra of CO2 adsorbed on MgO and GaO were measured in the wide region 700–4000 cm−1 at various amounts of adsorbed CO2 and temperatures of adsorption and desorption. It has been found that both uni- and bidentate carbonates are formed on MgO when a small amount of CO2 is adsorbed and that unidentate carbonates predominate as the amount of adsorbed CO2 is increased. On the other hand, only unidentate species were formed on CaO at room temperature independently of the amount of adsorbed CO2, but bidentate species were also formed on CaO when the temperature of adsorption was high. The unidentate carbonates formed on both MgO and CaO at room temperature partially changed to bidentate carbonates upon evacuation at higher temperatures. The correlation between Δv=|v1v5| and the partial charge on oxygen atoms of various oxides, which corresponds to basic strength on the surface, was examined.
  • Takayuki Yano
    1973 年 46 巻 6 号 p. 1619-1623
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The pyrolysis of diluted mixture of equimolar CH4 and CD4 were performed in a shock tube between ∼1500 K and ∼1600 K, and pyrolysis products were quantitatively determined. A small amount of oxygen contaminating the sample gases had no influence on the results. The isotope exchange reactions in the equimolar lean mixture of H2 and D2 were also performed under the same conditions of methane pyrolysis. The results explained that the isotope exchange reaction between H2 and D2 had no influence on the hydrogen isotopic distribution produced by the CH4-CD4 pyrolysis. From the hydrogen isotopic distribution of the products of CH4-CD4 pyrolysis, methyl radical mechanism was confirmed as the initiation step of methane pyrolysis.
  • Masayuki Katsumoto, Kazuo Fueki, Takashi Mukaibo
    1973 年 46 巻 6 号 p. 1624-1627
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The isotopic exchange between H2S and D2 has been studied in the temperature range from 480°C to 551°C on a pyrrhotite specimen. The isotopic exchange reaction proceeded via these steps:
    H2S+D2=D2S+H2
    H2+D2=2HD
    From the analysis of the kinetic data, the rate constant of the sulfurization of Fe1−XS by “hydrogen sulflde,” ki, and that of reduction by “hydrogen,” ki′, were determined. It was found that ki is inversely proportional to the sulfur activity of Fe1−XS, as, and that ki′ is independent of it. It was found that the rate equation for the sulfurization of Fe1−XS in the “hydrogen”-“hydrogen sulfide” gas mixture could be expressed in the form of v=kP“H2S”aS−1kP“H2. A possible mechanism of the reaction at the surface of Fe1−XS is discussed.
  • Toshio Nagatani, Kenji Yoshihara, Takanobu Shiokawa
    1973 年 46 巻 6 号 p. 1628-1631
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The behavior of the excited ions produced by positive ion impact in methylamine has been studied in the reaction chamber of a double mass spectrometer at elevated pressure. The ion-molecule reactions have been discussed for three energy regions. Metastable transitions taking place in the reaction chamber and in the Giese lens have also been studied in the corresponding regions.
  • Toru Iwaki
    1973 年 46 巻 6 号 p. 1631-1638
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The surface properties of rutile single crystals were studied by the measurement of the d.c. electrical conductivity. Upon successive thermal treatments in vacuo from 25 to 550°C, the electrical conductivity on the (110) plane increased remarkable, while the activation energy decreased. The addition of oxygen decreased the conductivity according to the oxidation temperature, whereas the reduction by hydrogen above 300°C increased the conductivity greatly. The number of carriers was also determined from the measurement of the Hall effect. These results, by reference to those of the photoconductivity, were interpreted in terms of the change in the energy band structure near the surface associated with the defect centers on the surface.
  • Masuo Aizawa, Shuichi Suzuki, Teruo Suzuki, Hiroshi Toyama
    1973 年 46 巻 6 号 p. 1638-1640
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The relationship between the rheological properties and the states of water in macromolecular gels is investigated by both the rheological and nuclear magnetic resonance methods. In accordance with the stress-strain curve, macromolecular gels are shown to be classifiable into: (1) an agarose type of gel which shows great gel strength and brittleness at breaking; (2) a κ-carrageenan type of gel showing great gel strength, but ductility at breaking, and (3) a λ-carrageenan type of gel, which has very little gel strength and is pasty. The dependence of the NMR line-width of water in gels on the polymer concentration and on the temperature reveals that the motional state of water in gels is restricted in this order: the agarose type of gel>the κ-carrageenan type of gel>the λ-carrageenan type of gel. These results show that the state of water is closely related with the rheological properties of macromolecular gels.
  • Yasuhisa Sano, Shin Sato
    1973 年 46 巻 6 号 p. 1641-1645
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The photolysis of hydrogen iodide at 2288 Å has been investigated in the presence of ethylene or propylene. The combinations studied were DI-C2H4, HI-C2D4, and DI-C3H6. In all combinations, the formation of a large amount of HD was observed; this may be attributed to the reaction of hot hydrogen atoms. The pressure dependence of the relative yields of HD and total hydrogen suggested that, of the two possible hot hydrogen atom reactions with ethylene, the abstraction reaction,
    D*+C2H4→C2H3+HD (2)
    does not occur, while the substitution reaction,
    D*+C2H4→C2H3D+H (3)
    is the important process. In the case of propylene, however, the abstraction of H by D* is important for the formation of HD. The measured ratios of C2H3D/HD in the DI–C2H4 system and of C2D3H/HD in the HI–C2D4 system were consistent with the above conclusion. Reaction (3) is probably not a real substitution reaction, but a combination of the addition reaction of a hydrogen atom to ethylene and the rapid decomposition of the excited ethyl radical produced.
  • Yoshio Taniguchi, Yasuzo Nishina, Noboru Mataga
    1973 年 46 巻 6 号 p. 1646-1649
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Formation of solvated ion radicals in the N-vinylcarbazole (VCZ)-and N-ethylcarbazole (ECZ)-electron acceptor systems in polar solvents has been studied by means of laser photolysis, transient photoconductivity and transient absorption measurements. Ion radical formation due to the encounter collision between an excited VCZ or ECZ and electron acceptor was confirmed directly. In the absence of electron acceptor, formation of cation radicals of carbazoles due to biphotonic process was observed in polar solvents. The Sn←S1 spectra of these molecules were observed both in polar and nonpolar solvents.
  • Tokuji Ikeda, Mitsugi Senda
    1973 年 46 巻 6 号 p. 1650-1656
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The polarographic behavior of D-xylose in several buffer solutions was investigated. The rate constants, k1, k2, k−1, and k−2, of the mutarotation of α-D-xylose, assumed as α\oversetk1\undersetk−1\ ightleftharpoonsγ\oversetk2\undersetk−2\ ightleftharpoonsβ, were calculated by the use of Wiesner’s method, but with a modified equation for the polarographic current. The overall mutarotation rate constant, ko, which is denned by ko=(k1k−2+k−1k2)⁄(k−1+k−2), was also determined. The rate constants, ko, k1, and k2, were analyzed as a linear function of the buffer concentration. It was revealed that the catalytic effects of the buffer salts were mainly due to their basic components for all the buffer salts investigated. The Bronsted plots of k1 and k2 for all the basic components gave straight lines with the same slope of 0.42. The rate constants for several amines deviated from the slope; this deviation was ascribed to the steric hindrance caused by their large molecular sizes.
  • Sadakatsu Nishikawa, Tatsuya Yasunaga, Nobuhide Tatsumoto
    1973 年 46 巻 6 号 p. 1657-1660
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The ultrasonic absorption in the mesomorphic state of octylamine water system was characterized by double relaxations. One in the lower frequency range has been explained by the structural relaxation theory of the two state model. In order to clarify the mechanism of the relaxation in the higher frequency range, the ultrasonic absorption in a relatively dilute aqueous solution was measured. The mechanism of the absorption was attributed to hydrolysis from the concentration dependence of the relaxation time. The rate constant kf for the proton transfer reaction, the equilibrium constant K=kbkf, and the standard volume change ΔV resulting from the reaction were determined to be 1.0×1010 M−1 sec−1, 7.6×10−3M, and 32 cc mol−1 respectively.
  • Kaoru Umeya, Takashi Kanno
    1973 年 46 巻 6 号 p. 1660-1663
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Dielectric behavior of the packing bed of alumina granules with various amounts of adsorbed water were determined in the frequency range 30 Hz–3 MHz. The dielectric relaxations characterized by a distribution in relaxation time were attributed to interfacial polarizations due to the adsorbed ions accumulated around the non-conductive points (i.e., discontinuous points on conducting paths consisting of water films adsorbed on alumina granules). Some of the adsorbed ions were carried away to the electrodes through the points of contact between the water films adsorbed on granules adjacent to each other (i.e., continuous conducting paths), giving rise to d.c. conductance and electrode polarization. When insulating sheets were inserted between the electrodes and surfaces of the packing bed, both the d.c. conductance and electrode polarization disappeared and another dielectric relaxation was observed. This was attributed to the interfacial polarization due to the ions accumulated at the interfaces between insulating sheets and water adsorbed on alumina granules.
  • Junichiro Mizusaki, Kazuo Fueki, Takashi Mukaibo
    1973 年 46 巻 6 号 p. 1663-1667
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The reaction rate at the Ag/Ag2S interface was determined as a function of silver activity of Ag2S in the temperature range 215–400°C. The silver activity of Ag2S at the interface was measured electrochemically by means of an Ag/AgI electrode. The reaction rate was measured by the direct sulfurization method (Wagner’s pellet method) and by Rickert’s method using Ag/AgI/Ag2S/Pt cell. The rates obtained by the two methods were in good agreement. It was found that this is a first-order reaction with respect to the activity of sulfur in Ag2S and that the rate equation is given by
    v=1.0×104{exp(−18000⁄RT)}aseqv cm−2s−1 (i)
    The following reaction mechanism prevails at the interface.
    2Ag(A)+S(Ag2S)→2Ag+(Ag2S)+S2−(Ag2S) (ii)
  • Yukio Nagaosa, Tatsuo Yonekubo
    1973 年 46 巻 6 号 p. 1667-1669
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Decomposition of the ternary molybdophosphoric acid of titanium(IV), vanadium(V), zirconium(IV) and niobium(V) by complexing agents such as oxalate, citrate or tartrate was found from a kinetic study to be of first-order with respect to each metal ion. The half lives and activation energies of decomposition were also examined. From the results chemical analysis of mixtures of the metals was studied by a logarithmic extrapolation method, utilizing the difference in decomposition rate. Metals in binary systems such as Zr–Nb, V–Zr, Nb–V, Ti–V and Ti–Nb could be determined simultaneously within a relative error of ±5%. Determination of 0.01∼0.2 mg of vanadium was carried out in the presence of titanium (0.1 mg), zirconium (0.5 mg), niobium (0.5 mg) and other diverse ions. Iron(III), aluminum, germanium(IV) and iodide interfered with the determination.
  • Masahiro Komatsu
    1973 年 46 巻 6 号 p. 1670-1674
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The application of anodic potential-step stripping voltammetry for the determination of metal ion was investigated. From the dependence of stripping current (ia,d) on electrode radius, the rotational speed of the stirring rod in electrodeposition and electrodeposition time for Cd(II) in 1 M KCl, the diffusion-controlled process could be theoretically predicted. The calibration curves of Cd(II), Mn(II), Ni(II), Zn(II), and Sb(III) were found to be linear in the range 0.01–0.1 ppm, and those of Tl(I), Cu(II), Pb(II), Sn(II), Bi(III), and In(III) in the range 0.02–0.2 ppm, by analysis at time t=1.25 sec on current-time curves. The ratio ia,dia,p increased in the order n=3<2<1, where ia,d is the anodic diffusion current obtained by the potential-step method, and ia,p the anodic peak current obtained by the linearly varying potential method. The ratio of irreversible electron transfer reaction differed from that of the reversible one. The coefficient of variation in the measurement of peak heights was ±3% for 0.1 ppm or 0.2 ppm of metal ion.
  • Makoto Aihara, Seizo Misumi
    1973 年 46 巻 6 号 p. 1674-1676
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The overall formation constants of cadmium- and zinc-halide complexes in acetonitrile were determined by potentiometric titration using a saturated metal amalgam indicator electrode. The effect of ion-pair formation was taken into consideration to elucidate the free halide ion concentration in the experiments. The values of logβ3 and logβ4 for cadmium-halide complex were found to be: I, 22.4 and 26.5; Br, 25.3 and 29.8; Cl, 29.2 and 34.0. The values for zinc-chloride complex were 20.1 and 23.4.
  • Hiroyasu Sakamura, Minoru Imaoka
    1973 年 46 巻 6 号 p. 1676-1680
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The change of the internal friction of sodium silicate and sodium borate glasses under an electric field was studied by means of a torsion pendulum technique. It was found that the internal friction increased under an electric field and that the increase was related to the numbers of vibration, the strength of the electric field, and the Na2O content. The increase in internal friction in the glasses with a high Na2O content was large because of the electrolysis of the glasses, which resulted in the removal of sodium ions. It was proposed that the internal friction increased because the removal of sodium ions was promoted by torsional oscillation under an electric field and that the deformation of the network took place around holes which were left behind by the removal of the sodium ions.
  • Masao Kiyama, Toshio Takada
    1973 年 46 巻 6 号 p. 1680-1686
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Ferric chloro, ferric aquo, and ferric sulfato complexes in acidic solutions have been hydrolyzed at temperatures below 70°C to form polynuclear complexes of iron(III). Magnetic and spectrophotometric studies have then been carried out in order to clarify the nature of the polynuclear complexes. From these studies, their empirical formulas are presumed to be Fe2(OH)2Cl2O, Fe2(OH)3(NO3)3, Fe2(OH)3(SO4)3⁄2, and Fe3(OH)2(SO4)7⁄2. The iron ions in these polynuclear complexes are in a high spin state, as are those in the ferric complexes, iron oxides, and oxyhydrates. It is proposed that, in all these polynuclear complexes except Fe3(OH)2(SO4)7⁄2, edge-shared octahedral dimer units are antiferromagnetically linked with one another by hydroxy or oxo bridging. When the hydrolysis temperature is raised, these polynuclear complexes are further hydrolyzed to form precipitates. The complexes of Fe2(OH)2Cl2O, Fe2(OH)3(SO4)3⁄2, and Fe3(OH)2(SO4)7⁄2 give β-FeOOH, α-FeOOH, and RFe3(OH)6(SO4)2 (R=Na, K or NH4) respectively, whereas the complex of Fe2(OH)3(NO3)3 gives α-FeOOH or α-Fe2O3, depending on the temperature.
  • Masaaki Kojima, Yuzo Yoshikawa, Kazuo Yamasaki
    1973 年 46 巻 6 号 p. 1687-1689
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The tris(2-methyl-1,2-propanediamine)cobalt(III) complex was prepared, and four possible isomers, geometrical and optical, were isolated by column chromatography on SP-Sephadex. Their configurations were assigned on the basis of the formation ratio and electronic, infrared, circular dichroism and PMR spectra: they were later confirmed by X-ray analysis.
  • Takeshi Kuwabara, Shigetaka Suzuki, Shun Araki
    1973 年 46 巻 6 号 p. 1690-1694
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The determination of arsenic(III) by anodic stripping using co-deposition with copper was worked out. A 0.24 M hydrochloric acid containing arsenic(III) and copper(II) was electrolyzed with a rotating platinum electrode (rpm=800) at a constant current. The deposit on the electrode was stripped by linear potential sweep method in 4 M hydrochloric acid. The stripping voltammogram was recorded in the span voltage −0.2–+1.2 volt vs. SCE. The stripping voltammogram showed two peaks, at zero volt and 0.5 volt vs. SCE. The area of the second peak was proportional to the concentration of arsenic. Linear dynamic range was 1–20 microgram per milliliter. The method was rapid and simple, the time required for analysis being about 35 minutes (electrolysis temperature, 25°C). X-ray and electron diffractions indicate that the second peak in the stripping voltammogram results from the dissolution of Cu3As.
  • Takaharu Honjo, Toshiyasu Kiba
    1973 年 46 巻 6 号 p. 1694-1698
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The behavior of trace amounts of mercury(II), cobalt(II), and zinc(II) in liquid-liquid extraction have been investigated with 1,1,1-trifluoro-4-(2-thienyl)-4-mercaptobut-3-en-2-one in cyclohexane, and the results applied to the separation of the three metals as their STTA complexes by extraction chromatography. A chromatographic column in which 10−3 M STTA in cyclohexane supported on Kel-F(poly-trifluorochloroethylene) powder was the stationary phase has been employed throughout this work. After the metal ions had been retained on the column by passing a sample solution of pH 5.5–6.0 through the column, the zinc(II) was eluted with an aqueous solution of pH 5.0 and then the mercury(II) was eluted with 1M hydrochloric acid. Last of all, since the cobalt had been caught so tightly on the column that it could not be removed even with concentrated hydrochloric acid, acetone was poured down the column in order to wash down all the organic phase together with the cobalt. The relation between the extraction chromatography and the liquid-liquid extraction in batches has been discussed with regard to the metal–STTA system under the same conditions.
  • Kiyoshi Isobe, Kenichiro Noda, Yukio Nakamura, Shinichi Kawaguchi
    1973 年 46 巻 6 号 p. 1699-1704
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The reactions of bis(acetylacetonato)nickel(II) with restricted amounts of dry hydrogen bromide have been performed in appropriate mixtures of dichloromethane and petroleum ether at room temperature or lower in order to isolate the intermediary products, Ni3Br(acac)5, Ni3Br2(acac)4, and Ni3Br4(acac)2. The essentially octahedral trinuclear structure of Ni3Br(acac)5 was established on the basis of elemental analysis, by molecular-weight and magnetic-moment determinations, and by studying the electronic and IR spectra. Ni3Br2(acac)4 and Ni3Br4(acac)2 were characterized less satisfactorily because of their lower solubilities. The reactions of these mixed complexes with pyridine have also been examined; a new complex NiBr(acac)(py)3 was thus obtained in addition to the known compound, Ni(acac)2(py)2.
  • Gurcharan Singh Manku
    1973 年 46 巻 6 号 p. 1704-1705
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Stability constants of the tervalent yttrium and lanthanoid complexes with 7-bromo-8-hydroxy-5-quinolinesulfonic acid have been determined in aqueous medium containing 0.100 M sodium perchlorate at 25±1°C by means of pH-titration. The trends in the order of the stability constants of these complexes are also discussed.
  • Taketoshi Nakahara, Hirohito Nishino, Makoto Munemori, Sôichir&o ...
    1973 年 46 巻 6 号 p. 1706-1711
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The determination of arsenic and selenium by atomic absorption spectropho tome try was established in premixed inert gas (entrained air)-hydrogen flames using a “multi-flame” burner. Arsenic and selenium electrodeless discharge lamps were used as the sources of radiation. The optimum operating conditions for the atomic absorption measurements for arsenic and selenium at 193.7 and 196.1 nm respectively were investigated. Under the optimum conditions, the sensitivities for 1% absorption were 0.17 and 0.15 ppm for arsenic and selenium respectively. Many other elements and acids interfered with the determination of arsenic and selenium in these low-temperature flames. Most of the interferences were found to be completely eliminated, in appearance, by adding a large amount (2000 ppm) of tin(II) chloride to the sample solutions. Furthermore, a gas-sampling technique for arsenic was studied in order to improve the arsenic sensitivity and in order to eliminate the interferences from other elements. The present method was applied to the determination of arsenic in sulfide ores and steels with satisfactory results.
  • Takayuki Matsushita, Tatsuo Yarino, Isao Masuda, Toshiyuki Shono, Koic ...
    1973 年 46 巻 6 号 p. 1712-1716
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    By the reaction of MnII(salen) (salen=N,N′-ethylenebis(salicylideneiminato) dianion) and its analogues with molecular oxygen in organic solvents, three types of complexes including as structural units the MnIII–O2–MnIII,–(–MnIV–O–)–n, and MnIV=O bonds respectively, have been obtained, and characterized by means of their electronic and infrared spectra, by thermogravimetric analysis, and in terms of their magnetic properties. The lower magnetic moments for [MnIII(salen)]2O2 and –[–MnIV(salen)–O–]–n than those expected have been interpreted in terms of antiferromagnetic interactions. The oxo complex was found to give the catena-oxo complex quantitatively in a DMF, DMSO, or Py solution. The effects of the oxygen partial pressure and the nature of the substituent in the organic part on the complex formation were investigated. A lower partial pressure of oxygen has the advantage of yielding the μ-peroxo complex in a higher yield. A discussion of the reaction mechanism is also included.
  • Tadaoki Okumoto, Tsugio Takeuchi
    1973 年 46 巻 6 号 p. 1717-1719
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The microstructure of ionically-chlorinated poly-α-methylstyrene with or without a catalyst and the distribution of chlorine in the aromatic nucleus of the polymers were studied by means of pyrolysis-gas chromatography. The degradation products, such as α-methylstyrene, p-chloro-α-methylstyrene, and 3,4-dichloro-α-methylstyrene, gave good information about substitution reactions on the aromatic nucleus in original poly-α-methylstyrene. The differences between two series of ionically-chlorinated poly-α-methylstyrene were also discussed on the basis of yield of α-methylstyrene and p-chloro-α-methylstyrene.
  • Toshihiko Amaya, Hidetake Kakihana, Masunobu Maeda
    1973 年 46 巻 6 号 p. 1720-1723
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The hydrolysis equilibria of Y3+, La3+, Gd3+, and Er3+ ions have been studied at 25°C in 3 M (Li)ClO4 by measuring the hydrogen-ion concentration with a glass electrode. All the test solutions containing hydrolyzed species prepared by the addition of alkali were acidified by means of constant-current coulometry. The data, which indicate a slight hydrolysis of the relevant ions, can be explained by assuming the formation of the following complexes: Y(OH)2+, logβ2,1=−17.0±0.1; Y2(OH)24+, logβ2,2=−14.04±0.01; LaOH2+, logβ1,1=−10.04±0.01; GdOH2+, logβ1,1=−8.20±0.01; Er(OH)2+, logβ2,1=−17.4±0.1; Er2(OH)24+, logβ2,2=−13.72±0.01.
  • Toshio Kawato, Hajime Kanatomi, Ichiro Murase
    1973 年 46 巻 6 号 p. 1723-1726
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Cobalt(II) complexes of diethylenetriamine-N,N′,N″-triacetic acid (DTTA) were prepared. From spectrophotometric and magnetic data, diaquo-DTTA-Co(II) was found to have an octahedral arrangement in which the N,N′-diacetate moiety and two water molecules are in the coordination sphere, and the terminal amino acid residue dangles outside. On heating the diaquo-complex, thermal rearrangement occurred with loss of water and the complex took a tetrahedral configuration. This was confirmed by its electronic spectrum and magnetic moment. The tetrahedral complex turned to another octahedral complex with absorption of water, the configuration of which seemed to differ from the original as judged by spectral difference. Cobalt(II) complexes of ethylenediamine-N,N′-diacetic acid (EDDA) were also prepared and investigated for the sake of comparison.
  • Chung-gi Shin, Yasuchika Yonezawa, Katsuhiro Katayama, Juji Yoshimura
    1973 年 46 巻 6 号 p. 1727-1729
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The reaction of α-nitroolefins with triethyl or diethyl phosphite was studied and structural assignment of the products was made by spectroscopic analyses. Ethyl α,β-unsaturated α-nitrocarboxylates (IV) and 1-nitroalkenes (V) reacted with triethyl phosphite to afford ethyl β-diethoxyphosphinyl-α,β-unsaturated-carboxylates (IX) and 2-diethoxyphosphinyl-1-alkenes (X), respectively. Compound (IV) reacted with diethyl phosphite to give ethyl β-diethoxyphosphinyl-α-nitrocarboxylates (VI). The geometrical isomerism in IX and the reaction mechanism were discussed.
  • Yukito Murakami, Junzo Sunamoto, Naomi Kanamoto
    1973 年 46 巻 6 号 p. 1730-1732
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    2-Chloro-3-pyridylmethyl phosphate was hydrolyzed in aqueous media. All runs were carried out in a pH range 1–3 where the reactive species are essentially of neutral and monoanion forms. The main reaction product was 3-hydroxymethyl-2-pyridone, the reaction following an apparent first-order kinetics with respect to both pyridone formation and liberation of inorganic phosphate. The hydrolytic elimination of the 2-chlorine atom was catalyzed to a great extent by the phosphate group. The dephosphorylation was effected by the presence of the 2-chlorine atom as well. The hydrolysis of the neutral phosphate species, which is in general inert to hydrolysis, was much accelerated in the present hydrolysis. A plausible mechanism was presented in terms of the concerted elimination of both 2-chlorine atom and phosphate moiety by their mutual catalytic participation. Besides the main reaction process, a normal hydrolysis affording 2-chloro-3-pyridylmethanol was also detected to proceed to a minor extent.
  • Fumio Toda, Nobuhiro Ooi
    1973 年 46 巻 6 号 p. 1733-1737
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Treatment of 3,4-bis(diphenylmethyl)cyclobut-3-ene-1,2-dione (I) with bromine in ROH (R=H, Me, Et, and i-Pr) afforded 3,4-bis(diphenylmethylene)cyclobutane-1,2-dione (IV) and 3-diphenylmethyl-4-alkoxydi-phenylmethylcyclobut-3-ene-1,2-dione (III) in various ratios depending on the steric bulkiness of R of ROH. Acidification of a solution of III in KOH–MeOH, in which III exists in the form of enolate anion (VIII), afforded III and IV in various ratios depending on the steric nature of the substituent R. Bromination of IV in 99% acetic acid afforded 3,4-bis(hydroxydiphenylmethyl)cyclobut-3-ene-1,2-dione (XI). Although the bromination of XI with phosphorus tribromide afforded IV, that with bromine afforded the 2,5-dihydrofuran derivative (XVII). The reaction of I with o-phenylenediamine to afford azamethylenecyclobutane derivatives XXV and XXVI is described.
  • Fumio Toda, Hisao Nakaoka, Kentaro Yuwane, Eishiro Todo
    1973 年 46 巻 6 号 p. 1737-1740
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Photolysis of 2,2-dimethoxy-3,4-bis(diphenylmethylene)cyclobutanone (I), 2,3-bis(diphenylmethylene)cyclobutanone (XIV), and 3,4-bis(diphenylmethylene)cyclobutanedione (XXV) in methanol was investigated. Photolysis of I afforded tricyclic compound(II) and dimethyl cyclobutanedicarboxylate (III) in 48 and 35% yields, respectively. Photolysis of XIV and XXV afforded the dihydronaphthalene derivatives (XIX) (88% yield) and XXIV (72% yield), respectively. The mechanisms of these reactions were also studied.
  • Shigeru Oae, Yuzuru Uchida, Ken Fujimori, Seizi Kozuka
    1973 年 46 巻 6 号 p. 1741-1745
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Specifically 18O-labeled p-substituted benzoyl cyclohexyl carbonates (1) were prepared and heated at 45, 70 and 75°C, and novel stepwise oxygen scrambling was found to take place in 1. On being heated at 45°C, the carbonic carbonyl oxygen atom and the oxygen atom sandwiched between the two carbonyl carbon atoms of 1 were found to scramble. The 18O-scrambling among the above two and carboxylic carbonyl oxygen atoms of 1 was found to take place at 70 or 75°C. A good first order kinetic dependence was observed for the first step of the scrambling at 45°C but no substituent effect. An intramolecular mechanism involving two steps of equilibration is proposed.
  • Norio Kunieda, Shigeru Oae
    1973 年 46 巻 6 号 p. 1745-1751
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The mechanistic investigations of the concurrent oxygen exchange and racemization reactions of 18O-labeled and optically active methyl p-tolyl sulfoxide (I) and phenyl p-tolyl sulfoxide (II) in sulfuric acid of various concentrations have been carried out by the determination of detailed kinetics. The kinetic data were analyzed in the lights of kexkrac values, activation parameters, correlations between the rates and acidity functions, solvent isotope effects, polar effects of substituents, etc.. A gradual change of mechanism of the reaction from an SN2 type process to a predominant A-1 like one (in above 95% sulfuric acid) with the increase of the concentration of sulfuric acid was observed. All these observations suggest that the A-1 like reaction takes place through a cation radical (–\overset+·S–) or a dication (–\overset++S–) intermediate at higher concentrations of sulfuric acid, while the SN2 type reaction that involves a water molecule as nucleophile in the rate-limiting step is the predominant path in less concentrated sulfuric acid.
  • Kenichi Murata
    1973 年 46 巻 6 号 p. 1752-1755
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The preparation, polymerization, and copolymerization of N-vinyl phthalimidine were investigated. The monomer was prepared by the dehydrochlorination of N-(β-chloroethyl) phthalimidine. Polymerization was carried out in the presence of radical or cationic initiators in bulk and in solution. It was found that polymerizability with cationic initiators was larger than that with radical ones. The resulting polymers had a softening point in the range of 160–180°C, the reduced viscosities being small. Copolymerization with acrylonitrile and styrene was carried out in dimethylformamide and benzene by radical initiators. The monomer reactivity ratios and Alfrey-Price Q, and e values calculated from the copolymerization data of the monomer (M1) and styrene (M2) were r1=0.05, r2=7.4, Q1=0.30, and e1=−1.80. Values for N-vinyl pyrrolidone (M1) were likewise determined for the sake of comparison, and found to be r1=0.02, r2=12.0, Q1=0.22, and e1=−1.99.
  • Kiyotada Matsui, Masatoshi Motoi
    1973 年 46 巻 6 号 p. 1755-1759
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The treatment of ethyl α-cyanophenylacetate with benzoyl chloride in the presence of 2 equivalents of aluminum chloride in nitrobenzene afforded 4-chloro-3-benzoyl-3-phenyl- (6% yield) and 4-chloro-3-benzoyl-3-(p-benzoylphenyl)-2-azetinone (28%) at 50°C. The same treatment of ethyl α-cyanopropionate afforded 4-chloro-3-benzoyl-3-methyl-2-azetinone (37%). The hydrolytic splitting of the chlorine atoms from the first two azetinones resulted in the formation of N-benzoyl-2,4-azetidinedione derivatives (36 and 20% respectively), whereas from the last we obtained N-benzoyl-α-carboxypropionamide (18%). These azetinone derivatives, when warmed with sodium methoxide in methanol, were converted into α-benzoyl α-cyano esters. The treatment of α-benzoyl α-cyano esters with aluminum chloride also afforded the azetinone derivatives in low yields.
  • Haruo Inoue, Mitsuhiko Hida, Tran Dinh Tuong, Takashi Murata
    1973 年 46 巻 6 号 p. 1759-1762
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The photo-amination reaction of sodium 1-amino-4-bromoanthraquinone-2-sulfonate (I) was studied. The experimental results may be summarized as follows: 1) The photo-reaction is evoked by the absorption of light corresponding to the first absorption band (490 nm) of (I); 2) no dark reaction is observed: 3) aromatic amines appeared not to photo-react with (I); 4) the larger the polarity of the solvents used, the greater the yield of the product; 5) in the absence of oxygen, the photo-reaction was stopped. The possible reaction schemes were discussed.
  • Toru Seita, Masayoshi Kinoshita, Minoru Imoto
    1973 年 46 巻 6 号 p. 1762-1764
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    5-Chloro-, bromo-, iodo-, N-ethylamino-, and N,N′-diethylamino-1-[(2′-dihydrogenphosphato)-ethyl]-uracil were synthesized from 1-(2′-hydroxyethyl)-uracil through the combination of halogenation, phosphorylation, and subsequent amination. These compounds were coupled with poly (vinyl alcohol) using N,N′-dicyclohexylcarbodiimide as a dehydrating agent to give polymers having 5-substituted uracils as pending groups.
  • Toshio Fuchigami, Eiichi Ichikawa, Keijiro Odo
    1973 年 46 巻 6 号 p. 1765-1770
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The reactions of N-chloroamidines with various dehydrochlorinating reagents were studied. N-Alkyl-N-chloroamidines were treated with sodium alkoxide, sodium hydroxide, and silver oxide to form O-alkylisoureas, ureas, and carbodiimides, respectively. However, N′-chloro-N′,N′-dialkylamidines did not afford corresponding products. The mechanisms for the rearrangements are discussed.
  • Kazuo Mitsumura, Y\={o}ji Hashida, Shizen Sekiguchi, Kohji Matsui
    1973 年 46 巻 6 号 p. 1770-1772
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Kinetic studies have been made of the coupling reaction of several diazonium salts with pyrrole, N-methylpyrrole, and N-ethoxycarbonylpyrrole. In the case of pyrrole, it was found, from the dependence of the apparent rate constant on the pH values, that the undissociated pyrrole reacted with diazonium salts in the pH range from 4.7 to 8.2, whereas in the pH region higher than 10.0 the reactive species was the conjugate base of pyrrole. The reactivity of the pyrrole anion was higher by a factor of 8 powers of ten than that of the undissociated pyrrole. The effects of the substituents of diazonium salts on the reaction rates were also investigated. The ρ-values (4.3–4.6) obtained in the Hammett plots were practically the same as those of diazo-coupling reactions which involve ordinary aromatic amines as coupling components.
  • Takahachi Shimizu, Takaaki Horaguchi, Akio Watanabe
    1973 年 46 巻 6 号 p. 1772-1776
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    5-Hydroxy-1-methoxyphenanthro[4,5-bcd]furan(I;R=MeO) was synthesized by dehydrogenation with 20% palladium on charcoal from 5,6,7,7a,8,9-hexahydro-1-methoxy-5-oxophenanthro[4,5-bcd]furan(XVII), which had itself been prepared via a naphthofuran derivative (XVI) starting from 5,8-dimethoxy-1-tetralone (VII).
  • Ryu-ichi Saito, Taeko Izumi, Akira Kasahara
    1973 年 46 巻 6 号 p. 1776-1779
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    Heck’s reaction of 4-chromanone enol esters with arylpalladium compounds in acetic acid afforded isoflavanones in a high yield. The structural elucidation of these products was accomplished by spectral inspections.
  • Kunio Okamoto, Koichi Komatsu, Susumu Tsukada, Osamu Murai
    1973 年 46 巻 6 号 p. 1780-1785
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The one-electron reduction of tropylium fluoroborate with Cr(II) was carried out in aqueous solution containing various anions (Cl, Br, SO42−, HSO4, BF4 and ClO4) which were added as proton acids or as sodium salts, and the reaction rate at 25°C was measured by the use of the flow method. It was found that Cl, Br, and SO42− exhibit the characteristic rate-accelerating effect, whereas BF4 and ClO4 show a slight rate-retarding effect. From the extrapolation of the anion concentration to zero, it was indicated that this reaction can proceed even in the absence of added anions. From these findings, together with the results of chemical and spectrophotometrical analyses of the Cr(III) species, it was concluded that the reduction of the tropylium ion with Cr(II) proceeds through an electron-transfer step where the anion (Cl, Br, or SO42−) or the water molecule acts as a weakly interacting electron-transfer bridge. This mechanism is essentially analogous to the “inner-sphere mechanism” known in the field of inorganic metal complex chemistry.
  • Kunio Okamoto, Koichi Komatsu, Osamu Murai, Osamu Sakaguchi, Yoshihisa ...
    1973 年 46 巻 6 号 p. 1785-1790
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    The one-electron reduction of the unsubstituted, methyl-, ethyl-, isopropyl-, t-butyl-, triphenylmethyl-, and phenyltropylium ions with Cr(II) in a 10% HCl solution gives, quantitatively, the dimer of the corresponding substituted tropyl radical. The measurements of the reaction rate at 25°C exhibit this order of reactivity: t-butyltropylium (k2=7.98 l/g·ion·sec), isopropyltropylium (8.22), ethyltropylium (10.3), methyltropylium (11.1), tropylium (74.0), phenyltropylium (144), and triphenylmethyltropylium (567) ions. The values of log k2 have a linear correlation with the transition energies of the charge-transfer bands observed for these carbonium ions with pyrene, and also with the polarographic half-wave potentials of the respective cations. These correlations indicate that the reactivity of the carbonium ion in the reduction with Cr(II) is determined mainly by the electron affinity inherent in the respective cations. The values of log k2 also have a good linear correlation with the pKR+ values, implying a parallelism between the electron affinity and the electrophilicity of these stable carbonium ions.
  • Jitsuo Kiji, Kazuyoshi Yamamoto, Shin-ichi Mitani, Susumu Yoshikawa, J ...
    1973 年 46 巻 6 号 p. 1791-1795
    発行日: 1973年
    公開日: 2006/03/27
    ジャーナル フリー
    A catalyst system of NiX2(R3P)2–NaBH4 or –R′ONa (X=halogen, R and R′=alkyl) was found to yield 2-methylenevinylcyclopentane (MVCP) and n-octatrienes (OT), depending on the amount of NaBH4 or R′ONa, which act as a reducing agent for the nickel halide. Less than an equimolar amount of the reducing agent provides a catalyst for MVCP, whereas an excess amount provides that for n-octatrienes. In the latter case, the nickel halide is reduced to zero-valent nickel, which then reacts with hydrogen halide to give a catalyst for MVCP again. The catalyst (<2:1 ratio of reducing agent: Ni) was also effective in the isomerization of 1,3,7-octatriene to MVP.
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