Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 41 , Issue 1
Showing 1-50 articles out of 70 articles from the selected issue
  • Tatsuya Sekine, Hidehiko Iwaki, Mitsuo Sakairi, Fumitake Shimada, Mari ...
    1968 Volume 41 Issue 1 Pages 1-7
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Liquid-liquid distribution behavior of sulfur(IV), selenium(IV) and tellurium(IV) in acid perchlorate media was studied at 25°C. The distribution of sulfur(IV) into carbon tetrachloride was determined by iodometry and that of selenium (IV) into methylisobutyl carbinol or of tellurium(IV) into hexane containing trioctylphosphine oxide was determined by radiometry. The changes in the distribution ratio caused by the changes in the hydrogen ion concentration were explained in terms of the distribution of sulfurous, selenious or tellurous acid as the non-charged form into the organic phase and the dissociation of these acids in the aqueous phase. The distribution constants as well as the dissociation constants of these acids were determined by a graphical method. In acid perchlorate media, sulfurous and selenious acids exist as neutral and mononegative species while tellurous acid exists as monopositive, neutral and mononegative species, and the neutral species exists only in a narrow hydrogen ion concentration range.
  • Kenji Sato
    1968 Volume 41 Issue 1 Pages 7-17
    Published: 1968
    Released: March 27, 2006
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    The condensation of methylolmelamine in the range of ca. pH 8–1 was investigated. An aqueous-dimethylsulfoxide (DMSO) solution (ca. 1 : 2, vol. ratio) was mainly used as the solvent, because it was revealed that the condensate in the latter stage of the condensation is soluble in DMSO solvent, and also that in this solvent methylolmelamine scarcely decomposes into a lower methylolmelamine liberating formaldehyde; then, the condensation mechanism of that methylolmelamine whose composition corresponds approximately to di-, tri-, and hexa-methylolmelamine, was investigated, not only in the early stage but also in the latter stage. It was found that the condensation rates of di- and tri-methylolmelamines (low methylolmelamines) in the early stage show maxima at ca. [HGl]/[methylolmelamine]=0.5 (molar ratio), i.e., at ca. pH= logK, where K is the equilibrium constant between the molecular form of the methylolmelamine and its conjugate acid, and that in hexa-methylolmelamine (high methylolmelamine) the above maximum appears at ca. [HCl]/[methylolmelamine]=0.5–1.0 (molar ratio). Also, the above maxima were found to shift toward smaller [HGl]/[methylolmelamine] (molar ratio) values as the condensation proceeded (the latter stage). From these results, a condensation mechanism was proposed for the early stage of the condensation.
  • K. L. Daluja, S. N. Srivastava
    1968 Volume 41 Issue 1 Pages 17-25
    Published: 1968
    Released: March 27, 2006
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    The stability of negative As2S3 sol of mean particle diameter 90 Å has been studied in presence of different valent cations viz. Na+, Ba2+, UO22+, Al3+ and Th4+ using D. L. V. O. theory. The zeta potential (assumed to be equal to the surface potential) of the sol particles was calculated from the electrophoretic measurements as a function of ionic strength. The knowledge of zeta potential permitted the calculation of repulsive energy VR, and the energy of attraction VA was estimated from physico-chemical data. The stability ratio, W was calculated from interaction profiles which were made from the combination of the two energies. Stability factor, F, was also estimated from the Derjaguin equation, but it was not satisfactory presumably owing to the exclusion of VA. In general, the interaction between As2S3 particles could be interpreted in the light of D. L. V. O. theory. The flocculation powers of cations were in the order of Al3+>Th4+>UO2+>Ba2+>Na+. The anomalous behaviour of thorium is perhaps due to its hydrolysis.
  • Seizo Misumi, Sigeo Kida, Toshiyuki Isobe, Akio Inazumi
    1968 Volume 41 Issue 1 Pages 25-33
    Published: 1968
    Released: March 27, 2006
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    The absorption spectra of praseodymium(III) and neodymium(III) complexes were measured in an aqueous alkaline solution with an excess of ligands. The experimental data being used, the Racah parameter, E3, and the Landè parameter, ζ4f, were calculated by the least-squares method on the assumption that the energy separation between J-levels of the 4fn-configuration is a function of E3 and ζ4f. The nephelauxetic effect in the Pr(III) and the Nd(III) complexes was then discussed by using the values of E3 thus obtained.
  • Jiro Tanaka, Masao Shibata
    1968 Volume 41 Issue 1 Pages 34-41
    Published: 1968
    Released: March 27, 2006
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    The electronic absorption spectra of three crystalline modifications of anthracene derivatives have been measured; they are the α and β form of 9, 10-dichloroanthracene and 9, 10-dibromo-anthracene. The assignment has been presented for each absorption band. The charge transfer absorption which is regarded to the transition between two stacked molecules has been observed in the α-form of 9, 10-dichloroanthracene; also a Rydberg type transition which has an out of plane polarization is found in this crystal starting at 290 mμ. It is unusually broad and is regarded as a band to band transition. The emission band has been measured at different temperature; it is found that excimer type emission is most prominent in the β-form of 9, 10-dichloroanthracene, in which intermolecular approach in the excited state will occur with less difficulty. A criterion for strong, medium, and weak interactions in the excited state is presented by comparing the shift, and the shape of the emission band with the intermolecular vibrational spacing. These results show that the charge transfer interaction and excimer formation are greatly dependent on the relative orientation of molecules, the π-electron overlap, and the difficulty of intermolecular approach in the excited state, particularly with its correlation to the steric repulsion of the bulky substituent groups.
  • Toshio Fukumi, Yuzuru Fujiwara, Yoji Arata, Shizuo Fujiwara
    1968 Volume 41 Issue 1 Pages 41-44
    Published: 1968
    Released: March 27, 2006
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    Proton exchange has been investigated in the system of water and isopropanol by means of high-resolution nuclear magnetic resonance. The rates of proton transfer have been obtained at different hydrogen ion concentrations and at different ratios of water and isopropanol. It has been shown that the exchange reaction is of higher order with respect to water and isopropanol concentrations. Possible mechanisms of proton transfer have been discussed, and values for their respective rate constants given.
  • Hisao Imai, Touji Hasegawa, Hiroshi Uchida
    1968 Volume 41 Issue 1 Pages 45-48
    Published: 1968
    Released: March 27, 2006
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    The composition of hexene isomers produced by the dimerization of propylene over a nickel oxide-silica-alumina catalyst has been examined under the following experimental conditions: 10–300 kg/cm2, 100 and 200°C. Under a typical set of experimental condition (50 kg/cm2, 200°C), eight hexene isomers, i.e. 4-methyl-trans-2-pentene, 4-methyl-cis-2-pentene, 2-methyl-1-pentene, trans-2-hexene, cis-2-hexene, 3-methyl-trans-2-pentene, 3-methyl-cis-2-pentene, and 3-methyl-1-pentene, have been found to be the primary products of the dimerization. Among these, more trans isomers are produced initially than the corresponding cis isomers for 4-methyl-2-pentenes and 2-hexenes, but the reverse is true for 3-methyl-2-pentenes. Under higher pressures, 2,3-dimethylbutenes are also produced at 200°C. A reaction scheme assuming the intermediates of cyclobutane derivatives has been proposed to explain the above findings. The scheme may also explain the unique order of the activity of the present catalyst for a series of n-olefins.
  • Sumio Ichiba, Mitsuo Mishima, Hiroshi Sakai, Hisao Negita
    1968 Volume 41 Issue 1 Pages 49-52
    Published: 1968
    Released: March 27, 2006
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    Molecular complexes of tin tetrachloride with some aliphatic compounds, such as alcohols and esters, were investigated by means of the Mössbauer effect due to 119Sn, irradiation being made by 23.8 keV γ-rays from the 119mSn in tin dioxide. Most of these complexes show quadru-pole splittings resulting from the addition of organic molecules to tin tetrachloride, although broad absorption curves are observed in some cases. The isomer shifts range from 0.30 to 0.45 mm/sec. They are much smaller than that of tin tetrachloride itself. The results are interpreted by taking account of the electronic structures of the complexes.
  • Morizo Tsuda, Kenji Kuratani
    1968 Volume 41 Issue 1 Pages 53-60
    Published: 1968
    Released: March 27, 2006
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    With the use of a single pulse shock tube of a magic hole type, the thermal decomposition of ketene was studied at temperatures from 1140 to 1530°K. The formation of carbon monoxide, that is, the disappearance of ketene, followed a kinetic order of 1.5 with respect to ketene and its rate constant was represented by
    k=10^14.2exp[(-65600±1100)/RT]l^1/2mol^-1/2sec^-1.
    The thermal decomposition of mixtures of ketene and ethylene in argon was also studied, and the formation of methylene radicals during the pyrolysis of ketene is deduced from the presence of propylene and cyclo-propane in the products of these three component reactants. The rate of ketene disappearance was not affected by the addition of ethylene, or nitric oxide. A chain mechanism in which methylene radicals play a principal part, and a combined molecular mechanism of first, and second orders were proposed tentatively to explain the observed 1.5th order reaction rate.
  • Tsutomu Okuda, Akira Nakao, Masaharu Shiroyama, Hisao Negita
    1968 Volume 41 Issue 1 Pages 61-64
    Published: 1968
    Released: March 27, 2006
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    The Zeeman effect of 35Cl pure quadrupole resonance was studied on a single crystal of the 2SbCl3·C6H6 molecular complex at room temperature; it was found that the Cl–Sb–Cl bond angles of two nonequivalent SbCl3 molecules are 96.2°, 94.7°, 92.2°; 94.5°, 92.8°, and 95.2°, with an uncertainty of 1°. The asymmetry parameters for the six chlorine atoms were found to be 0.085±0.001, 0.055±0.004, 0.117±0.005, 0.119±0.005, 0.112±0.005, and 0.160±0.007, listed in the order of decreasing resonance frequencies. The bond character of the Sb–Cl bond was also calculated from the quadrupole coupling constant. It was found that the Sb–Cl bond corresponding to the lowest resonance lines in each nonequivalent SbCl3 molecule has a larger ionicity than the remainder. Moreover, the former has less of a temperature dependence than the latter. Finally, this complex may be assigned to the Ci or C1 symmetry class from the patterns of zero-splitting and from the intensity ratios of the multiplet of the spectrum.
  • Isao Mochida, Jun-ichiro Take, Yasukazu Saito, Yukio Yoneda
    1968 Volume 41 Issue 1 Pages 65-70
    Published: 1968
    Released: March 27, 2006
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    In order to discriminate the natures of solid acids, the reactivity of methylene chloride with solid acids like alumina, silica-alumina and alumina-boria to give carbon monoxide and methyl chloride was studied with a pulse technique. The reactivities varied about ten thousandfold among these solid acids. The methyl chloride formation was predominant on alumina particularly at low reaction temperatures, with a distinctly small activation energy in comparison with that on silica-alumina or alumina-boria. The nature of the active sites for this reaction was discussed in connection with the effect of the calcination temperature as well as of the sodium ion-poisoning on activity. Furthermore, it was found that the feature of this reaction was in marked contrast with the typical solid acid catalysis such as the dealkylation reaction of alkylbenzenes. The reaction of methylene chloride with a set of the surface hydroxyl group and the oxidizing site is assumed to give methyl chloride through a radical mechanism.
  • Fumio Hine, Shusei Inuta
    1968 Volume 41 Issue 1 Pages 71-75
    Published: 1968
    Released: March 27, 2006
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    The solubility of chlorine in a concentrated HCl solution at various conditions of concentration, partial pressure, and temperature was determined. The concentration of chlorine in a solution as the sum of Cl2 and Cl3 was found to be proportional to the partial pressure of chlorine in the gas phase, and its slope was a function of the HCl concentration and the temperature Empirical equations representing these relations and the solubility of chlorine were obtained. It was confirmed that the results agreed with the experimental data in the 2–10 N HCl concentration range at partial pressures of chlorine lower than 1 atm and at 30–90°C. Such physico-chemical properties as the Gibbs free-energy change were considered by using the data of solubility, and the behavior of the system consisting of Cl, Cl2, and Cl3 was discussed.
  • Kozo Hirota, Jun’ichi Takezaki
    1968 Volume 41 Issue 1 Pages 76-82
    Published: 1968
    Released: March 27, 2006
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    Mass spectra of eight aliphatic mono- and di-ethers have been measured with apparatuses of both ordinary and high resolution type, and scission probability of their skeletal bonds has been determined. By application of the molecular orbital theory on bond-scission by electron impact, the scission probability of the skeletal bonds has been evaluated, using only a few constants peculiar to the C–O bond so as to determine the molecular orbital. Comparison between theory and experiment has been found satisfactory on such ethers, even though they have lone-pair electrons in the inner part of the molecules. Thereby, scission of the skeletal bond has been shown explainable quite well by the primary processes in most ethers, except highly symmetric or large ethers.
  • Takako Amano, Haruo Kuroda, Hideo Akamatu
    1968 Volume 41 Issue 1 Pages 83-87
    Published: 1968
    Released: March 27, 2006
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    The polarized absorption spectra of the single crystal were observed for six molecular compounds which involve chloranil as the electron acceptor and aromatic amines as the electron donor. The molecular compounds of N,N-dimethylaniline, 1-naphthylamine, and N,N-dimethyl-2-naphthylamine have a non-ionic ground state. In these cases, the locations of the charge-transfer bands in the crystal spectra are similar to those of the corresponding bands of the 1 : 1 molecular complexes formed in the solution. The solid molecular compounds of p-phenylenediamine, N,N,N′,N′-tetramethyl-p-phenylenediamine, and diaminodurene can be regarded as ionic crystals composed of the positive ion of the donor and the negative ion of the acceptor. In these cases, the absorption bands associated with the component ions are observed in the crystal spectra, but they are broadened and appreciably shifted to a higher energy as compared with the case of the solution spectra of the ions. The absorption band associated with the charge transfer between ions is observed in the near-infrared region of the crystal spectra of these molecular compounds.
  • Yoshimasa Takashima, Shigeru Ohashi
    1968 Volume 41 Issue 1 Pages 88-93
    Published: 1968
    Released: March 27, 2006
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    The Mössbauer spectra have been measured for sixteen samples of natural minerals, including siderite, vivianite, garnets, olivines, pyroxenes, and other silicate minerals, The spectra were analyzed for the isomer shifts and quadrupole splittings, and the information thus obtained was correlated with the oxidation states of irons and the crystal structure of minerals. The relative abundances of the various sites present in a given mineral were also estimated by measuring the relative intensities of the absorption peaks in the resolved spectrum of the mineral. All the basic Mössbauer spectral patterns observed for the natural minerals are presented in graphic form.
  • Goro Yamaguchi, Kazutaka Suzuki
    1968 Volume 41 Issue 1 Pages 93-99
    Published: 1968
    Released: March 27, 2006
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    Besides the so-called β-Al2O3 (R2O·11Al2O3; R=Na or K), there have been found two kindred compounds with approximate formulas, R2O·7Al2O3 (β′-Al2O3) and R2O·5Al2O3(β″-Al2O3). The structure determination of the latter two compounds was undertaken; the results are compared with the structure of β-Al2O3 in the present paper. These three structures are composed of spinel layers of the same configuration. The structures of β and β′ are very similar to each other, both equally bearing a layer-stacking according to a two-fold screw symmetry, while β″ differs from these two in exhibiting another way of layer-stacking, according to a three-fold screw symmetry.
  • Taichi Sato
    1968 Volume 41 Issue 1 Pages 99-105
    Published: 1968
    Released: March 27, 2006
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    The partition of uranium(VI) between sulphuric acid solutions and solutions of di-n-octyl-amine (DOA) in benzene has been investigated at different concentrations of sulphuric acid, solvent and aqueous uranium, and at different temperatures. The acidity and the water content of the organic phase, and the effect of the organic solvent on the extraction have also been examined. An infrared spectral study has been made of the organic solutions. The mechanism of the extraction of uranium from sulphuric acid solutions by DOA is discussed on the basis of the results obtained, and a composition is proposed for the complex formed in this extraction system.
  • S. K. Ramalingam, S. Soundararajan
    1968 Volume 41 Issue 1 Pages 106-110
    Published: 1968
    Released: March 27, 2006
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    Diphenyl sulphoxide complexes of nine lanthanide perchlorates of the general composition [Ln(DPSO)6](ClO4)3 where Ln=La, Ce, Pr, Nd, Sm, Gd, Ho and Yb and Y have been synthesised and characterized. Infrared studies indicate coordination through the oxygen atom of the ligand and the retention of the Td symmetry of the perchlorate group. The molar conductance and cryoscopic studies suggest a coordination number of six for the metal ions. Cryo-scopic studies in DMSO indicate that DMSO is a better donor than DPSO. DTA and UV data are also presented.
  • Akiko Furuhashi, Kunihiko Watanuki, Akira Ouchi
    1968 Volume 41 Issue 1 Pages 110-114
    Published: 1968
    Released: March 27, 2006
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    New compounds of the type M(C5H7S2)2Cl4, where M is Mn(II) or Hg(II), were obtained by passing hydrogen chloride and hydrogen sulfide through ethanol solutions containing acetylacetone and metal chlorides. Such adducts seem to be isostructural to iron compounds, and are stable in the solid state. They seem to decompose when brought into contact with such solvents as water, methanol and dimethylformamide. Their magnetic susceptibilities show that these compounds are all bivalent. The infrared spectra and electronic spectra resemble those of the dithioacetylacetonato iron compound.
  • Toshikazu Mitsuji
    1968 Volume 41 Issue 1 Pages 115-119
    Published: 1968
    Released: March 27, 2006
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    The behavior of Pa (IV) during extraction with TTA was investigated in perchlorate, chloride, and sulfate solutions (pH 0.4–1.1). In perchlorate and chloride solutions, the extraction equilibrium may be written as:
    Pa(OH)_2^2++4HT\ ightleftharpoonsPaT_4+2H_2O+2H^+
    On the other hand, the extraction by TTA from the sulfate solution may be described as:
    Pa(SO_4)(OH)^++4HT\ ightleftharpoonsPaT_4+HSO_4^-+H_2O+2H^+
    Therefore, the formation of the sulfato-complex of Pa(IV) is considered to occur as follows:
    Pa(OH)_2^2++HSO_4^-\ ightleftharpoonsPa(SO_4)(OH)^++H_2O
    The equilibrium constant for the above reaction has been determined to be 320 at the ionic strength of 0.50 (temperature: 10±0.5°C).
  • Takanori Suzuki, Tomihito Kambara
    1968 Volume 41 Issue 1 Pages 119-126
    Published: 1968
    Released: March 27, 2006
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    The line intensities of Si and Mn appear much more strongly in the spectrochemical analysis of high-carbon low-alloy steels when a low-voltage spark is employed. Considering the change in the line intensity with the time under various excitation conditions with graphite and zinc counter-electrodes, the present authors have established an improved method for the spectrochemical determination of Si and Mn. The effect of the heat-treatment on the metallurgical structure has been investigated by means of an electron-probe microanalyzer, and the results compared with the spectrochemical data.
  • Mutsuo Kodama, Chifumi Sasaki
    1968 Volume 41 Issue 1 Pages 127-130
    Published: 1968
    Released: March 27, 2006
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    The solution equilibria between BT and lead(II)-NTA or cadmium(II)-EDTA-OH chelates were studied spectrophotometrically, and the composition and the stability constants of the BT chelates of these metal ions were determined. In the presence of an excess amount of NTA or EDTA-OH, lead(II) and cadmium(II) ions join with BT to form a chelate with a 1-to-1 composition. The magnitude of the stability constants (1013.19 and 1012.74 respectively, μ=0.30) can explain satisfactorily the well-known experimental fact that BT can be used as a metallochromic indicator in Pb(II)- and Cd(II)-EDTA titrations.
  • Muraji Shibata, Hiroaki Nishikawa, Kinya Hosaka
    1968 Volume 41 Issue 1 Pages 130-135
    Published: 1968
    Released: March 27, 2006
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    When a hundred per cent excess of racemic α-alanine was reacted, in the presence of activated charcoal, with a reaction mixture of tricarbonatocobaltate(III) and L-asparate, water-insoluble β-tris(alaninato) cobalt (III) was precipitated. The recovery of alanine from this triscomplex showed a partial resolution; the D form of alanine was preferentially complexed, and the optical purity of the alanine recovered was about 38%. Spectroscopic measurements (absorption, ORD and CD) showed that the predominantly-existing species in the above reaction mixture was the (−)-[Co CO3(L-asp)2]3− anion, and that the reaction of this complex anion with racemic alanine led to the predominant formation of β(−)-[Co(D-ala)2(L-ala)] (the (−) sign refers to the sign of the Cotton effect in the first absorption band region). Similar experiments were carried out with D-aspartate and L-glutamate in place of L-aspartate. Through all the experiments, we have found that the complexes which are effective for the resolution of racemic alanine and the product or tris(alaninato) cobalt (III) have the same sign of the Cotton effect in their first-band regions.
  • Shuichi Hamada, Tadao Sato, Toshiaki Shirai
    1968 Volume 41 Issue 1 Pages 135-139
    Published: 1968
    Released: March 27, 2006
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    The viscoelastic behavior of selenium and of partially-chlorinated selenium was studied by the dilatometric method. The glass transition temperature, Tg, of selenium was determined to be 32.0°C at a cooling rate of 0.2°C/min. The glass transition temperature decreased linearly with the reciprocal of the average chain length of selenium. The chain length was calculated using the degree of chlorination. An abrupt increase in Tg was observed at a chlorine content of about 0.013%. The volume-time curves obtained by the determination of the volume of selenium in the neighborhood of Tg were superposed on each other by sliding them along the abscissa. The values of the shift factor and of Tg fit well in Williams, Landel and Ferry’s equation. The parameters in the WLF equation, C1g and C2g, of selenium were calculated to be 6.86 and 28.6 respectively. Both the parameters increased with an increase in the chlorine content up to 0.0125%, and reached the values of usual polymers above 0.0125%. The WLF fg value of selenium was calculated to be 6.33×10−2. This value decreased with an increase in the chlorine content, and reached the universal value of usual polymers (2.5×10−2) when the chlorine content was more than 0.0125%. The chlorine content corresponds to 0.0125% when all the radicals at both ends of the linear chain molecules of selenium have been used in forming bonds with chlorine atoms. Therefore, it may be concluded that the existence of radicals at the molecular ends of selenium chains brings about an augmentation of the fraction of the free volume at Tg.
  • Motoo Yasuda
    1968 Volume 41 Issue 1 Pages 139-141
    Published: 1968
    Released: March 27, 2006
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    The viscosities of aqueous solutions containing cobalt complexes formed with ammonia, ethylenediamine (en), propylenediamine (pn), 2,2′-bipyridine (bip), 1, 10-phenanthroline (phen), and ethylenediaminetetraacetic acid (H4edta) were determined with a Cannon-Fenske capillary viscometer. Measurements were made in a Shibata viscosity bath maintained at 25±0.01°C. The Jones-Dole viscosity B-coefficients of Co(III) complex cations formed with NH3, en, pn, bip, and phen increase in that order. There is no significant difference between the B-coefficients of [Cobip3]3+ and [Cobip3]2+, or [Cophen3]3+ and [Cophen3]2+. On the other hand, a pronounced difference is found between the B-coefficients of [Coedta] and [Coedta]2−. This might suggest that there is a marked difference in the structure of [Coedta] and [Coedta]2− anions.
  • Koji Kusashio, Masaharu Yoshikawa
    1968 Volume 41 Issue 1 Pages 142-149
    Published: 1968
    Released: March 27, 2006
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    Several reactions accompanied by the phosphorylation of 2′, 3′-O-isopropylidene nucleosides with phosphoryl chloride in the absence of an organic solvent were investigated. When the reaction temperature exceeded 30°C, 2′, 3′-O-isopropylideneinosine gave 5′-chloro-5′-deoxy 2′, 3′-O-isopropylideneinosine and 5′-deoxy-2′, 3′-O-isopropylidene-3, 5′-cycloinosine. This cycloinosine, was then further subjected to rapid cleavage in a pyrimidine ring to give 5-amino-4-carbamoyl-N5, 5′-cyclo-1-β-D-(5′-deoxy-2′, 3′-O- isopropylideneribofuranosyl)-imidazole, 5-amino-4-cyano-N5, 5′-cyclo-1-β-D-(5′-deoxy-2′, 3′-O-isopropylideneribofuranosyl)-imidazole, and the N5-formyl derivative of the latter. Similar sequences of the chlorination at the 5′-position and the cyclization between 3 and 5′-positions were observed in the case of 2′, 3′-O-isopropylideneguanosine, but the resulting 5′-deoxy-2′, 3′-O-isopropylidene-3, 5′-cycloguanosine was not susceptible to ring cleavage under the conditions used. The factors affecting these reactions were described, and possible mechanisms were proposed.
  • Masao Iwamoto, Sadao Yuguchi
    1968 Volume 41 Issue 1 Pages 150-155
    Published: 1968
    Released: March 27, 2006
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    A new catalyst consisting of a cobaltous chloride-ditertiary phosphine complex and an organoaluminum compound was found to be effective for the selective preparation of 1, 4-hexadiene by the reaction of butadiene with ethylene. The effects of the reaction variables on the activity and on the selectivity in 1, 4-hexadiene formation were studied. It is considered that a coordination of the ditertiary phosphine on the catalytically activated intermediate is essential for the selective catalysis. A reaction mechanism is proposed which involves an activated hydrido-cobalt complex as intermediate.
  • Junji Furukawa, Tsuneo Kakuzen, Hiroyuki Morikawa, Ryuzo Yamamoto, Osa ...
    1968 Volume 41 Issue 1 Pages 155-158
    Published: 1968
    Released: March 27, 2006
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    Trimethylcyclododecatriene was prepared by the oligomerization of pentadiene, using the diethylaluminum chloride-titanium tetrabutoxide system as a catalyst. The resulting oligomer was fractionated by vapor-phase chromatography into geometrical (cis and trans) and structural (head-to-tail and head-to-head) isomers with respect to the pentadiene units involved. The structures of these isomers were proposed on the basis of infrared and NMR spectra of the oligomers and their hydrogenated products. The results of the oxidative degradation of the oligomers were compatible with the proposed structures. Further, the existence of stereoisomers was shown by resolution and asymmetric oligomerization. The resolution of d- and l-enantiomers was carried out through the asymmetric hydroboration of the oligomers, while the asymmetric oligomerization was achieved using the titanium menthoxide-diethylaluminum chloride system as a catalyst.
  • Yoshinobu Takegami, Yoshihisa Watanabe, Takeaki Mitsudo, Isao Kanaya, ...
    1968 Volume 41 Issue 1 Pages 158-161
    Published: 1968
    Released: March 27, 2006
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    The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4, and K2Fe2(CO)8) and olefin oxides has been studied. Styrene oxide reacts readily with these carbonylates and with carbon monoxide under an atmospheric pressure and at 30°C. As the reaction products, styrene, ethylbenzene, and α- and β-phenylethyl alcohol are obtained. The major product is styrene or β-phenylethyl alcohol for the reaction of K2Fe(CO)4 or KHFe(CO)4 and K2Fe2(CO)8 respectively. The effects of solvents and additives are examined. Further, propylene oxide and epichlorohydrin are found to react with K2Fe(CO)4 and carbon monoxide to give not only carbonylated products, but also propylene. The results indicate that olefin oxides are generally reduced with K2Fe(CO)4 and carbon monoxide to give the corresponding olefins and carbon dioxide.
    (Remark: Graphics omitted.)
  • Masaru Iwanami, Toshiko Numata, Masuo Murakami
    1968 Volume 41 Issue 1 Pages 161-165
    Published: 1968
    Released: March 27, 2006
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    By the hydrolysis of pyridoxal-5-phosphate Schiff bases, pyridoxal-5-phosphate was prepared in a crystalline form without any further purification. Pyridoxal-5-phosphate Schiff bases were prepared in good yields by the phosphorylation of pyridoxal Scruff bases and were easily purified by alkali-acid reprecipitation. The pyridoxal-5-phosphate thus obtained was demonstrated to be identical with an authentic sample by a study of its UV, IR, and NMR spectra.
  • Akio Sakurai, Hiroshi Midorikawa
    1968 Volume 41 Issue 1 Pages 165-167
    Published: 1968
    Released: March 27, 2006
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    The reactions of ethyl acetoacetate with cyclic ketones and aromatic methyl ketones by using excessive ammonium acetate gave some heterocyclic compounds, such as 2-hydroxy-4-methyl-5, 6, 7, 8-tetrahydroquinoline (III), 2-hydroxy-4-methyl-6, 7-dihydro-5H-1-pyrindine (IV), and 2-hydroxy-4-methyl-6-alkyl-pyridines (VI). The structures of these compounds were investigated by means of their infrared and NMR spectra.
  • Youji Komatsu
    1968 Volume 41 Issue 1 Pages 167-171
    Published: 1968
    Released: March 27, 2006
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    Xylenes, mainly consisting of ρ-xylene and o-xylene, were selectively synthesized by the dehydrocyclization of 3-methyl heptatriene-1, 4, 6 (MHT) using a chromia-alumina catalyst. MHT was easily converted to xylenes in a good yield; this reaction proceeded even under mild conditions, as at 200°C. The effects of the catalyst composition, and the influence of the reaction temperature on the conversion of MHT, the xylene yield, the by-products, etc., were studied.
  • Tsutomu Kagiya, Tomizo Kondo, Shizuo Narisawa, Kenichi Fukui
    1968 Volume 41 Issue 1 Pages 172-176
    Published: 1968
    Released: March 27, 2006
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    The copolymerization of N-phenylethylenimine and β-propiolactone was carried out at 0°C in an acetonitrile solution. N-Phenylethylenimine and β-propiolactone copolymerized without any catalyst to give a powdery or a resinous polymer. From the results of a study of the infrared spectrum, X-ray diffraction, differential thermal analysis, and hydrolyses of the copolymer, it was concluded that the homopolymerization of neither monomer took place, and that the copolymer contained the ester structure of (Remark: Graphics omitted.)-in the main chain. The monomer reactivity ratios of N-phenylethylenimine (r1) and β-propiolactone (r2) were estimated to be r1=7.5 and r2=0.15.
  • Michinori Oki, Hiizu Iwamura, Jun-ichi Aihara, Hiroshi Iida
    1968 Volume 41 Issue 1 Pages 176-182
    Published: 1968
    Released: March 27, 2006
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    The O–H stretching absorption (νO–H) spectra of some keto-alcohols have been examined. The νO–H shift to the lower frequency due to the intramolecular O–H··· bonding can roughly be correlated to the geometry of the hydroxyl group relative to the n-electrons on the carbonyl oxygen. When the bonding is forbidden because of the conformational restriction, a weaker interaction between the hydroxyl group and the π-electrons on the carbonyl group is observable as the lower shift of the νO–H by 10–30 cm−1 as far as the conformation is favorable for the interaction.
  • Noriyoshi Inukai, Kohzi Nakano, Masuo Murakami
    1968 Volume 41 Issue 1 Pages 182-186
    Published: 1968
    Released: March 27, 2006
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    The phenol resin is useful as support of the solid phase peptide synthesis. Its use is particularly advantageous for the synthesis of the N-protected peptide fragments, and those which have the intramolecular disulfide bond, such as oxytocin. In the latter case, the application of S-ethylmercapto group as the protector of thiol group of cysteine residue was combined successfully. Oxytocin and physalaemin derivatives were thus synthesized.
  • Yoshio Iwakura, Keikichi Uno, Nobuo Nakabayashi, Takakazu Kojima
    1968 Volume 41 Issue 1 Pages 186-191
    Published: 1968
    Released: March 27, 2006
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    Reactive monomers derived from p-vinylbenzoic acid have been prepared which have both a vinyl group and another functional group for addition reaction or condensation reaction. The radical polymerization of these monomers gives high polymers. Monomer reactivity ratios in relation to styrene were obtained for three of these monomers. Plots of Alfrey-Price’s e value vs. Hammett’s σ value show a linear relationship in the case of substituted styrenes. σ values are then estimated by this relation, using e values based on the monomer reactivity ratios. The σ constants assumed for the COCl, (Remark: Graphics omitted.), and NCO substituents are 0.71, 0.64, and 0.27 respectively. These σ values are confirmed by other supporting facts.
  • Takashi Maeda, Kazuo Tori, Masako Ohtsuru, Kanji Tokuyama
    1968 Volume 41 Issue 1 Pages 191-197
    Published: 1968
    Released: March 27, 2006
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    The PMR spectra of 2,2′-anhydro-2-C-hydroxymethyl-l,3 : 4,6-di-O-isopropylidene-L-sorbitol were examined in several solvents to confirm its structure. The conformation of this molecule is also discussed.
  • Yoshio Okamoto, Heimei Yuki, Shunsuke Murahashi
    1968 Volume 41 Issue 1 Pages 197-203
    Published: 1968
    Released: March 27, 2006
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    The anionic polymerization of trans-β-methylstyrene by n-butyllithium was carried out in hydrocarbon solvents and in tetrahydrofuran. In hydrocarbon solvents the monomer was consumed by n-butyllithium, but gave no polymer insoluble in methanol. In tetrahydrofuran the polymerization proceeded rapidly, giving a polymer insoluble in methanol. This polymer was produced by the normal addition polymerization of a C=C double bond. The relatively lower degree of polymerization of poly-β-methylstyrene indicated a chain transfer in the reaction. The chain transfer reaction due to the active hydrogen of a methyl group in this monomer was also observed by means of the electronic spectra of the reaction mixtures. The polymer anion was converted to inactive anions at high temperatures.
  • Takayuki Otsu, Toshio Ito, Yoshihiro Fujii, Minoru Imoto
    1968 Volume 41 Issue 1 Pages 204-207
    Published: 1968
    Released: March 27, 2006
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    In order to clarify the effects of the alkyl substituents on the reactivities of methacrylate monomers toward the attack of a radical, the copolymerizations of a series of nuclear-substituted phenyl methacrylates with styrene were investigated. From the results, the monomer reactivity ratios and the Alfrey-Price Q, and e values were determined. It was found that the relative reactivities toward the polystyryl radical were not correlated with the ordinary Hammett equation, but a linear relationship was obtained with a modified Hammett equation which contained a term of the resonance contribution by the substituents. Accordingly, it was considered that the reactivities of substituted phenyl methacrylates depend on both polar and resonance effects caused by the substituents.
  • Tetsuo Nozoe, Shuichi Seto, Takashi Toda
    1968 Volume 41 Issue 1 Pages 208-211
    Published: 1968
    Released: March 27, 2006
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    The structure of the condensation product of 2-amino-3-ethoxycarbonyl-1-azaazulene and formamide is proved not to be the expected cyclohepta[2,3]pyrrolo[5,4-d]pyrimidine derivative, but 5,6-pentamethylene-7H-pyrrolo[2,3-d]pyrimidin-4(3H)-one. The chemical properties of the obtained pyrrolo-pyrimidine are investigated, and then the tautomerism of the above compound is discussed.
  • Takao Oshika, Hiroyoshi Tabuchi
    1968 Volume 41 Issue 1 Pages 211-217
    Published: 1968
    Released: March 27, 2006
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    Norbornene and such of its derivatives as exo-5,6-trimethylene norbornene (exo-TMN) and endo-dicyclopentadiene (endo-DCPT) have been polymerized via ring cleavage to high-molecularweight polymers, soluble in aromatics, by the use of MoCl5, WCl6, and ReCl5 catalysts in a carbon tetrachloride solvent. The ring-opening polymers obtained by MoCl5 have a trans-structure almost exclusively, on the other hand the polymers obtained by ReCl5 are rich in cis structures and those obtained by WCl6 are mixtures of the two. The reactivities of the monomers on those catalysts have been found to have the order of decreasing reactivity: exo-TMN>NE>endo-DCPD. In the ring-opening polymerization of norbornene by MoCl5, carbon disulfide and carbon tetrachloride have been found to be effective solvents. The yield increases with the rise in temperature and also upon the addition of a catalytic amount of tertiary amines in the midst of the polymerization procedure, while the structures of the polymers obtained do not change. The Co-catalyst H2O is not necessary. Chlorine atoms are found in the polymers. Those results suggest that the ring-opening polymerization of norbornene over MoCl5 occurs through a specific coordinated mechanism.
  • Takeo Sato, Sadatoshi Akabori, Masatsune Kainosho, Kazuo Hata
    1968 Volume 41 Issue 1 Pages 218-221
    Published: 1968
    Released: March 27, 2006
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    The NMR spectra of [2.2]metacyclophane have been shown to be held unchanged over a wide range of temperature, ca. −80 to 190°C, indicating that the ten-membered ring system undergoes no inversion and is frozen in a chair conformation. It may, then, be expected that suitably substituted derivatives of [2.2]metacyclophane would become disymmetric due to restricted inversion; such was proved to be the case by carrying out the optical resolution of the 4, 14-di-substituted derivatives. The 4,14-dimethyl derivative was resolved by means of a complex formation with Newman’s reagent, [α]57826=−3.4 and +4.2°. 4,14-Dicarboxylic acid was also resolved by converting it to the quinine salt, [α]D22=+5.0°.
  • Takeo Sato, Akihiko Takatsu, Yoshitaka Saito, Takafumi Tohyama, Kazuo ...
    1968 Volume 41 Issue 1 Pages 221-225
    Published: 1968
    Released: March 27, 2006
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    The reaction of dimethyl sulfoxide-polyphosphoric acid mixture with benzylic alcohols has been shown to afford a complex mixture of the products; this is in contrast to the case of aliphatic alcohols, which yield the corresponding acetal as the major product. By carrying out reactions using several benzylic alcohols and a series of benzyl alcohols, it was found that, in addition to the acetal formation reaction, dehydration and oxidation reactions, as well as a methyl thioether-formation reaction, were occurring. Possible pathways for the formation of these products are presented.
  • Kazuhide Miyazaki
    1968 Volume 41 Issue 1 Pages 225-229
    Published: 1968
    Released: March 27, 2006
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    The fundamental effects of carbon monoxide on UO2-pellet densification are described. A high density of more than 95% of the theoretical level is attained using carbon monoxide as the sintering atmosphere at a low sintering temperature of 1400°C for laboratory-processed UO2powders. An approximate prediction of the density for any given UO2 powder may be made from the following two experimental criteria: (a) The experimental activation energy for the rate of dissolution of the material into nitric acid may be taken as a measure for the low-temperature sinterability. The density of sintered oxides rises to a maximum at a point where the value of the activation energy for dissolution is about 20 kcal/mol, which is actually very close to the value for the diffusion of oxygen in uranium oxides. (b) The relative intensity of the (220) peak of the X-ray diffraction pattern furnishes another foundation for judging the densification behavior of the UO2 sample.
  • Tamon Moriya, Toichi Oki, Seiki Yamaguchi, Shiro Morosawa, Akira Yokoo
    1968 Volume 41 Issue 1 Pages 230
    Published: 1968
    Released: March 27, 2006
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  • Kensuke Takahashi, Ryuzo Asami
    1968 Volume 41 Issue 1 Pages 231-232
    Published: 1968
    Released: March 27, 2006
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  • Norio Kunieda, Shigeru Oae
    1968 Volume 41 Issue 1 Pages 233
    Published: 1968
    Released: March 27, 2006
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  • Shûichi Hayashi, Nanao Hayashi, Katsumi Yano, Masayoshi Okano, T ...
    1968 Volume 41 Issue 1 Pages 234-236
    Published: 1968
    Released: March 27, 2006
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  • Tadashi Sasaki, Shoji Eguchi, Takeshi Toru
    1968 Volume 41 Issue 1 Pages 236-238
    Published: 1968
    Released: March 27, 2006
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  • Tadashi Sasaki, Shoji Eguchi, Takeshi Toru
    1968 Volume 41 Issue 1 Pages 238-240
    Published: 1968
    Released: March 27, 2006
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