Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 12
Showing 1-50 articles out of 55 articles from the selected issue
  • Janusz Dabrowski, Krystyna Kamienska-Trela
    1966 Volume 39 Issue 12 Pages 2565-2571
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared spectra of several chloro-, bromo- and iodovinyl ketones and their partly deuterated derivatives were investigated in the liquid state and in solutions. A Raman spectrum of one of these substances was also obtained. It has been shown that, unlike enamino- and hydroxyvinyl ketones, the title compounds exhibit fairly characteristic absorption bands due to carbonyl and skeletal vibrations. The splittings observed in the double bond stretching region are accounted for by rotational isomerism. Several assignments of the group frequencies are proposed.
  • Yukiteru Katsube, Yoshio Sasada, Masao Kakudo
    1966 Volume 39 Issue 12 Pages 2572-2576
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to determine the angular orientation of the rigid atomic group, such as benzene ring, in a molecular crystal, a new method for interpreting a distribution of peaks near the origin of two-dimensional Patterson function has been described in this paper. Similar methods for solving the Patterson function by the aid of the rigid groups have been proposed by several authors, but the present method, vector-set seeking method, differs from them in the procedure to find a satisfactory fit of a vector-set of the rigid group on the Patterson function and in a criterion for a correct choice of the angular orientation. Satisfactory results for the known structures of salicylamide and α-pyridone and the unknown structure of m-hydroxybenzamide were quickly obtained by the application of this method.
  • Yukiteru Katsube, Yoshio Sasada, Masao Kakudo
    1966 Volume 39 Issue 12 Pages 2576-2583
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Crystals of m-hydroxybenzamide are monoclinic with four molecules in a unit cell of dimensions a=11.59, b=5.03, c=15.53 Å, β=136.1°, space group P21c. An approximate angular orientation of the molecule in the cell was quickly obtained by an application of the vector-set seeking method. The location of the molecule was then determined with the help of the orientation. The positional and anisotropic thermal parameters of the carbon, nitrogen and oxygen atoms were refined by means of the least-squares method with three-dimensional intensity data. The final R factor was 0.138. The carboxyamide group and benzene ring twist to each other about the C-C bond by an angle of 24.4°. The interatomic distances and bond angles are close to those expected. The molecules are linked by three types of hydrogen bonds to form the infinite double-layered sheets perpendicular to the c axis, and the crystal structure shows somewhat different features from those of the related compounds.
  • Akira Sugimori
    1966 Volume 39 Issue 12 Pages 2583-2588
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Coordinated oxalates in metal complexes are more reactive under γ-irradiation than are ionic oxalates. This suggests that the covalency between the metal ion and the ligand in oxalato metal complexes promotes the reactivity of the ligand. The reaction of the ligand is also affected by the central metal ions. In K3[Co(C2O4)3]·3H2O and K3[Fe(C2O4)3]·3H2O, the coupled reduction of central metal ions with the oxidative decomposition of the ligand to carbon dioxide occurs at relatively high G values. In K3[Cr(C2O4)3]·3H2O, the redox reaction of the central metal ion is small and the ligand decomposes into carbon dioxide and carbon monoxide. In K3[Al(C2O4)3]·H2O, the formation of glyoxal and formic acid instead of carbon monoxide is significant.
  • Takuji Miwa, Masao Koizumi
    1966 Volume 39 Issue 12 Pages 2588-2597
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The fluorescence and absorption spectra and the quenching of the fluorescence of N, N-dimethyl-2-naphthylamine by methylbenzoate have been measured in cyclohexane, benzene, p-dioxane, isopropyl ether, ethyl ether, ethyl acetate, tetrahydrofuran, acetone and N, N-di-methylformamide (in the order of DK values). The fluorescence and the absorption spectra show a red-shift with the polarity of the solvent. By the method of Lippert and Mataga, the dipole moment of the excited fluorescer molecule has been estimated to be 4. ID. In nonpolar and weakly polar solvents, the methyl benzoate-added systems give fluorescence spectra with a swell or a shoulder on the long wavelength side, but this does not occur in N, N-dimethylformamide. When methyl benzoate is used as the solvent, two peaks of fluorescence are observed. The new emission has been interpreted as a charge-transfer emission, and the temperature-dependence of the fluorescence spectra has led to the conclusion that an encounter of fluorescent and quencher molecules is prerequisite for the appearance of CT emission. The quenching efficiencies in different solvents have been dealt with in reference to that in N, N-dimethylformamide, since the quenching in this solvent has been found to be almost encounter-controlled. A general correlation has been found between the quenching efficiency and the polarity of the solvent. The quenching mechanism and also the appearance of the CT emission have been discussed.
  • Tomoko Komiyama, Takuji Miwa, Masao Koizumi
    1966 Volume 39 Issue 12 Pages 2597-2602
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The quenching action of N, N-dimethylaniline, nitrobenzene, s-trinitrobenzene and tetracyano-ethylene on the fluorescence of acridine orange (AO) has been studied using ethanol and dioxane as solvents. In these solvents AO exists as cations or neutral molecules. In the former solvent, the quenching actions of the above substances on these two species have been investigated separately. The quenching constants, K’s (in reference to the Stern-Volmer equation) of the above substances (in the above sequence) in ethanol are (34–35), (19.6), (53.6) and (∼90) for cations and (8.4), (72.8), (−), and (−) for neutral molecules (in l./mol.). Thus, when quenchers are electron acceptors, K increases with the accepting power: nitrobenzene<s-trinitrobenzene<tetracyanoethylene. Further, acceptors are more efficient quenchers on neutral molecules than on cations (nitrobenzene), whereas the reverse is true for donors (N, N-dimethylaniline). In dioxane the quenching constants are generally somewhat smaller than in ethanol, but a basic similarity has been confirmed. All the results support the view that the present quenching phenomena are closely related to a charge-transfer process.
  • Naoto Yamamoto, Yoshihiro Nakato, Hiroshi Tsubomura
    1966 Volume 39 Issue 12 Pages 2603-2608
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Flash photolysis studies of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) were made in various solvents at room temperature. The transient absorption spectrum of the cation, TMPD+ , was observed in polar solvents. The transient was also observed in a viscous, non-polar solvent. It has a spectrum different from that of TMPD+ . Its absorbance is proportional to the flash-light intensity, and it decays exponentially, with τe=82 μ sec. This absorption is attributed to the triplet-triplet transition of TMPD. With aerated solutions, no transient spectrum was observed. The fluorescence and the phosphorescence of TMPD caused by direct excitation were investigated, together with those induced by the recombination of electrons and TMPD+ in non-polar matrices stimulated either thermally or by infrared light. The absorption spectra of TMPD in a non-polar matrix at a low temperature were investigated by means of the cross-illumination method, and the time dependence of the absorption was followed. The ionization and the recombination processes were then discussed by the use of these results.
  • Tetsu Takeyama, Hajime Miyama
    1966 Volume 39 Issue 12 Pages 2609-2612
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Mixtures of ammonia and oxygen in argon were heated by reflected shock waves to temperatures between 1600 and 2100°K, and the ultraviolet radiation from OH(2Σ+) was observed by means of monochromator and a photomultiplier. The radiation profiles showed two types of radiation: a strong spike which appeared after an induction period, and a weak and constant-level emission, which followed the spike and persisted for up to 500 μsec. The former emission was observed also in the oxidation of hydrogen, methane, and acetylene, but the latter emission was observed only in the oxidation of methane and acetylene. The temperature coefficients of the intensities of the latter emission divided by the sum of spectral emissivities were found, for the oxidation of ammonia, not large enough to be explained by the thermal excitation of the ground-state OH(2π) to the 2Σ+ state. Possible reaction processes for this chemiluminescence were proposed to explain the experimental results.
  • Akira Sugimori, K\={o}ichi Nakata, Hachiro Hirai
    1966 Volume 39 Issue 12 Pages 2613-2615
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The radiation-induced reaction of o-nitrobenzaldehyde in the solid state was investigated. Isomerization to o-nitrosobenzoic acid preferentially took place. This suggests that the γ-ray irradiation produces effectively the excited o-nitrobenzaldehyde which is identical with that produced by ultraviolet irradiation.
  • Michio Ashida, Natsu Uyeda, Eiji Suito
    1966 Volume 39 Issue 12 Pages 2616-2624
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Thin films of phthalocyanine compounds formed on cleaved surfaces of muscovite by the vacuum-condensation method showed well-defined single-directional orientation when their substrates were preheated at 300°C for one hour and then kept at 150°C. Their electron diffraction patterns were fiber diagrams, the fiber period of which coincided with the unit-cell length of the b-axis of the individual compounds. When the substrates were preheated at 400°C for one hour and then kept at 150°C, the films formed on the muscovite surface were composed of discrete crystals with a different orientation. Electron-diffraction patterns from the films revealed that the b-axis of the crystal was inclined to the substrate surface. The cross-grating patterns of the (h0l) plane were obtained when the inclination of the films was properly adjusted to the incident beam. The unit-cell constants of platinum-phthalocyanine vacuum-condensed on muscovite were revealed to be as follows with the monoclinic space group C2⁄c: a=23.18 Å, b=3.818 Å, c=23.84 Å, and β=91.9 °. Films of Cu-, Co-, Fe-, Ni- and metal-free phthalocyanines exhibited an orientation similar to that of the platinum derivative. High-resolution electron-diffraction patterns revealed that all the compounds assumed a conspicuous isomorphism with one another and occurred in the metastable forms of their dimorphs.
  • Michio Ashida
    1966 Volume 39 Issue 12 Pages 2625-2631
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    When substrate muscovite is preliminarily heated at 300°C for one hour and then kept at 150°C to 200°C during deposition in vacuo, Cu-phthalocyanine films condensed on it show parallel b-axis orientations, including single- and triple-directional orientations. The b-axis of the crystal runs parallel to the substrate face. On the other hand, when the substrate is preliminarily heated at 400°C and then kept at 150°C, films vacuum-condensed on it occur in a standing b-axis orientation. The high-resolution electron-diffraction pattern of the film reveals that the a-, b- and c-axes of the crystal are inclined to the normal of the substrate face at angles of about 75°, 32° and 118° respectively. An electron micrograph of the film shows that as discrete crystals grow they orient themselves in either of two different directions. The crystal which assumes the standing b-axis orientation has its (31\bar3) plane almost parallel to the substrate face. Pt-phthalocyanine film also assumes the standing b-axis orientation, in which the a-, b- and c-axes of the crystal are inclined to the normal of the substrate face at angles of about 74°, 35° and 120° respectively. It turns out that the molecular plane comes in contact with the muscovite surface in the case of the standing b-axis orientation. A plausible explanation of the origin of these orientations is presented in terms of the dehyroxylation of the surface mica layer caused by the thermal treatment.
  • Michio Ashida
    1966 Volume 39 Issue 12 Pages 2632-2638
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Cleaved faces of KCl, KBr and NaCl crystals were used as substrates. When copper-phthalocyanine is vacuum-condensed onto either KCl or KBr, the films on it take a standing b-axis orientation, which shows a C4v symmetry. The major planes of symmetry coincide with those of KCl and KBr. The crystals on KBr show an azimuthal angular shift of about +12° or –12° in respect to the major symmetry axes, [010] and [100], of the substrate crystal. When the films have the standing b-axis orientation, the planar molecule in the crystal comes into parallel contact with the cleavage face of the substrate. It may be presumed that the bridge nitrogen atoms in a phthalocyanine molecule are placed on the potassium ions in the (001) planes of KCl and KBr. The films on KCl and KBr are composed of finely-divided rectangular crystals and dendrites; the former are concentrated at steps on the cleavage face to produce a decorative pattern, while the latter appear on the smooth surface. The formation in various types of crystals are interpreted in terms of the rate of nucleation and growth. The films vacuum-condensed onto NaCl are composed of laminar crystals which have a random orientation.
  • Kozo Hirota, Yoshie Hironaka
    1966 Volume 39 Issue 12 Pages 2638-2642
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The catalytic hydrogenation of propene with deuterium gas and its isotopic exchange reaction with deuterium oxide have been carried out at room temperature, and the remaining propene has been subjected to microwave spectroscopic analysis so as to determine the isotopic isomer-distribution of propene-d1 and -d2. From the results, the following conclusions have been drawn: (1) the rate-determining step in the hydrogenation on platinum as well as nickel and palladium catalysts is the addition of hydrogen to the half-hydrogenated species; (2) the kinds of chemisorbed species and their distribution prior to the rate-determining step are not always the same, but depend on the metals, and (3) the life-time of the chemisorbed propene is shorter than the successive time interval of its exchange process on nickel, but this is not the case on platinum nor, probably, on palladium.
  • Koji Shigehara
    1966 Volume 39 Issue 12 Pages 2643-2645
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The amounts of water of ionic and nonionic hydration were calculated for sodium alkyl sulfate in the state of molecular dispersion from the data obtained by the author and under the assumptions usually adopted: (a) the solution, as a whole, consists of several volume elements of different compressibilities; (b) the ionic radical together with its hydration water is incompressible; (c) the compressibility of the water of nonionic hydration for the CH2 group of the hydrocarbon chain is the same as that of ordinary ice; (d) the compressibility and the molar volume of the CH2radical in the state of molecular dispersion are the same as those in the micellar state. The water of hydration was calculated to be 2.1 mole per mole of the CH2 radical, and 4.9 mole per mole of the ionic radical, the latter value being the same as that of the solute in the micellar state previously reported. The molar volume of the water of nonionic hydration is found to be slightly less than that of free water, in accordance with the prediction of others. The dehydration of sodium alkyl sulfate caused by the addition of inorganic electrolyte has also been observed.
  • Tsutomu Koide, Tsutomu Oda, Osamu Washio, Kazuo Fujita
    1966 Volume 39 Issue 12 Pages 2645-2647
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    2-Bromo-1,1,1-trichloro-2-methylpropane gives a plastic crystal, named by Timmermans (J. Chim. Phys., 35, 331 (1938)), which is optically isotropic and which has a density of 1.97 g./cc. at 25°C. The X-ray data can be interpreted with a body-centered cubic lattice, with 7.42 Å for the unit cell length containing two molecules. The symmetry interpretation gives a crystal structure of a disordered orientation of molecules. It was found, by means of optical measurements and differential thermal analysis, that there is a phase transition at about −62°C, below which the crystal is in a lower symmetry.
  • Tatsuo Matsuura, Tetsuo Hashimoto
    1966 Volume 39 Issue 12 Pages 2647-2652
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The recoiling behavior of [Co(C2O4)3]3−, [Co(NO2)6]3− and [Co(CN)6]3− ions on in anion-exchanger was studied both by the dynamic and the static methods under various conditions. As the stability of the complex decreases, the separable yield increased as a general trend, and the effectiveness of the dynamic method in obtaining higher yield than the static method was clearly demonstrated. On the other hand, specific activity increased with increasing stability of the complex, i. e., with decreasing G values. The increase of pH generally decreased the separable yield and increased the specific activity. The effects of mesh size of resin and preirradiation by gamma rays were also studied. Since the observed tendency that the separable yield decreased with increasing stability constant of the complex ion seems to be a general one, a theoretical interpretation for this relationship was attempted.
  • Kosiro Hashimoto, Goro Yamaguchi, Yoshitomo Toda
    1966 Volume 39 Issue 12 Pages 2652-2655
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The super-homogeneous coprecipitation method, in which the binary solution reactants made to mix and react in a moment, thus reducing a super-homogeneous precipitate, has been used recently in the preparation of catalysts. The coloring temperature of the cadmium sulfoselenide red pigment can be lowered to 350°C by this method, while, when the usual wet method is used, the temperature is between 450 and 650°C. This is because a very homogenous solid solution can be formed by the super-homogeneous coprecipitation method. This method is also effective in making an anionic solid solution of A(X, Y) with different anions of X and Y. Spectral reflectance measurements and X-ray analysis in the present work have shown that the coloring temperature has been considerably lowered and the transformation of the β-Cd(Se, S) into the a form has been accelerated by the method.
  • Yoshiki Moriguchi
    1966 Volume 39 Issue 12 Pages 2656-2665
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The hydrolysis of some oligophosphates (tetra-, penta- and hexaphosphates) has been studied at 45°C in the absence and in the presence of a metal complex, and the relation between the nature of the complex catalyst and the composition of the degradation products has been investigated on oligophosphates as substrates, especially on pentaphosphate. In the presence of the Cu(II)-en (1:1) complex, the intermediate chain of pentaphosphate is attacked to produce trimeta- and pyrophosphates as the main products; the hydrolytic reaction is apparently of a first-order kinetics which depends on the concentration of the catalyst. The Cu(II) - Poly-Lys complex shows a strong catalytic activity and attacks pentaphosphate exclusively, thus producing orthophosphate as the main product. The optimum conditions for the catalytic effect on the hydrolysis of pentaphosphate are as follows: 1) the ratio of the NH2 repeat unit of Poly-Lys to a mole of pentaphosphate ([-NH2]i/[P5]i) is about 1.6 at pH 8, the concentration of Cu(II) being constant; 2) the molar ratio of Cu(II) to the NH2 repeat unit of Poly-Lys ([Cu]i/[-NH2]i) is 1.0: 3) the activity reaches a maximum at about pH 10. Attempts have been made to explain these results on the basis of the structure of the Cu(II) - Poly-Lys complex.
  • Sarju Prasad, K. C. Pathak
    1966 Volume 39 Issue 12 Pages 2666-2668
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Ammonium telluro-vanadomolybdate, 6(NH4)2·TeO3·3V2O5·4MoO3·15H2O, has been synthesized, its properties studied, and its composition determined by analytical methods. Copper, silver, calcium, strontium, barium and lead salts have then been prepared from the ammonium salt. D. T. A. of ammonium and strontium salts have been carried out to investigate the thermal changes. The infrared spectra of the ammonium salt and its dehydrated product have been recorded, and the characteristic frequencies assigned.
  • J. Mohan Rao, U. V. Seshaiah
    1966 Volume 39 Issue 12 Pages 2668-2671
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The formation of an orange-red coloured water soluble chelate between uranyl ion an p-aminosalicylic acid with maximum absorption at 460 mμ is reported. The colour of the complex is fairly stable and attains maximum intensity at a pH 4.5. The composition of the complex has been evaluated by Job’s and mole ratio methods employing absorbance data and has been found to be 1 : 1 with respect to metal and ligand. The stability constants of the uranyl chelates of certain nuclear substituted salicylic acids, such as, 3-nitrosalicylic, 5-sulpho-salicylic, β-resorcylic and p-aminosalicylic acids have been determined and the validity of the linear relationship between ligand basicity and the metal chelate stability studied. Based on pH and adsorption studies, tentative structures for the above uranyl chelates have also been proposed.
  • Kazuko Ogino (née Ebata), Nobuyuki Tanaka
    1966 Volume 39 Issue 12 Pages 2672-2677
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The one-electron reduction wave of hexamminechromiuni(III) ions at the dropping mercury electrode splits into two steps by the presence of manganese (II) and ethylenediaminetetraacetato-manganate(II) (MnY2−; Y4− represents a quadrivalent ethylenediaminetetraacetate anion) ions. The limiting current of the first step was considered to depend on the rate of the formation of CrY2− by the substitution reaction of MnY2− and chromium(II) ions which were produced at the electrode by the reduction of the chromium(III) complex ions. From the change in the limiting current of the first step by the change of the concentrations of Mn2+, MnY2− and H+ the rate constants of the complex-forming reaction
    (Remark: Graphics omitted.)
    were obtained to be K1f=8×107 l.mol−1sec−1,K1b=4×104 l.mol−1sec−1 (ionicstrength 1.0, 25°C)
  • Seizo Misumi, Makoto Aihara
    1966 Volume 39 Issue 12 Pages 2677-2680
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The successive chelate formation constants for In(III)- and Eu(III)-IDA complexes were obtained by potentiometric titration and calculation by Bjerrum’s method. The values of logK1 and logK2 for the In(III)-IDA complex are 9.54 and 8.87, and those for the Eu(III)-IDA complex are 6.22 and 4.72, respectively. The electrode reactions of these complexes were studied polarographically and found to be irreversible and diffusion-controlled. The ionic states of these complexes before reduction in the vicinity of the electrode surface were estimated to be [InY2(OH)]2− or InY2 and Eu(H2O)x3+. The rate constant, (kf°)B, of the electron transfer for the Eu(III)-IDA complex was calculated to be 1.3×1020 cm.sec−1.
  • Tatsuya Sekine, Akira Koizumi, Mitsuo Sakairi
    1966 Volume 39 Issue 12 Pages 2681-2684
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The distribution of scandium(III) at a tracer concentration was determined between chloroform with acetylacetone or thenoyltrifluoroacetone and 0.1 M aqueous perchlorate solutions at 25°C. The change in the distribution ratio of the metal ion with the change in the chelating acid concentration or with the change in the hydrogen-ion concentration was explained in terms of the extraction of the tris chelate complexes into the organic phase and the formation of the primary complexes in the aqueous phases. The equilibrium constants in these systems were determined graphically, by a curve-fitting method to be as follows:
    Kex=[ScA3]org[H+]3⁄[Sc3+][HA]3org
    K1=[ScA2+]⁄[Sc3+][A]
    (Remark: Graphics omitted.)
  • Tadashi Nozaki, Takayasu Okuo, Hiroyuki Akutsu, Michiaki Furukawa
    1966 Volume 39 Issue 12 Pages 2685-2690
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The excitation curve for the 14N(p, α)11C reaction was measured up to a proton energy of 15 MeV.; the reaction was found to have a fairly high cross section for a sensitive determination of nitrogen by radioactivation. A convenient technique was developed for the rapid quantitative conversion of the irradiated graphite into carbonate within a closed system. This technique makes possible the determination of a trace (down to several p.p.b.) of nitrogen in pyrolytic graphite. Discussions of the possible interference (i. e., that of boron by the 11B(p, n)11C reaction) will also be given. The nitrogen content of the pyrolytic graphite sample was found to vary markedly according to the starting material and to the preparation conditions.
  • Fumihiro Honda, Yoshihiko Mizutani, Tsutomu Sugiura, Shinya Oana
    1966 Volume 39 Issue 12 Pages 2690-2695
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Volcanic gases from several active volcanoes in Japan have been analyzed for iodine and chlorine: Showashinzan (I=0.025–0.20 mg.I/kg.H2O, Cl=238–1830 mg.Cl/kg.H2O), Iwatesan (I=0.053–0.19, Cl=2720–3360), Issaikyoyama (I=0.030–0.087, Cl=104–213), Nasudake (I=0.16–3.9, Cl=188–9460), Yakedake (I=0.58–0.93, Cl=1250–1730), Kuju-Ioyama (I=0.13–1.3, Cl=266–8000), Kirishima-Ioyama (I=0.036–0.84, Cl=200–4200), and Miharayama (I=0.45–1.5, Cl=1640–2180). Each volcano has a characteristic I/Cl ratio. Analyses have also been made of hot-spring waters from the environs of Nasudake, Kuju-Ioyama, and Kirishima-Ioyama. It is indicated that the hot-spring waters are similar in I/Cl ratio to the volcanic gases from the same area.
  • Sueo Machi, Miyuki Hagiwara, Masao Gotoda, Tsutomu Kagiya
    1966 Volume 39 Issue 12 Pages 2696-2702
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The gamma-radiation-induced polymerization of ethylene was carried out/over the wide range of temperature from 30 to 200°C at pressure ranging from 100 to 400kg./cm2 and at dose rates from 2×103 to 4×105 rad./hr. It was shown that the rate of polymerization is rapidly accelerated at 30°C, that the degree of acceleration decreases with an increase in the reaction temperature, and that above 100°C the rate is independent of the time. It was correspondingly shown that the molecular weight of the polymer increases with the reaction time, at 30°C, that its increment for a unit of time decreases with an increase in the temperature, and that the molecular weight is independent of the time above 100°C. By means of a kinetical discussion it was concluded that the rate of the termination reaction, which is almost eliminated at 30°C, increases with the temperature and attains a value comparable to that of initiation above 100°C. The dose rate exponents of the polymerization rate and molecular weight were shown to vary with the reaction temperature. Namely, the exponents were evaluated as 0.9 and 0 at 30°C, 0.8 and −0.1 at 100°C, and 0.7 and −0.2 at 140 and 200°C, for the polymerization rate and the molecular weight respectively. It was assumed from these high exponents that the termination may occur above 100°C in a first-order reaction to a considerable extent. Under a constant pressure, the polymer yield was shown to decrease with the temperature from 30 to 60–80°C, and then to increase at high temperatures from 80 to 200°C. On the other hand, the molecular weight of the polymer simply decreases with the temperature from 30 to 200°C. The chain transfer reaction is considered to be almost negligible at 30–70°C. The number of polymer chains for a constant reaction time and monomer concentration is independent of the temperature from 30 to 70°C, while it increases with the temperature from 70 to 200°C. The effects of pressure on the polymer yield and molecular weight were also investigated at 140°C.
  • Kazuhiro Sasaki
    1966 Volume 39 Issue 12 Pages 2703-2706
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Four isomeric methylpseudoionones and two isomeric pseudoionones were separately synthesized by the Wittig reaction of citral a or citral b with the corresponding phosphonates. Two isomeric pseudoionones were also synthesized by the Wittig reaction of citral a or citral b with 2-oxopro-pylidenetriphenylphosphorane. The configurations and the conformations of the dienone systems in four methylpseudoionones and two pseudoionones were discussed on the basis of the infrared and ultraviolet absorption data.
  • Masahisa Hashimoto, Jiro Aritomi
    1966 Volume 39 Issue 12 Pages 2707-2713
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    β-p-Methyl, chloro, cyano and nitrobenzyl-L-aspartates were synthesized, and the respective homopolymers and copolymers of these β-(p-substituted benzyl)-L-aspartates with β-benzyl-L-aspartate were prepared. The introduction of a methyl, chloro, or cyano group into the para position of the aromatic ring in the side chain of poly-β-benzyl-L-aspartate (PBLA) also causes a reversal from the left- to the right-handed in the helical sense of the polypeptide in a chloroform solution, as in the case of the nitro group. The residue of the copolymers where the transition takes place contained: nitro, 20–30; cyano, 40–50; chloro, ca. 50; and methyl group, ca. 70mol.-%. These values may indicate the relative stabilities between the PBLA helix and poly-β-(p-substituted benzyl)-l-aspartate helices. These series of copolymers had no absorption band in the longer wavelength region except for a nitrobenzyl series, which had an absorption band at around 330 mμ. The absence of an absorption band resulted in a normal b0 value. The results suggest that the factors which determine the helical sense of the PBLA helix are not very simple and that the left-handed helix of PBLA is much less stable.
  • Masahisa Hashimoto
    1966 Volume 39 Issue 12 Pages 2713-2720
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The observation of the circular dichroism (240–290 mμ) due to the aromatic side chain indicates that, in a chloroform solution, even the side-chain aromatic rings of the copolyaspartate chain in the right-handed helix are in a regular arrangement to form an outer helix. On the contrary, for the copolyaspartate chain in the left-handed helix, the aromatic rings are much less regular. The ORD measurements indicate that, in a dimethylformamide solution, the poly-β-benzyl-L-aspartate chain is essentially in a random coil form, whereas the para-substituted derivatives are essentially in a right-handed helix. Accordingly, for each series of copolymers, the transition from a random coil form to a right-handed helix is observed as the molar content of the para-substituent is increased. The copolypeptide chain of β-benzyl-L-aspartate and β(p-methylbenzyl)-L-aspartate (molar ratio, 1:1) takes either the left-handed helix in a chloroform solution or the right-handed helix in a dimethylformamide solution. Accordingly, for this copolypeptide, the transition from the left to right-handed conformation is observed at the mixing volume ratio, 90 : 10, of the chloroform-dimethylformamide solution.
  • Teruaki Mukaiyama, Hajime Kouda, Kyoko Kodera
    1966 Volume 39 Issue 12 Pages 2721-2723
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Various alkyldihydrogen phosphates were obtained in good yields by reacting alcohols, dibenzylhydrogen phosphite, and bromine in the presence of triethylamine, followed by catalytic hydrogenation. When benzyl alcohol and diethyl phosphite were used in the above reaction, only the oxidation of the latter took place, giving diethylhydrogen phosphate in an excellent yield. These results suggest that the above phosphorylation of alcohol proceeds through a quaternary phosphonium salt, i. e., dibenzyloxyalkyloxyhydroxy phosphonium bromide, which is then converted into an alkylbenzylhydrogen phosphate. The effect of tertiary amines on this type of phosphorylation was also examined.
  • Hiroshi Minato, Hiroo Tateno, Hiroshi Yokokawa
    1966 Volume 39 Issue 12 Pages 2724-2728
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Benzalphenylhydrazone was oxidized with amyl nitrite and with sodium hypoiodite, and the products of the oxidation were analyzed. The products identified were dibenzaldiphenyltetrazone, α-benzilosazone and unoxidized benzalphenylhydrazone. The mechanism of the oxidation was discussed.
  • Kanji Tokuyama, Mitsuru Katsuhara
    1966 Volume 39 Issue 12 Pages 2728-2733
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    1, 3, 4, 5-Tetra-O-acetylsorbopyranosylureas were prepared from sorbopyranosyl chloride via 1, 3, 4, 5-tetra-O-acetylsorbopyranosylisocyanates. 1-Ureido- and 6-ureidosorbofuranoses were obtained from the corresponding aminosorboses. The transformations of the ureas thus obtained into N-(sorbose)thymines were achieved, although with difficulty, by the direct condensation of halogeno- or tosylsorboses with metal salts of thymine.
  • Michio Kobayashi, Asami Yamamoto
    1966 Volume 39 Issue 12 Pages 2733-2735
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Attempts to prepare a sulfinyl azide resulted in the formation of the sulfonyl azide, disulfide, and thiolsulfonate; of these products, the first two were considered to be disproportionation products of the intermediate, sulflnyl azide. The reaction of a sulfinic acid with hydrazoic acid gave a sulfonamide. No rearrangement similar to the Curtius or the Schmidt reaction was observed.
  • Michio Kobayashi, Asami Yamamoto
    1966 Volume 39 Issue 12 Pages 2736-2738
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Anhydrous hydrazine reacted with sulfinic esters under mild reaction conditions to give disulfides, which were in turn, upon prolonged heating, reduced by hydrazine to mercaptans. Aromatic thiolsulfonates and sulfonyl chlorides were also reduced by hydrazine, whereas aromatic sulfoxides and sulfinic acids were not reduced under comparable reaction conditions. A mixture of hydrazine with a sulfinic ester or another of the reducible sulfur compounds described above can hydrogenate carbon-carbon double bonds and triple bonds. A mechanism involving the intermediate formation of diimide is proposed.
  • Teruzo Asahara, Hideo Kise
    1966 Volume 39 Issue 12 Pages 2739-2744
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The telomerization of butadiene with its hydrochlorides (1-chlorobutene-2 and 3-chloro-butene-1) at low temperatures in the presence of cationic catalysts was investigated. The aim of the present investigation is to’ explore methods to control the molecular weight of the products with various reaction conditions, and to determine the properties and structure of the telomers obtained. The activity of several cationic catalysts at −50–−40°C, and the effects of the conversion and the ratio of chlorobutene to butadiene (RCl/Bu) on the yield and average molecular weights of the telomers were investigated. The products were divided into simple adducts and higher telomers by vacuum distillation. The fraction of the 1 : 1 adduct contained three isomers, one of which was 1-chlorooctadiene-2, 6. The structure and properties of the higher telomers were investigated by the aid of the infrared spectra, the average molecular weight, the iodine value, and elementary analysis. On the basis of the results, the reaction mechanism was discussed.
  • Mitsuo Masaki, Masatoshi Sugiyama, Suehiro Tayama, Masaki Ohta
    1966 Volume 39 Issue 12 Pages 2745-2749
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction of 1-chloro-2-oximino-3-butanone (I) with thiourea at 50–60°C gave S-(2-oximino-3-oxobutyl)thioformamidine hydrochloride (II), which upon being heated in an aqueous solution, then gave 2-amino-4-(1-oximinoethyl)thiazole (III). The treatment of I with amino-acetonitrile gave a mixture of N-(2-oximino-3-oxobutyl)aminoacetonitrile (IV) and N, N-bis(2-oximino-3-oxobutyl)aminoacetonitrile (V), which were confirmed as the corresponding amidoxime and benzoyl or p-nitrobenzoyl derivatives respectively. The reaction of I or 3-chloro-2-oximino-propiophenone with barium thiocyanate gave the corresponding acyclic thiocyanates (VI), while the reaction of anti-bromoacetophenone oxime with barium thiocyanate yielded 2-amino-4-phenylthiazole-3-oxide. That the cyclization reaction between the oximino and the cyano groups of V or VI did not occur seemed to favor the syn-chloromethyl conformation of the oximino group in I, a mechanism for which is hereby proposed.
  • Motoyoshi Oshima, Kan Kashima, Teruo Kubo, Haruro Tabata, Hiroshi Wata ...
    1966 Volume 39 Issue 12 Pages 2750-2755
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The raw material for the hydrocracking was prepared by treating alcohol fermented sulfite waste liquor with lime, desulfonating the thus-prepared slurry by heating, and deashing the precipitate with sulfur dioxide. The hydrocracking was run with a high-boiling fraction of lignin-hydrogenated oil as the solvent (pasting oil) and with Fe-promotor-sulfur as the catalyst. The yield of monophenols was 24% (based on klason lignin) with a 100% recovery of the pasting oil under reaction conditions of a temperature of 430°C, an initial hydrogen pressure of 130 kg./cm2, and a catalyst dosage of 3% (based on the lignin). The higher reaction pressure resulted in a slight increase in the yield of monophenols. The formation of non-volatile pitch decreased with the increase in the initial pressure up to 130 kg./cm2 but a further increase of the pressure exerted no effect. The higher reaction temperature gave more hydrogen absorption and a higher yield of monophenols, and less pitch formation and pasting oil recovery. However, it is essential to select reaction conditions where the highest yield of monophenols is obtained with a 100% recovery of the pasting oil.
  • Motoyoshi Oshima, Kan Kashima, Teruo Kubo, Haruro Tabata, Hiroshi Wata ...
    1966 Volume 39 Issue 12 Pages 2755-2759
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The components of the hydrocracking products of alcohol-fermented softwood sulfite waste lignin were identified by rectification, gas chromatography, and IR spectrophotometry. In the acidic fraction (b. p. 170–232°C phenol, o-cresol, 2,6-xylenol, m-cresol, p-cresol, 2-ethylphenol, 2, 4-xylenol, 2, 5-xylenol, 4-ethylphenol, 3-ethylphenol, 3, 5-xylenol, 2-(n-propyl)phenol, 3, 4-xylenol, 4-(n-propyl) phenol and 3-(n-propyl) phenol were identified. In the neutral fraction (b. p. 170–232°C) naphthalene, 2-methylnaphthalene, and tetralin were identified. In the fraction (b. p. 135–170°C) ethylbenzene, m-xylene, p-xylene, o-xylene, and N-propylbenzene were found. In the fraction boiling between 57 and 135°C toluene was identified.
  • Motoyoshi Oshima, Kan Kashima, Hiroshi Watanabe, Haruo Tabata, Teruo K ...
    1966 Volume 39 Issue 12 Pages 2760-2763
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Three types of raw material for lignin hydrocracking were prepared and their reactivities were compared in relation to the refined lignin reported in the authors’ previous paper (Bull. Chem. Soc. Japan, 39, 2750 (1966)). The raw materials were prepared; 1) by autoclaving the alcohol-fermented sulfite waste liquor (heat-precipitated lignin); 2) by drying the liquor (dried SWL), and 3) by concentrating the liquor (concentrated SWL). Although these three types of lignin are less costly to prepare, they showed poor reactivities in the hydrocracking process. Heat-precipitated lignin gave a 16–20% monophenol yield [Analyzed by rectification and gas chromatography (no alkaline extraction was conducted).] at a 100% recovery level of pasting oil. No definite monophenol yield figures could be concluded in the runs with dried or concentrated SWL because of the scattered data. The poor reproducibility of data in the cases of these two types of lignin is discussed.
  • Motoyoshi Oshima, Kan Kashima, Haruro Tabata, Hiroshi Watamabe, Teruo ...
    1966 Volume 39 Issue 12 Pages 2763-2767
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to find a more active catalyst than the standard catalyst (Bull. Chem. Soc. Japan, 39, 2750) (1966)), some seventeen materials were tested in the hydrocracking reaction of lignin. Although no catalyst was found that would alter the economic picture of the process, several interesting pieces of information were obtained. Selenium and zinc iodide gave a very high hydrogen absorption, indicating their activities as the catalyst. The reaction mechanism with these catalysts, seemed, however, very different from that with the standard catalyst. They resulted in high neutral yields and poor phenol yields. Cobalt octacarbonl, cobalt sulfide, ammonium molybdate, Raney iron, iron pentacarbonyl, nickel oxalate, and Ni-S showed fair activities. A closer evaluation of some of the above catalysts revealed that the standard catalyst was, at least at present, the most preferable catalyst.
  • D. S. Deorha, Padma Gupta
    1966 Volume 39 Issue 12 Pages 2768-2770
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • C. David Bass, Jack S. Margolis
    1966 Volume 39 Issue 12 Pages 2770-2771
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Kazuhiro Maruyama
    1966 Volume 39 Issue 12 Pages 2772-2773
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Hiroshi Kato, Hideyuki Konishi, Teijiro Yonezawa
    1966 Volume 39 Issue 12 Pages 2774-2775
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Masuo Murakami, Kozo Takahashi
    1966 Volume 39 Issue 12 Pages 2775-2776
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Yuko Hasegawa, Tatsuya Sekine
    1966 Volume 39 Issue 12 Pages 2776-2778
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Yoshiyuki Okamoto, J. C. Goswami
    1966 Volume 39 Issue 12 Pages 2778
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Harumitsu Kuwano, Michio Kondo
    1966 Volume 39 Issue 12 Pages 2779-2780
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Junko Kondo, Toshio Uchijima, Yukio Yoneda
    1966 Volume 39 Issue 12 Pages 2781-2782
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Kensuke Takahashi
    1966 Volume 39 Issue 12 Pages 2782-2783
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
feedback
Top