Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 41 , Issue 7
Showing 1-50 articles out of 61 articles from the selected issue
  • Toshio Tanaka, Yoshio Matsumura, Rokuro Okawara, Yoshihiko Musya, Susu ...
    1968 Volume 41 Issue 7 Pages 1497-1500
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Assignments are given for the infrared spectra of bis-pyridine complexes of SnX4, (CH3)2SnX2(X=Cl,Br and I), and (C2H5)2SnCl2 in the 80–1610 cm−1 region. These complexes show the Sn–N stretching band near 200 cm−1. Most pyridine vibrations shift to a higher or a lower frequency upon complex formation. Among these, the ν10, in-plane ring deformation vibration is the most sensitive to the substituents on the tin atom as well as to the complex formation. Thus, the frequency may be a qualitative measure of the tin-pyridine coordination bond strength. The infrared spectra suggest a cis-configuration for the tin tetrahalide complexes and a distorted octahedral configuration for the dimethyltin diiodide complex. The remaining complexes may be assumed to have trans-alkyl and cis-halogen configurations.
  • Masatoshi Hirayama, Taro Isobe
    1968 Volume 41 Issue 7 Pages 1502-1512
    Published: 1968
    Released: March 27, 2006
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    ESR spectra are observed for the anion radicals of methyl p-, m- and o-nitrobenzoates, methyl ester of p-phthalaldehydic acid, and methyl and ethyl p-cyanobenzoates. Both the electrolytic and alkali-metal reduction methods are used for the radical generation. The spin densities calculated by McLachlan’s procedure only with the adjustment of the resonance-integral parameter for the ester group-ring bond are in good agreement with those obtained experimentally for most of the substituted positions in these radicals. The result for the methyl o-nitrobenzoate anion suggests that the ester group is twisted considerably by the large steric hindrance between the ester and nitro groups. The ring-proton splittings of three p-substituted methyl benzoate anions show that the known order of electron-withdrawing effects of the substituents, NO2>CHO>COCH3>COOCH3>CN, holds also for these anions. And it is suggested that the electron-withdrawing power of a XM+ group produced on the alkali-metal reduction increases in the order of free NO2, NO2Cs+,NO2K+,NO2Na+ and NO2Li+, and that the groups CHONa+ and CHOK+ are more electron-withdrawing than a free CHO group. The ring-proton splittings obtained from the VB-superposition calculations for all the anions except for the o-derivative are in satisfactory agreement with those from the MO calculations. Structural models of ion complexes are proposed for the p- and m-nitro derivatives and methyl ester of p-phthalaldehydic acid with the assistance of MO calculations.
  • Yoshihisa Matsuda, Shoji Makishima, Shigeo Shionoya
    1968 Volume 41 Issue 7 Pages 1513-1518
    Published: 1968
    Released: March 27, 2006
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    The purpose of this paper is to clarify whether intramolecular energy transfer in europium chelates occurs via the triplet state of the ligand. It is attempted to excite the triplet state of europium dibenzoylmethide (EuD) by utilizing intermolecular triplet-triplet energy transfer from lanthanum dibenzoylmethide (LaD). In mixed solutions of EuD and LaD, the intensity and decay time of the ligand phosphorescence of LaD decreases with increasing molar fraction of EuD at liquid nitrogen temperature. Nearly in proportion to this, the intensity of the europium emission of EuD is enhanced, veryfying the occurrence of energy transfer from LaD to EuD. This fact is taken as clear evidence that intramolecular energy transfer takes place via the triplet state.
  • Hiroshi Kawabe, Masaya Yanagita
    1968 Volume 41 Issue 7 Pages 1518-1524
    Published: 1968
    Released: March 27, 2006
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    Chloromethylated polystyrene is quantitatively aminated by n-butylamine or n-dibutylamine in dioxane, but the plot of the logarithmic term in the simple second-order rate equation against the time is not represented by a single straight line, but is divided into two lines which intersect nearly at the half-amination point. These results are interpreted in terms of the step-by-step amination resulting from the steric effect of the already-aminated neighbors which have bulky alkyl groups. By assuming two distinct reactivities of chloromethyl groups according to their neighboring environment, rate equations for two separate steps are derived; these equations give k1, the rate constant in the first step, and k2, that in the second step. In the presence of a large excess of amine, the over-all kinetics can be expressed by:
    dx/dt=[ab/(2k_1-k_2)][2k_1-(k_2)e^-2k_1at+k_1-k_2e^-k_2^at],
    where x is the concentration of chloride ions at time t; a is the initial concentration of amine, and b, that of the chloromethyl group. The equation is found to be substantially valid for the values of k1 and k2 computed by the equations for the individual steps.
  • Takehiko Chiba, Gen Soda
    1968 Volume 41 Issue 7 Pages 1524-1532
    Published: 1968
    Released: March 27, 2006
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    Deuteron magnetic resonance study was made on single crystals of NiSiF6·6D2O and NiSnCl6·6D2O. Deuteron quadrupole coupling tensors were determined at various temperatures. In NiSiF6·6D2O, the quadrupole coupling at −116°C is that of stationary D2O, at 23°C and at 70°C that of D2O under rapid 180°-flip motion and at 150°C that of rapid Ni(D2O)62+ reorientation. The eqQh values at −116°C, 238.3±1.3 kc and 235.7±1.9 kc do not appear to show marked effect of strong coordination. In NiSnCl6·6D2O, the quadrupole coupling corresponding to D2O under 180°-flip motion is observed at −53°C, at 25°C, and at 55°C. Spectra corresponding to a stationary D2O are not observed even at 77 °K. From the orientation of quadrupole tensors probable crystal structures of these compounds are proposed. Line width transitions were observed from which the reorientation rate was derived. The estimated activation energies of the 180°-flip motion of D2O are 7.6 and 4.3 kcal/mol in the fluosilicate and chlorostannate, respectively, and that of Ni(D2O)62+ reorientation in the fluosilicate is 19 kcal/mol. Additional measurements of 19F and 1H resonances indicate the setting in of the SiF62− reorientation at −110°–−120°C in NiSiF6·6H2O, and that of the Ni(H2O)62+ reorientation in the chlorostannate at approximately the same temperature as the fluosilicate.
  • Tetsuo Morimoto, Mahiko Nagao, Fujiko Tokuda
    1968 Volume 41 Issue 7 Pages 1533-1537
    Published: 1968
    Released: March 27, 2006
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    The desorbability of water molecules chemisorbed on the surfaces of metal oxides has been investigated in the cases of α-Fe2O3, TiO2 (rutile) and ZnO. Water vapor adsorption isotherms were determined on the samples treated at various temperatures in a vacuum of 10−5 Torr. The BET Vm-values of water adsorption were plotted against the temperature of the pretreatment. The curves obtained show a sharp increase at a moderate temperature which is varied by the nature of solid substance. This fact makes us conclude that, at this temperature, the chemisorbed water on oxide surfaces starts to be removed. The variation in the desorption temperature due to the nature of metal oxide is considered to come from the magnitudes of the bonding force of the surface hydroxyl groups to the surface metal atoms on each solid.
  • Hiroshi Hotta, Nobutake Suzuki
    1968 Volume 41 Issue 7 Pages 1537-1539
    Published: 1968
    Released: March 27, 2006
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    The autoxidations of benzene, toluene and ethylbenzene were investigated at 70°C by using the oxygen-18 enriched Fenton’s reagent. The oxygen-18 atom percentage in the products suggests that all the oxygen of benzaldehyde from toluene and of acetophenone from ethylbenzene is donated by molecular oxygen dissolved in the aqueous phase, while the oxygen of the hydroxylation products, namely, phenol from benzene, benzyl alcohol from toluene and methyl phenyl carbinol from ethylbenzene, is donated partly from water and partly from molecular oxygen. From the latter finding, the rate of the carbonium cation formation from the intermediate radicals without their oxidation to the peroxide is in the order of phenyl>α-methyl-benzyl>benzyl.
  • Sachio Murakami, Mituo Koyama, Ryoichi Fujishiro
    1968 Volume 41 Issue 7 Pages 1540-1545
    Published: 1968
    Released: March 27, 2006
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    The heats of mixing were measured at 25.0°C for binary mixtures of chloroform+tetrahydrofuran,+furan, and +2-methyl furan systems and for cyclohexane+chloroform,+tetrahydrofuran,+furan, and +2-methyl furan systems. Using these data and the treatment described in a previous paper [Bull. Chem. Soc. Japan, 37, 1776 (1964)], the intermodular hydrogen bond energies between chloroform and cyclic ethers were estimated to be ΔH=−12 kJ for the chloroform-tetrahydrofuran-cyclohexane system, ΔH=−4 kJ for the chloroform -2-methyl furan-cyclohexane system, and ΔH=−3 kJ for the chloroform-furan-cyclohexane system. From these results, two types of intermolecular hydrogen bonds between chloroform and cyclic ethers are discussed.
  • Koichi Kikuchi, Hiroshi Kokubun, Masao Koizumi
    1968 Volume 41 Issue 7 Pages 1545-1551
    Published: 1968
    Released: March 27, 2006
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    It has been shown that the delayed and normal fluorescence can be measured accurately by a usual flash apparatus. Such measurements, combined with that of T–T absorption, have enlarged the potentiality of a flash technique to a large extent. As an example, a simple method of differentiation between E-type and P-type delayed fluorescence has been presented. Detailed studies have been made on the T–T annihilation process of anthracene (A) and the probability for Process AT+AT→A+A*, has been decided. The value obtained is 0.077±0.005. E-Type delayed fluorescence of eosine and proflavine have been studied and the value of kt·φST (kt, the rate constant of Process, T\ ightharpoonupS*; φST, the probability of the intersystem crossing) have been evaluated, to be 3.36 and 2.78 sec−1 respectively. Some advantages of the present method over the sector method have been discussed.
  • Kanekichi Kagami
    1968 Volume 41 Issue 7 Pages 1552-1557
    Published: 1968
    Released: March 27, 2006
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    By studying the relation between the concentration and the oxidation activity of various metal catalysts, mostly naphthenates, oleates, linoleates, and caprates of manganese, cobalt, and nickel salts, as well as mixed catalysts of two kinds, it has been established that, in general, there is an anomalous effect of the catalyst concentration-namely, the catalytic activity disappears above a certain point in the concentration of the catalyst. The anomalous concentration effect of a catalyst is observed in the oxidation of toluene and p-xylene with all the catalysts, but chromium naphthenate is a lone exception in the oxidation of p-xylene. It has been shown that the anomalous effect is due to the association of the catalyst in the hydrocarbon solvent to be oxidised, and that the associated catalyst does not act to promote oxidation. The association is reversible, being dependent on the concentration of the catalyst, so the anomalous concentration effect of a catalyst disappears on dilution.
  • Ken Hirotsu, Taiichi Higuchi, Akira Shimada
    1968 Volume 41 Issue 7 Pages 1557-1563
    Published: 1968
    Released: March 27, 2006
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    Crystals of 1,1′-bis(pentamethyldisilanyl)ferrocene, (π-C5H4Si(CH3)2Si(CH3)3)2Fe, are monoclinic, with a=6.84, b=30.87, c=12.67 Å and β=96.80°. The space group is P21/n and there are four molecules in a unit cell. The structure was solved by Patterson and minimum functions, and further refined by Fourier and difference syntheses, and finally by a least-squares method. The final R value is 14.4% for 883 observed reflections. The two cyclopentadienyl rings are planar, approximately parallel to each other, separated by 3.28Å and deviated by about 6° from the fully eclipsed configuration. The molecular configuration is gauche with respect to the two side-chains. The mean values of the bond distances are found to be Fe–C(cyclopentadienyl rings)=2.05, C–C=1.45, C(cyclopentadienyl rings)–Si=1.87, C(methyl groups)–Si=1.90 and Si–Si=2.34 Å. All intermolecular separations correspond to the normal van der Waals interactions.
  • Kiyoshi Matsuda, Reita Tamamushi
    1968 Volume 41 Issue 7 Pages 1563-1568
    Published: 1968
    Released: March 27, 2006
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    The frequency dependence of the faradaic impedance and its phase angle of an electrode process with a preceding chemical reaction was studied with the Cd(II)-EDTA system. The experimental results were analyzed by means of Smith’s equation, and the rate constant of the reaction, Cd2++HY3−→CdY2−+H+, was estimated to be equal to 2·3×109 l mol−1 sec−1 at the ionic strength of 0.5 and at 25°C. In connection with this study, the faradaic impedance behavior of simple electrode processes was re-examined with the Cd(II)-, Pb(II)-, and Zn(II)-KC1 systems.
  • Reita Tamamushi, Kiyoshi Matsuda
    1968 Volume 41 Issue 7 Pages 1568-1572
    Published: 1968
    Released: March 27, 2006
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    The admittance and its phase angle of the polarographic reduction of peroxodisulfate and ferricyanide ions in solutions containing no supporting electrolytes were measured at very low frequencies. The series resistance components, measured at 30 cps, of these systems gave anomalously small values at the electrode potentials where the falling-off of the cathodic current was observed on the direct current polarograms. This anomaly in the alternating current polarization behavior was attributed to the negative charge-transfer resistance due to the double layer effect on the charge-transfer process.
  • Shinji Takahashi
    1968 Volume 41 Issue 7 Pages 1573-1577
    Published: 1968
    Released: March 27, 2006
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    The diffusion coefficients of 14CO2 in argon and in binary mixtures of normal carbon dioxide and argon were measured at the temperatures of 25, 50 and 75°C in the 15—250 atm pressure range. The measurements were made through a plug of porous bronze in the diffusion cell using the radioactive tracer technique. The products of the binary diffusion coefficient of 14CO2 in argon and the density increase with an increase in the density. This tendency is not predicted by Enskog-Thorne’s mixed dense gas theory, which requires that the products decrease with an increase in the density. The products of the diffusion coefficient of 14CO2 in the mixtures and the density increase slightly with an increase in the density in the region of lower density at each temperature. However, in the region of higher density they decrease slightly at 25 and 50°C and are nearly constant at 75 °C. The values extrapolated to 1 atm agree fairly well with the experimental findings of Holsen et al. and those predicted by kinetic theory.
  • Tamotsu Wasa, Sôichirô Musha
    1968 Volume 41 Issue 7 Pages 1578-1582
    Published: 1968
    Released: March 27, 2006
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    Formaldehyde (I), acetaldehyde (II), propionaldehyde (III), n-butyraldehyde (IV), n-caproaldehyde (V), and n-octaldehyde (VI) condense with o-phenylenediamine (OPD) to yield products, each of which gives a single, irreversible but well-defined oxidation wave (E12 vs. SCE at pH 8.0: −0.240 V for I, −0.242 V for II, −0.263 V for III, −0.290 V for IV, −0.316 V for V, and −0.338 V for VI). From these findings, it has been deduced that the condensation products of aldehydes with OPD would be benzimidazoline derivatives, which would be oxidized to benzimidazole derivatives at the dropping mercury electrode. Linear relations between the limiting currents of the condensation products with OPD and the concentrations of aldehydes [(1–20)×10−4 M], except for I, were obtained under the following conditions: (pH, 6–8(pHimax); the concentration of OPD, 2×10−2 M; the temperature, 25°C; and the condensation time, 15–60 min. The method was then applied practically in the determination of the purity of a commercial product of II and the quantity of II in the presence of glyoxal.
  • Tetsuo Noguchi, Masao Mizuno
    1968 Volume 41 Issue 7 Pages 1583-1587
    Published: 1968
    Released: March 27, 2006
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    A liquidus curve in the system ZrO2-MgO was investigated by the use of a heliostat type solar furnace. The cooling curves of a composition were obtained by the specular reflection method with a brightness pyrometer. Quenched specimens from the melt were examined with an X-ray technique and a petrographic microscope. Newly found anomalies on the liquidus curve were 7.5, 12.5 and 17.5 mol% MgO compositions. The composition of 12.5 mol% MgO quenched from the melt showed the new cubic-like phase of which optic angle of 2 V equals to −74°C and decomposed easily into monoclinic and tetragonal forms by reheating at 1300°C.
  • Tsutomu Sugiura
    1968 Volume 41 Issue 7 Pages 1588-1600
    Published: 1968
    Released: March 27, 2006
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    Fluorine and chlorine contents of volcanic rocks were examined with respect to the characteristics of the rocks. Fluorine showed rather linear relationships with some chemical components of the rocks and also with stages in the differentiation of magmas. But any universal relationship covering all the rock types was not found. The cause of this fact is expected to be the loss of halogens from rocks resulted from the interaction between rocks and water vapor, which is believed to be ubiquitous in magma and is gradually emanated from it during or after the formation of rocks. So, in order to make clear the role of water vapor in the distribution of halogens in rocks, the author has distilled fluorine and chlorine from rock samples with water vapor at elevated temperatures and studied following relations; (1) the relationship between the amount of distilled halogens and the fluorine and chlorine contents of the rocks, and (2) the relationship between the amount of distilled halogens and the characteristics of the rocks. In distillation of fluorine and chlorine with water vapor, almost all fluorine remained in each rock specimen at low temperatures below 300°C, and at temperatures above 700°C the ratio of the amount of distilled fluorine to the initial amount of fluorine in rocks fluctuated among specimens. However, there was no relation between patterns of the distilled fluorine and the fluorine content of the rocks, and also the characteristics of the rocks. Meanwhile, distillation curve of chlorine showed various patterns without having any relation to chlorine content of the rocks, and indicated that chlorine was retained more in basic rocks than in acidic rocks at higher temperatures, although no relation was observed between the chlorine content of the rocks and the characteristics of the rocks. Generally the ratio of distilled fluorine to initial fluorine in rocks is smaller than the ratio of distilled chlorine to initial chlorine in rocks at low temperatures. The results of the distillation experiments suggest that the distillation process of halogens with water vapor controlls the distribution of halogens in volcanic rocks more than does the chemical and mineralogical nature of the rocks.
  • Takuji Ito, Tadao Kenjo
    1968 Volume 41 Issue 7 Pages 1600-1605
    Published: 1968
    Released: March 27, 2006
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    Selectivity coefficients of various anions vs. chloride or nitrate and water uptake at a saturated vapor pressure with polymeric pentamethylene cobalticinium exchanger were calculated from the experimental data and compared with those of anion-exchange resins. The selectivity coefficient sequence was nearly identical with that for quaternary ammonium type anion-exchangers, and the position of hydroxide ion indicated that the cobalticinium type anion-exchanger was a strong base type. Inspection of selectivity coefficients data revealed that strong base anion-exchangers were more selective than weak base anion-exchangers. The cobalticinium type anion-exchanger was found to have a high selectivity coefficient of iodide vs. bromide, even in comparison with strong base anion-exchange resins. Column separation of bromide and iodide using the cobalticinium type anion-exchanger was easily accomplished. The separation factor was three times that of the quaternary ammonium type anion-exchanger. The water uptake at a saturation vapor pressure by the cobalticinium type anion-exchanger in a given form increased with decreasing selectivity coefficient for the same anion. These trends were similar to those for quaternary ammonium type anion-exchanger. The relation between selectivity coefficient sequence of various anions vs. a common anion, and solubilities of the salt whose cation was the ionogenic group and anion adsorbed ion was discussed.
  • Yoshinaga Oka, Toyoaki Kato, Akira Yamadera
    1968 Volume 41 Issue 7 Pages 1606-1610
    Published: 1968
    Released: March 27, 2006
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    The most prominent (γ, n) reaction products with half-lives from 10 sec to about 1 min formed by irradiation of some 7 elements with 20 MeV bremsstrahlung have been determined in order to study the applicability of these products to photoactivation analyses. Irradiation was carried out for 1 min with 20 MeV bremsstrahlung radiation with a dose rate of 107 R/min. The reactions investigated are 24Mg(γ, n)23Mg, 76Ge(γ, n)75mGe, 78Se(γ, n)77mSe, 92Mo(γ, n)91mMo, 140Ce(γ, n)139mCe, 142Nd(γ, n)141mNd and 159Tb(γ, n)158mTb. The yields of these reactions have also been obtained through the absolute measurement of resultant activities. The isomeric yield ratios have been discussed on the basis of the nuclear properties of the residual nuclides. The observed ratios generally favor the isomer whose spin is closer to that of the target nucleus. For the elements studied, the lower limits of detection averaged about 1 μg under present experimental conditions.
  • Tsunenobu Shigematsu, Masayuki Tabushi, Masakazu Matsui, Megumu Munaka ...
    1968 Volume 41 Issue 7 Pages 1610-1614
    Published: 1968
    Released: March 27, 2006
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    The coprecipitation and direct-photometric method was applied to the uranium β-diketonate system; uranyl ion was coprecipitated as dibenzoylmethanate with o-phenylphenol and determined spectrophotometrically after the precipitate was dissolved in butyl acetate. The effect of ligand concentration on the per cent coprecipitation-pH curve was studied and the curve was not affected by the ligand concentration in the range from 2×10−2 to 4×10−4 M. Over the 200 mg of o-phenylphenol, an almost quantitative coprecipitation was obtained, though the absorbance slightly decreased with the increase in the coprecipitant amount (about 2% per 1g o-phenylphenol). As many diverse ions interfered with the determination of uranium, the solution of calcium EDTA chelate was used as a masking agent. When a small amount of alkylamine was added, the recovery of uranium became more complete. The effect of alkylamine was probably caused by the adduct formation of uranium chelate with alkylamine.
  • Kazuko Ogino, Tasuku Murakami, Kazuo Saito
    1968 Volume 41 Issue 7 Pages 1615-1618
    Published: 1968
    Released: March 27, 2006
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    The rate of aquation of pentamminecobalt(III) complexes of the general formula [Co(NH3)5amH]3+ (amH stands for an amino acid molecule with proton on the nitrogen atom), containing unidentate glycine, β-alanine, sarcosine and betaine, has been measured at 55°C, and ionic strength 0.1 and 1.0 in the acid concentration range up to 0.5 M. The kinetic term is expressed by
    Rate=[complex](k_H_2O+k_H^+[H^+])
    The kH2O and kH+ values for glycine, β-alanine, sarcosine and betaine complex are respectively as follows (at μ=1.0): kH2O, 0.40×10−6, \lesssim0.2×10−6, 0.25×10−6, and 0.44×10−6 sec−1; kH+, 2.0×10−6, 26×10−6, 1.8×10−5, and 1.0×10−6 M−1 sec−1. The kH+ alues increase with increase in pKa values of the amino acids, but are smaller than those for the aquation of carboxyl-atopentamminecobalt(III) complexes. This difference seems to be due to the electrostatic shielding of the car boxy late group by the protonated amino group.
  • Toshiaki Nomura
    1968 Volume 41 Issue 7 Pages 1619-1621
    Published: 1968
    Released: March 27, 2006
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    Cyanide ion reacted with mercury(II)-methylthymolblue (Hg-MTB) complex to form a mixed ligand complex. Since the resulting mixed ligand complex had a considerable absorption at 615 mμ, the spectrophotometric determination of cyanide ion was performed by measuring the increase in absorption of mercury (II)-methylthymolblue complex caused by formation of this mixed ligand complex. After excess MTB methanol and mercury (II) nitrate solutions were added to a cyanide sample solution which was adjusted to a definite pH value between pH 7.3 and 7.6 with phosphate buffer solution, it was diluted to exactly 50 ml with water. After standing for about 25 min, the absorbance of this solution was measured at 615 mμ against the reagent blank solution. Beer’s law was obeyed in the concentration range of cyanide ion from 5 to 80 μg per 50 ml, and the molar extinction coefficient was found to be about 5100. Taking 55.0 μg of cyanide ion, the standard deviation and variation coefficient of absorbances in the mean value of 10 runs were 0.0019 and 0.90%, respectively. The molar ratio of cyanide ion to Hg-MTB in the mixed ligand complex was found to be 1 : 1.
  • Hiroshi Ogino, Nobuyuki Tanaka
    1968 Volume 41 Issue 7 Pages 1622-1628
    Published: 1968
    Released: March 27, 2006
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    Kinetics of electron-transfer reactions of ethylenediaminetetraacetatochromate(II) ions with some isothiocyanatoammine complexes of chromium (III), Cr(NCS)n(NH3)6−n(3−n)+(n=0, 1,4 and 6) have been studied. The former ions are present in the forms of both CrII(H2O)edta2− and CrII(H2O)Hedta, but the reaction of CrII(H2O)Hedta with Cr(NCS)n(NH3)6−n(3−n)+ is not significant in the pH range from 3.6 to 5.3. Second-order rate constants (l mol−1sec−1) of the reactions between CrII(H2O)edta2− and Cr(NCS)n(NH3)6−n(3−n)+ at ionic strength 1.0 and 25°C are <10−2 Cr(NH3)63+, 0.2 for CrNCS(NH3)52+, 2.3 for Cr(NCS)4(NH3)2, and 28.2 for Cr(NCS)63−.
  • Tsutomu Mizoroki, Mikitake Nakayama
    1968 Volume 41 Issue 7 Pages 1628-1633
    Published: 1968
    Released: March 27, 2006
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    The reaction of methyl iodide with carbon monoxide in the presence of cobalt (II) iodide as the catalyst has been investigated to know the effect of methyl iodide on the acetic acid synthesis from methanol and carbon monoxide catalyzed by the same catalyst. The reaction, CH3I+CO+H2O→CH3COOH+HI, does not take place before the methyl iodide used has been hydrolyzed completely into methanol and sodium iodide by adding enough amount of sodium acetate (CH3I+CH3COONa+H2O→CH3OH+NaI+CH3COOH). Methyl iodide also strongly inhibits the reaction of methanol with carbon monoxide catalyzed by cobalt (II) ion or dicobalt octacarbonyl, although iodide ion promotes the reaction effectively. The promotion effect of iodide ion has been discussed by considering the effect of an additive on carbonylation reactions in terms of a labilizing ligand and a non-labilizing ligand and a possible reaction scheme of methanol with carbon monoxide catalyzed by cobalt(II) iodide has been proposed.
  • Hiroshi Watanabe, Shigeru Kuwata, Kenzo Naoe, Yoshiteru Nishida
    1968 Volume 41 Issue 7 Pages 1634-1638
    Published: 1968
    Released: March 27, 2006
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    DL-β(2-Pyridyl)-α-alanine has been synthesized in a good yield by the condensation of α-picolyl chloride and diethyl acetamidomalonate and by the subsequent hydrolysis of the product. The N-carbobenzoxy derivative of this amino acid, quite different from 3-pyridylalanine reported by Griffith and Harwood, could easily be prepared in a good yield. Only the carbodiimide method and the N-bromosuccinimide method proved to be successful in bringing the N-carbobenzoxylated amino acid into a peptide-coupling reaction with an amine component. Other methods, i. e., the mixed anhydride method, the azide method and the p-nitrophenyl ester method, were unsuccessful. It is noteworthy that, in the former cases, the activation of the carboxyl group occurs in situ in the presence of an amine component. No difficulties were encountered in the coupling reaction of the alkyl ester of this amino acid with usual N-protected amino acids. The alkaline hydrolysis of the protected dipeptide ester afforded the N-protected peptide in a good yield. The catalytic hydrogenation could be used to remove the benzyl ester group as well as the carbobenzoxy group without any damage to the pyridine ring. Decarbobenzoxylation also proceeded smoothly with hydrogen bromide in acetic acid.
  • Takeo Saegusa, Shiro Kobayashi, Kiwami Hirota, Yoshiharu Okumura, Yosh ...
    1968 Volume 41 Issue 7 Pages 1638-1642
    Published: 1968
    Released: March 27, 2006
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    The reaction of a thiol with an isocyanide proceeds in two directions. In the first reaction (course a), the carbon atom of isocyanide with lone-pair electrons is inserted into the sulfur-hydrogen bond of thiol to produce thioformimidate (I). In the second reaction (course b), isothio-cyanate (II) and the alkane (III) from the alkyl group of thiol are formed. The proportion of the participation of two reactions depends upon the alkyl group of thiol and upon the reaction conditions including whether or not a catalyst is employed. Primary thiol prefers course a to course b, whereas tertiary thiol prefers course b. In the reactions at 15°C, the Group IB and IIB metal compounds, e. g., copper compounds, catalyzed the course a reaction preferably. At higher temperatures, e. g. at 100°C, thiol reacts with isocyanide quite rapidly, even in the absence of a catalyst. However, the catalyst effect favoring course a is seen even in the high-temperature reactions. The mechanism of the reaction, especially course b, has been discussed. Syn-anti structures of thioformimidate were also studied by NMR.
  • Yoshiyuki Kiso, Mitsue Kobayashi, Yoshinori Kitaoka, Keizo Kawamoto, J ...
    1968 Volume 41 Issue 7 Pages 1642-1647
    Published: 1968
    Released: March 27, 2006
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    Phosphoric esters of hexoses were subjected to neutrons and the resulting 32P-labeled recoil products were separated by paper chromatography and paper electrophoresis. The main recoil products were phosphorous and phosphoric acids, independent of the chemical form of the target material and the kind of its salt. A small amount of inorganic acids containing a P–P or P–O–P bond was also found. The yield of the retention product was less than a few percents. The presence of organic diphosphorus compound was supposed by paper electrophoretic analysis. An addition of a small amount of water to the target material before irradiation favored formation of 32P-labeled phosphorus oxyacids in lower oxidation state. The results from irradiation of aqueous solution gave an unexpected chromatographic behavior owing to some unstable complex of recoil 32P atom with water molecule.
  • Yoshio Iwakura, Shinsaku Shiraishi, Masayasu Akiyama, Masahiro Yuyama
    1968 Volume 41 Issue 7 Pages 1648-1653
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Terephthalonitrile di-N-oxide and isophthalonitrile di-N-oxide were synthesized from the corresponding hydroxamic chlorides by dehydrochlorination with triethylamine. Their chemical properties and the polycycloadditions with diolefins were examined. The polymers obtained were amorphous and their molecular weights were not so high. The thermal gravimetric analyses of them showed that the polymers were stable up to 300–350°C in air.
  • Yoshio Iwakura, Shinsaku Shiraishi, Zin Asakawa, Masayasu Akiyama, Nob ...
    1968 Volume 41 Issue 7 Pages 1654-1657
    Published: 1968
    Released: March 27, 2006
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    Polyurethans with isoxazoline or isoxazole linkages in the polymer main chains were prepared by polyadditions of diols with isoxazoline or isoxazole rings and diisocyanates. The diols were prepared by 1,3-dipolar cycloaddition reactions of tere- and iso-phthalonitrile di-N-oxides with allyl or propargyl alcohol. Polyurethans of the same structures were also prepared by 1,3-dipolar polycycloadditions of the nitrile oxides with bisallyl or bispropargyl carbamates.
  • Tadashi Sasaki, Shoji Eguchi, Atsuyuki Kojima
    1968 Volume 41 Issue 7 Pages 1658-1664
    Published: 1968
    Released: March 27, 2006
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    (5-Nitro-2-furyl)diazomethane (2), 3-(5-nitro-2-furyl)diazopropene (4), and 1-(5-nitro-2-furyl)diazoethane (6) were prepared by the oxidation of the corresponding hydrazones with active manganese dioxide. The relative stabilities of these diazo compounds were then compared with p-nitrophenyldiazomethane in their ethanolic solutions and in their solid states by measuring their decomposition rates spectroscopically; it was found that the stability decreased in the following order:
    2& 6\backsimeqp-nitrophenyldiazomethane>2\backsimeq4 & & in ethanol
    & p-nitrophenyldiazomethane>2>4>6 & & in the solid state.
    The reactivities of these diazo compounds were also investigated in the decomposition reactions; the thermal and photolytic decomposition of 2 afforded l,2-di(5-nitro-2-furyl)ethylene (7) in a low yield, but 4 cyclized readily to 3-(5-nitro-2-furyl)pyrazole (8) in a good yield and 6, to an azine (9) even upon standing at room temperature. 2 was treated with benzoic acid in ether to give 5-nitro-2-furfuryl benzoate (10) in a quantitative yield, and with triphenylphosphine in the same solvent to afford the triphenylphosphazine (13) in a 75% yield; this last substance liberated nitrogen very easily in the presence of cuprous ions to give the phosphonium ylid (14), one of the Wittig reagents. 14 was then considered as a possible starting material for preparing (5-nitro-2-furyl)ethylenic compounds. Similarly, 3-(5-nitro-2-furyl)acrolein triphenylphosphazine (17) was prepared from 4 and triphenylphosphine.
  • Rikuhei Tanikaga
    1968 Volume 41 Issue 7 Pages 1664-1668
    Published: 1968
    Released: March 27, 2006
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    The photochemical reduction of azoxybenzene to azobenzene has been investigated. The direct irradiation of azoxybenzene leads to a rearrangement to 2-hydroxyazobenzene and to cis-trans isomerization, whereas the sensitized irradiation leads to a reduction to azobenzene in the presence of a sensitizer with a triplet excitation energy greater than ca. 62 kcal/mol. 2-Hydroxyazobenzene and cis-azoxybenzene seem to be formed from the excited singlet state of azoxybenzene, and azobenzene, from the excited triplet state. Even without a sensitizer, the irradiation of benzo[c]cinnoline N-oxide, which is incapable of undergoing rearrangement or isomerization, brings about a photochemical reduction, which is affected by a sensitizer or a quencher, and also by the hydrogen-donating ability of the solvent used (isopropanol>ethanol>cumene>toluene). Acetone is yielded when isopropanol is used as the solvent. On the basis of these results, a mechanism in which benzo[c]cinnoline is formed from the excited triplet state of benzo[c]cinnoline N-oxide, followed by hydrogen abstraction from a solvent, is proposed.
  • Hisao Yokota, Masatsune Kondo, Tsutomu Kagiya, Kenichi Fukui
    1968 Volume 41 Issue 7 Pages 1668-1671
    Published: 1968
    Released: March 27, 2006
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    We investigated the acetylation of the endgroups of the polymer chain resulting from the polymerization of formaldehyde in liquid carbon dioxide in the presence of acetic anhydride. The thermal stability and the toughness of the resulting polymer were examined. All of the endgroups of polymer chains were satisfactorily acetylated by means of heating, between 140 and 150°C, the solid polymer, which was separated by discharging the unreacted monomer and carbon dioxide after polymerization. The acetic anhydride which was added in the beginning of the polymerization at a concentration of 5 mol% per monomer, was sufficient to stabilize the polymer thermally. On the acetylating of the polymer, the presence of air or acetic acid in the amount used to initiate the polymerization had no effect on the properties of the acetylated polymer. A simplified purification procedure for the acetylated polymer was presented.
  • Hisao Yokota, Masatsune Kondo, Tsutomu Kagiya, Kenichi Fukui
    1968 Volume 41 Issue 7 Pages 1672-1679
    Published: 1968
    Released: March 27, 2006
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    The influence of acetic anhydride on the polymerization of formaldehyde, which was carried out by means of initiation with an acidic catalyst in liquid carbon dioxode, was studied at 20 to 40°C. Acetic anhydride decreased the polymer yield and the degree of polymerization of the polymer resulting from the polymerization with acetic acid. Moreover, the over-all rate of polymerization with acetic acid in the presence of acetic anhydride deviated from a first-order equation with respect to the monomer concentration. On the other hand, the polymerization which was initiated by dichloroacetic acid was not affected by the presence of acetic anhydride. On the basis of a kinetical consideration, it can be said that the termination which was proportional to the square of the concentration of the initiating species was caused by the presence of acetic anhydride in the polymerization with acetic acid. The rate constants and the activation energies of the elementary processes were estimated, and a rate equation satisfying the experimental results was presented.
  • Yoshikazu Ikutani
    1968 Volume 41 Issue 7 Pages 1679-1681
    Published: 1968
    Released: March 27, 2006
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    The N,N-dimethyl derivatives of neutral amino acids, such as glycine. L-alanine, DL-alanine, L-valine, DL-valine, L-leucine, L-phenylalanine, and L-tyrosine, were prepared by the catalytic reductive condensation of the corresponding amino acids with formaldehyde. The N-oxides were satisfactorily synthesized by the oxidation of the N,N-dimethyl derivatives with an aqueous mixture of hydrogen peroxide and acetic acid. The reaction conditions, the analytical data, and some properties of the products are presented.
  • Tsutomu Kagiya, Tomizo Kondo, Kenichi Fukui
    1968 Volume 41 Issue 7 Pages 1682-1686
    Published: 1968
    Released: March 27, 2006
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    In the copolymerization of N-phenylethylenimine with β-propiolactone, the mechanisms of the initiation and propagation reactions were investigated. The rate of the copolymerization was markedly increased by the addition of propionic acid. When a mixture of triethylamine and propionic acid was used as additive, the rate decreased with an increase in the amount of triethylamine, while with an equimolar mixture the rate was almost equal to that without any catalyst. No polymer was obtained with an excess of triethylamine. With Brönsted acid, the composition of the copolymer was independent of the concentration of the catalyst, but it varied with the pKa value. The monomer reactivity ratio of N-phenylethylenimine increased with a decrease in the pKa value. While that of β-propiolactone decreased.
  • Kentaro Yoda, Kazuyuki Kimoto
    1968 Volume 41 Issue 7 Pages 1687-1689
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The ring-opening polymerization of cyclic bis(ethylene isophthalate) (I) was carried out in the presence of various metallic compounds as catalysts. Among the polycondensation catalysts for ethylene terephthalate, antimony and tin compounds were very effective in the ring-opening polymerization of I. On the other hand, titanium, zinc, calcium, and aluminum compounds did not show high catalytic activity. The polymerization of I proceeded even at temperatures below the melting point of I. As the melting point of the resulting poly(ethylene isophthalate) was much lower than the polymerization temperature, the reaction system gradually melted in consequence of the progress of the polymerization reaction.
  • Kenichi Murata, Akira Terada
    1968 Volume 41 Issue 7 Pages 1690-1694
    Published: 1968
    Released: March 27, 2006
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    A method of preparing new-type anion-exchange resins from 1-phthalimido-, 1-succinimido-, and 2-phthalimido-1,3-butadiene polymers is shown. The procedure consists of two steps, the hydrolysis of the imido groups into free amine, followed by heating with hydrochloric acid to make the amino groups into the hydrochloride, and N-methylation by the Schotten-Baumann method. The anion-exchange resins obtained from the former two polymers show high exchange capacities, such as 5.85 and 7.21 meq/g of dry resin respectively. However, their salt-splitting capacities are not high. The mechanisms of their crosslinking on hydrolysis and of their heat-aging are also discussed.
  • Takeo Saegusa, Takashi Ueshima, Kunioki Kato
    1968 Volume 41 Issue 7 Pages 1694-1696
    Published: 1968
    Released: March 27, 2006
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    Two aluminum silanolates, diethyl(trimethylsiloxy)aluminum (I) and tris(trimethylsiloxy)-aluminum (II), were compared with the corresponding aluminum alcoholates in terms of their acid strength and in their catalyst behavior in the polymerizations of cyclic ethers and vinyl ether. The reference aluminum alcoholates were diethylaluminum t-butoxide (III) and aluminum t-butoxide (IV). The Lewis acid strength was examined by means of two methods, the Hammett indicator method and the shift of the IR carbonyl band (ΔνC=O) of n-butyraldehyde. Four aluminum compounds, I–IV, were weaker Lewis acids than triethylaluminum; i.e., the replacement of the ethyl group of triethylaluminum with either a siloxy group or an alkoxy group brought about a decrease in the acid strength. The acid strength of I and II were demonstrated to be stronger than that of the reference alcoholates, III and IV. A difference in polymerization catalyst activity was also observed between aluminum silanolates and the reference alcoholates; it was reasonably explained by the difference in acid strength.
  • Waichiro Tagaki, Tsutomu Tada, Ryuichi Nomura, Shigeru Oae
    1968 Volume 41 Issue 7 Pages 1696-1700
    Published: 1968
    Released: March 27, 2006
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    Free radical copolymerization reactions of ketene diethylmercaptal (I) and p-methyl-mercaptostyrene (III) with styrene have been carried out. The Q-values for I and III are found to be 2.7 and 3.3 respectively, and these and other related observations are discussed in terms of electron-sharing conjugation involving 3d-orbital of sulfur atom.
  • Matsuji Takebayashi, Toshikazu Ibata
    1968 Volume 41 Issue 7 Pages 1700-1707
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The decomposition of α-diazoacetophenone (I) in benzene solution has been studied using a silver benzoate-triethylamine catalyst at 50°C in an atmosphere of nitrogen. The reaction gave 3-benzoyl-4-hydroxy-5-phenylpyrazole (II) and β-phenylpropiophenone (III). In the decomposition of the substituted compounds, such as p-methoxy-, p-methyl- and p-nitro-α-diazoacetophenones, the corresponding substituent products of II and III were also obtained. The formation of II and III is reasonably explained by assuming two kinds of reactions between phenylketene and I.
  • Tadashi Suehiro, Shuji Hibino, Tadashi Saito
    1968 Volume 41 Issue 7 Pages 1707-1711
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Benzoylphenylacetylperoxyd und Benzoyl-p-chlorphenylacetylperoxyd zerfallen photolytisch in Toluol bei −5–−10°C in die Benzoyloxy und Benzyl bzw. p-Chlorbenzyl Radikale unter Bildung von Kohlendioxyd, Benzoesäure, Benzoesäure-benzyl- bzw. -p-chlorbenzyl-ester, Bibenzyle, Methyldiphenylmethane, Diphenylmethane und Methyldiphenyle. Eine Umlagerungsreaktion vom Peroxyd in den Benzylkohlensaurebenzoesäureanhydrid verläuft nebenbei und dieser Anhydrid liefert durch Einwirkung auf Benzoesaure, Kohlendioxyd, Benzylalkohol und Benzoesäureanhydrid. Die freie Radikale Reaktion und die Umlagerung in den Kohlensäureanhydrid vom Peroxyd finden im Verhältnis ca. 2:1 statt. Aus dem Lösungsmittel, Toluol, entsteht Benzyl Radikale wahrend der Photolyse durch Einwirkung von Benzoyloxy Radikal, dies wurde durch das Vorkommen von Bibenzyl und p-Chlorbibenzyl bei der Photolyse von Benzoyl-p-chlorphenylacetylperoxyd in Toluol nachgewiesen.
  • Renji Okazaki, Naoki Inamoto
    1968 Volume 41 Issue 7 Pages 1711-1716
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Reactions of dimethylaniline with some resonance-stabilized radicals were studied. 2-Cyano-2-propyl radicals and 2-methoxycarbonyl-2-propyl radicals reacted to give N-methyl-N-(3,4-dicyano-3,4-dimethylpentyl) aniline and the corresponding 3,4-dimethoxycarbonyl derivative, respectively, while benzyl radicals and α-methoxycarbonylbenzyl radicals did not give reaction products with dimethylaniline. Mechanism of these reactions was proposed and it was pointed out that electron transfer from dimethylaniline to radicals was an important stage in these reactions.
  • Jumpei Ando, Takashi Akiyama, Matsusaburo Morita
    1968 Volume 41 Issue 7 Pages 1716-1723
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Fluorine forms a previously unknown compound MgNH4HFPO4 (MAFP) when monoammonium phosphate made from wet-process phosphoric acid is treated with magnesium hydroxide above about 75°C in the presence of moisture. When treatment is conducted with a large quantity of water, fluorine forms a gelatinous material which resembles MAFP in chemical composition. Wet-process phosphoric acid ammoniated and reacted with magnesium hydroxide above about 75°C gives a very thick slurry, which almost solidifies due to the formation of gelatinous material, while the acid treated in the same way after being defluorinated gives a less viscous slurry in which most of the magnesium is present in the form of MgNH4PO4·H2O (MH). Fluorine shows less effect at lower temperature. When treated below about 60°C, most of the magnesium combines to form MgNH4PO4·6H2O (M6H) and Mg(NH4)2(HPO4)2·4H2O (M4H). M6H and M4H decompose during drying at about 100°C, losing ammonia and water of crystallization to form amorphous materials. The decomposition is promoted by the presence of potassium salts resulting in the formation of water-insoluble potassium. Another previously unknown compound, MgKHFPO4 (MKFP), which is isomorphic with MAFP has also been identified. MKFP is less soluble in water while MAFP decomposes in water to precipitate amorphous material and M6H. Solid solutions of MAFP and MKFP are often present in commercial fertilizers, and provide a small amount of water-insoluble potassium. M4H decomposes rapidly in water to precipitate M6H. M6H and MH are less soluble in pure water but are considerably soluble in water which contains acidic salts, such as monoammonium phosphate.
  • Zennosuke Suzuki, Ken-ichi Morita
    1968 Volume 41 Issue 7 Pages 1724-1725
    Published: 1968
    Released: March 27, 2006
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  • Yoichi Utsunomiya, Hiroshi Kuyama
    1968 Volume 41 Issue 7 Pages 1726-1727
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tadao Okutani
    1968 Volume 41 Issue 7 Pages 1728-1729
    Published: 1968
    Released: March 27, 2006
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  • Kazuhide Miyazaki
    1968 Volume 41 Issue 7 Pages 1730-1732
    Published: 1968
    Released: March 27, 2006
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  • Kunikatsu Shirahata, Nobuo Abe, Tadahiro Kato, Yoshio Kitahara
    1968 Volume 41 Issue 7 Pages 1732-1733
    Published: 1968
    Released: March 27, 2006
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  • Kinya Unoura, Masayuki Aikawa, Meiseki Katayama
    1968 Volume 41 Issue 7 Pages 1734
    Published: 1968
    Released: March 27, 2006
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  • Nobufumi Maki, Taihei Hamazaki, Shukichi Sakuraba
    1968 Volume 41 Issue 7 Pages 1735
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
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