Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 10
Showing 1-50 articles out of 59 articles from the selected issue
  • Tanekazu Kubota, Hiroshi Miyazaki
    1966 Volume 39 Issue 10 Pages 2057-2062
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Polarograms of twenty-three pyridine N-oxide derivatives substituted at γ- and β-positions were extensively measured at various pH’s. The half-wave reduction potential, E1⁄2, was expressed by the form −E1⁄2=a[pH]+b. The wave height due to the reduction of the \eqslantgtrN→O group decreased with an increase in the pH in a pH region over ∼6. This phenomenon was common to all the compounds studied here; it was thought to be useful in identifying an aromatic N-oxide group by the polarographic method. The E1⁄2 plot against Hammett’s σ value of the substituent satisfied a linear relation well, and the slope of Hammett’s ρ value was positive. This indicates that the reduction process is nucleophilic. The linear relation was explained qualitatively on the basis of the MO theory by applying the second-order perturbation method.
  • Yoshihide Kotera, Kazuo Sato, Akihiro Miyayama
    1966 Volume 39 Issue 10 Pages 2063-2066
    Published: 1966
    Released: March 27, 2006
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    A recording, photometric, particle-size analyzer has been developed which is useful in measuring the particle-size distributions of powdered materials in the subsieve range. Provision for continuously moving the optical system upwards allows for rapid analysis of the finer particles, while by moving the system downwards accurate analysis of the particles with a larger density is possible. It was ascertained that the movement of the optical system has no effect on the results obtained.
  • Kunio Ohashi, Kazuo Sasaki, Shigeo Nagaura
    1966 Volume 39 Issue 10 Pages 2066-2071
    Published: 1966
    Released: March 27, 2006
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    The formation and reduction rates of the oxide layer of the platinum electrode were investigated by triangular-wave voltammetry and chronopotentiometry. A rate equation for the anodic process has been proposed in order to describe the fact that the electrode potential increases linearly with an increase in the surface concentration of oxygen. The cathodic reduction of surface oxide obeys the second-order rate law with respect to the amount of oxide covering the surface.
  • Takeo Ozawa
    1966 Volume 39 Issue 10 Pages 2071-2085
    Published: 1966
    Released: March 27, 2006
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    This paper presents a rigorous new theory of differential thermal analysis, taking account of the temperature gradient in the sample. From this consideration, a new quantitative method is proposed, where a solid-cell holder of low thermal conductivity is set between a sample cell and a metal block, and a thermocouple is inserted tightly between the outside wall of the cell and the cell holder. By means of this arrangement, the peak area becomes proportional to the heat of transformation, irrespective of the kinds and the states of samples and operational variables. The experimental verification using various samples and the effect of several operational variables, such as the heating rate, the concentration of a diluent, the packing density, and the depth of the packing sample, are also shown; satisfactory results are obtained. Two new concepts, the sensitivity and the response time of the system, are proposed and evaluated. Conventional methods are criticized, and the inherent limitations of differential thermal analysis are discussed.
  • Leo-Wang Chen, Ju Kumanotani
    1966 Volume 39 Issue 10 Pages 2085-2094
    Published: 1966
    Released: March 27, 2006
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    The deterioration of oxidative polymerized films, such as films of polymerized oils, alkyd resins, and phenolic varnishes, was studied by means of dynamic-mechanical measurements, in addition to such conventional methods as infrared spectral and elementary analysis. The visco-elastic changes induced by thermo-oxidation were correlated with the network structure of the films. The baked films are more stable than the air-dried films. The aliphatic chains decomposed more easily when a comparison was made among air-dried film and baked film of alkyd resin modified by unsaturated fatty acid; this is because of the existence of more hydroperoxyl and conjugated carbonyl groups and the effect of the drying agent contained in the air-dried film. After thermo-oxidation, the glass-transition temperature and the degree of crosslinking of the film showed an increase, an increase which is considered to be the result of the oxidative decomposition and cross-linking of aliphatic chains. It was also observed that the impact strength of baked film decreased upon thermo-oxidation.
  • Takayuki Fueno, Tadashi Okuyama, Junji Furukawa
    1966 Volume 39 Issue 10 Pages 2094-2101
    Published: 1966
    Released: March 27, 2006
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    The effects of ring substituents on the stability of silver ion complexes of benzene and styrene are discussed in terms of the delocalization energies as calculated by the simple LCAO MO method. It is demonstrated that the delocalization energy responsible for the formation of the σ -type molecular bond can predict the relative stabilities of the complexes; the calculated energies are linearly correlated with Hammett’s sigma values. The π-type molecular bond energy arising from the delocalization of silver d-electrons decreases linearly with the increase in the σ-type bond energy. In cases where the two energies are comparable in magnitude, the substituent effects may well be controlled by the entropy term, as has previously been demonstrated experimentally. This apparent paradox encountered in the interpretation of substituent effects may best be reconciled by assuming that the behavior of the silver 4d-orbital in complexation is more closely associated with the entropy change than that of the 5s-orbital of the same atom.
  • Toyosaburo Takeuchi, Michiaki Honma, Hideo Takeda
    1966 Volume 39 Issue 10 Pages 2101-2104
    Published: 1966
    Released: March 27, 2006
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    The catalytic oxidation of propylene by the flow method was carried out in order to investigate the correlation between the activity and the physical properties of the catalyst, using the oxides of zinc, copper, nickel, cobalt, iron, manganese, chromium, vanadium and titanium, all of which were supported with alumina. The analysis by means of gas chromatography indicated that the main products of the reaction were carbon dioxide and water. An abrupt increase in the rate of conversion against the temperature, denoted by CT, was irrespective of the amount of oxide and was characteristic of each oxide. The CT was expressed as a function of the % d character of the metal of the oxide, as well as a function of the heat of formation per gram-atom of oxygen in the oxide. The mechanism of the abrupt change in the rate of conversion was discussed in relation to the ability of oxygen to be removed from the oxide and the amount of propylene adsorbing on the oxide during the reaction.
  • Shinji Takahashi, Hiroji Iwasaki
    1966 Volume 39 Issue 10 Pages 2105-2109
    Published: 1966
    Released: March 27, 2006
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    The self-diffusion coefficients of carbon dioxide were measured over a pressure range from 2 to 250 atm. at 25, 50, and 75°C. The measurements of self-diffusion through a plug of porous bronze were made using the radioactive tracer technique. The products of the density and the diffusion coefficient increase slightly with the density in the region of lower density, below about 10 mol./l., for both isotherms at 50 and 75°C, but they decrease in the region of higher density. These results agree with the results obtained by O’Hern et al., but not with Enskog’s dense gas theory, and not with the values calculated by the generalized chart of Slattery et al.
  • Teijiro Yonezawa, Isao Morishima, Mutsuo Fujii
    1966 Volume 39 Issue 10 Pages 2110-2114
    Published: 1966
    Released: March 27, 2006
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    A molecular orbital interpretation of the directly-bonded 13C–H spin-spin coupling constant without the concept of hybridization is presented. The observed values of JC–H for some saturated and conjugated compounds are shown to be proportional to the square of the bond order between the 2S atomic orbital of the hydrogen atom and the 2S atomic orbital of the carbon atom, P2, which is calculated using the extended Hückel molecular orbital method.
  • Satya Prakash, Som Prakash, Shobhay Laxmi
    1966 Volume 39 Issue 10 Pages 2114-2116
    Published: 1966
    Released: March 27, 2006
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    From the experimental data on the ultrasonic velocity and viscosity of thorium nitrate, lanthanum acetate and lanthanum chloride, it has been found that the product of adiabatic compressibility and viscosity is fairly constant over the concentration range studied. From those data the relation between ultrasonic velocity and viscosity has been derived which can explain the variation in sound velocity with the concentration.
  • Kenichi Fukui, Hiroshi Fujimoto
    1966 Volume 39 Issue 10 Pages 2116-2126
    Published: 1966
    Released: March 27, 2006
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    A simple molecular orbital theoretical treatment of the sigma-pi interaction caused by chemical reactions of planar-conjugated systems has been developed. The problem of the streo-selection of the two alternative directions of configuration altering due to the hybridization change at the centers of interaction has been considered by means of a simple perturbation treatment. Two theoretical indices, which represent the conjugation stabilization by way of the sigma-pi and reagent-pi interactions, have been introduced for this purpose. The theoretical results are consistent with the results of experience so far accumulated in various organic reactions, such as additions, eliminations, substitutions, and rearrangements, of conjugated molecules.
  • Ryokichi Tarao
    1966 Volume 39 Issue 10 Pages 2126-2132
    Published: 1966
    Released: March 27, 2006
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    The polarization data on the Raman lines of Al(CH3)3·(CH3)2O, [Al(CH3)2OCH3]3, [Al(C2H5)2OCH3]3, and [Al(C2H5)2OC2H5]2 have been obtained in the 3100–130 cm−1 region. Most of the infrared absorption bands and Raman lines of these four compounds in the skeletal vibration region (720–130 cm−1) have been tentatively assigned with the aid of these polarization data and on the assumption that the symmetries of these four compounds are as given in the previous paper. The Raman spectra of Al(CH3)3·(CD3)2O, [Al(CH3)2OCD3]3, and [Al(C2H5)2-OC2D5]2 have been measured in the 3100–130 cm−1 region. Most of the infrared absorption bands and Raman lines of Al(CH3)3·(CH3)2O, [Al(CH3)2OCH3]3, [Al(C2H5)2OCH3]3, and [Al(C2H5)2OC2H5]2 in the CH-stretching region (3100–2700 cm−1) have been assigned with the aid of the spectroscopic data of the above-mentioned partly-deuterated substances.
  • Ryokichi Tarao
    1966 Volume 39 Issue 10 Pages 2132-2134
    Published: 1966
    Released: March 27, 2006
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    The infrared and Raman spectra of a mixture of trimethylaluminum and dimethyl sulfide (molar ratio, 1 : 1) have been measured (IR: 3100–300 cm−1, Raman: 3100–130 cm−1). The spectra obtained are entirely different from the superposition of the spectra of the two components. Tentative assignments for most of the infrared bands and Raman lines have been suggested. The CS stretching vibration lines of dimethyl sulfide shift to frequencies lower by about 5 cm−1 when it is mixed with trimethylaluminum. These findings, together with the measurement of the Raman spectrum of the mixture in a 10-volume-percent benzene solution, indicate that the 1 : 1 mixture of trimethylaluminum and dimethyl sulfide forms a pure coordination complex, Al(CH3)3·(CH3)2S, which does not dissociate into its components appreciably in either the liquid state or the benzene solution.
  • Tadamitsu Kiyoura
    1966 Volume 39 Issue 10 Pages 2135-2140
    Published: 1966
    Released: March 27, 2006
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    The exchange reactions of oxygen atoms between oxygen and carbon dioxide on metal oxides were studied by the static batch method in the temperature range from 150 to 600°C. The order of the catalytic activity of the oxides in the reaction was found to be; (higher activity) Co3O4>MnO2>NiO>Fe2O3>Cr2O3>V2O5>TiO2. A very close similarity of the change in the reactivity of these oxides was found in the exchange between oxygen and oxides. There is an approximately linear relationship between the catalyst activity of the metal oxides and the heat of the formation of these oxides. At any temperature examined, carbon dioxide exchanged their oxygen atoms with those of oxide rapidly. The rate of isotopic exchange decreased in the following order on any oxide examined: CO2-Oxide>O2-Oxide>O2-CO2 on oxide. The exchange between oxygen and carbon dioxide was observed only when the exchange between oxygen and oxide took place. According to these results, it was concluded that the exchange between oxygen and carbon dioxide takes place through the exchange between these gases and oxygen atoms of oxide, and that the rate-determining step is the exchange with oxygen.
  • Tatsuya Sekine, Mitsuo Sakairi, Yuko Hasegawa
    1966 Volume 39 Issue 10 Pages 2141-2144
    Published: 1966
    Released: March 27, 2006
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    The distribution of barium(II) at a very low concentration was determined between a carbon tetrachloride solution of 0.1 M thenoyltrifluoroacetone and 0.2 M tributylphosphate and aqueous solutions of 1 M Na(ClO4) at 25°C. The net distribution ratio is decreased when a part of the perchlorate ions are replaced by sulfate or oxalate ions. This decrease was explained in terms of the complex formation of Ba2+ with these ligands. The stability constants were determined graphically from the experimental data as follows:
    (Remark: Graphics omitted.)
  • Hideaki Chihara, Masako Otsuru, Syûzô Seki
    1966 Volume 39 Issue 10 Pages 2145-2152
    Published: 1966
    Released: March 27, 2006
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    The binary system, carbon tetrachloride- t-butyl iodide, was studied by the proton magnetic resonance, the dielectric measurements and the X-ray diffraction. The complete phase diagram, constructed by the differential thermal analysis, shows a solid solution region where carbon tetrachloride is more than 50 mole%. Detailed studies of the solid solution containing 6.6 mole% of t-butyl iodide reveals that the solution can be described by the theory of regular solutions; its molecular polarization above the transition temperature obeys the Debye formula giving the dipole moment of t-butyl iodide a value of 1.6 debye units. The high-resolution nuclear magnetic resonance experiments with the same phase shows that carbon tetrachloride molecules diffuse in the solid solution with an energy of activation of 6.8 kcal./mole. The transition temperature varies with the composition, and below it the rotational motion of the solute molecules is more hindered. Pure t-butyl iodide shows motional narrowing around –150°C in the NMR line shape, above which temperature a reorienting molecular model can account for the magnitude of second moment of the nuclear magnetic resonance absorption.
  • Takeshi Ukaji, Kozo Kuchitsu
    1966 Volume 39 Issue 10 Pages 2153-2156
    Published: 1966
    Released: March 27, 2006
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    The bond distance and its mean square amplitude for the iodine molecule were measured at 80°C, 300°C, and 500°C by gas electron diffraction. The observed temperature dependences of the above parameters were in good agreement with those calculated on the basis of an anharmonicoscillator model and experimental spectroscopic constants.
  • Keniti Higasi
    1966 Volume 39 Issue 10 Pages 2157-2160
    Published: 1966
    Released: March 27, 2006
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    Dielectric data from dilute solution studies consist of two slopes, a′ and a″, as defined by ε′=ε1′+ac2 and ε″=ac2. In this article it is shown that the Debye equations for dilute solutions can be described by the use of a′ and a″. These equations are obtained by replacing dielectric constant and loss, ε′ and ε″ in Debye’s equations for polar liquids by a′ and a″. As applications of these new equations based on a′ and a″ following topics are discussed: Symth’s a′, a″ plot in the complex plane; Scaife’s method of polarizability plot; the familiar loss tangent method originated by Debye for obtaining the relaxation time in solution; and Gopola Krishna’s new method for the same purpose.
  • Kazuo Chitoku, Keniti Higasi
    1966 Volume 39 Issue 10 Pages 2160-2168
    Published: 1966
    Released: March 27, 2006
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    A brief description is made of the experimental methods for measuring microwave dielectric constants and losses of solutions in the frequency range 10–50 Gc./sec. Dielectric data obtained in this experiment were analysed from the viewpoint of molecular interaction between the solute and the solvent molecules. Six benzene derivatives with the amino group, aniline (A), N,N′-di-methylaniline (B), N,N′-diethylaniline (C), 2, 6-dimethylaniline (D), p-nitroaniline (E) and N-methylaniline (F) were chosen as solutes. Benzene and dioxane were used as solvents. The relaxation times of A, D and E obtained in dioxane are about three or five times larger than the corresponding relaxation times in benzene. The relaxation times of B and G in dioxane were about twice or one and half of the corresponding values obtained in benzene. The dielectric behavior of F is intermediate between A and B. These results are attributable to the hydrogen-bond formation between an oxygen atom of the dioxane molecule and an amino-hydrogen atom (F) or atoms (A, D and E).
  • Asha V. Rangnekar, S. M. Khopkar
    1966 Volume 39 Issue 10 Pages 2169-2172
    Published: 1966
    Released: March 27, 2006
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    A method has been described for the extractive spectrophotometric determination of rhodium (III) with 2-thenoyltrifluoroacetone (TTA) in an acetone-xylene mixture. The bright yellow rhodium(III)-TTA chelate solution in an acetone-xylene solvent mixture obeys Beer’s law over the concentration range of 1.95–19.5 μg. of rhodium per ml. Around pH 6.0 quantitative extraction is possible with 0.015 M TTA -acetone-xylene. The colour of the complex is quite stable up to 72 hr. Rhodium(III) can be extracted in the presence of a large number of ions.
  • Saburo Yanagisawa, Noboru Yamate, Shumpo Mitsuzawa, Masaki Mori
    1966 Volume 39 Issue 10 Pages 2173-2178
    Published: 1966
    Released: March 27, 2006
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    Continuous determinations of nitric oxide and nitrogen dioxide in the atmospheric air by the use of a modified Saltzman reagent will be described. Measurement was made intermittently, once every 30 min., by an automatic continuous analyzer equipped with a single-path colorimeter. The response of the analyzer was obtained as an average of the concentration of nitrogen oxides over a period of 25 min. Two bubblers were used for absorbing nitrogen oxides into the modified Saltzman reagent, whose transmittance was measured for the determination. One bubbler was designed to absorb nitrogen dioxide, and the other, nitric oxide plus nitrogen dioxide after the oxidation of the nitric oxide by permanganate. The oxidizing efficiency of the permanganate was 96–100 per cent. The acetic acid in the Saltzman reagent was replaced with n-propyl alcohol in the modified Saltzman reagent; the spontaneous coloration and corrosive quality of the reagent was decreased by this substitution. The concentration of nitric oxide was obtained from the difference between the two responses of the analyzer, while the concentration of nitrogen dioxide could be read directly from the indication of the recorder. The transmittance ratio method was applied to the measurements, accurate determinations were possible, even at high blank values. Therefore, the reagent was used repeatedly by cycling it on the basis of measuring the difference in the coloration of the reagent before and after the absorption of nitrogen oxides. The analyzer could be used for a long period without changing the reagent.
  • R. C. Aggarwal, A. K. Srivastava
    1966 Volume 39 Issue 10 Pages 2178-2180
    Published: 1966
    Released: March 27, 2006
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    The iron(III)-sulfosalicylate complex has been used as the indicator for the direct complexometric determination of thallium(III). This indicator permits the rapid and accurate determination of both micro and macro quantities of thallium(III). The titrations are best carried out at about pH 2.6. Most of the divalent cations, such as calcium, strontium, barium, magnesium, manganese and mercury, and trivalent cations, such as chromium and aluminum, do not interfere in the determination.
  • Hayami Yoneda, Yukiyoshi Morimoto
    1966 Volume 39 Issue 10 Pages 2180-2182
    Published: 1966
    Released: March 27, 2006
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    The proton magnetic resonance spectra of [Co en3]Cl3, [Co tn3]Cl3, [Co pn2]Cl3 and [Co den2]Cl3(den=diethylenetriamine) dissolved in trifluoroacetic acid were measured. All of the observed spectra consist of broad bands, which were assigned on the basis of intensity considerations and by comparing them with the spectra of the corresponding deuterated species. In case of the ethylene-diamine complex, the double-resonance method was applied, measurements at different temperatures were made, and the origin of the breadth of the bands was discussed. The NH2 signals of the ethylenediamine and trimethylenediamine complexes show AB-type features. This was confirmed by comparing the spectra obtained at 60 Mc. and at 100 Mc. The AB-type features of the NH2 signal were explained in terms of the crystal structure of the complex.
  • Kaoru Ueno, Michio Hoshi
    1966 Volume 39 Issue 10 Pages 2183-2187
    Published: 1966
    Released: March 27, 2006
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    The distribution ratios, Kd, for zirconium and hafnium were measured in the hydrochloric acid-TBP-celite system, the acid concentration being varied from 5 N to 8 N. The data obtained showed that the separation factor for the above elements, KdzrKdHf, is fairly high, –4, in the 7–8 N hydrochloric acid range. Thus, the separation of these elements was carried out in 7.1 N hydrochloric acid by the use of a TBP-celite column.
  • Nobuyuki Tanaka, Yumiko Kobayashi, Minoru Kamada
    1966 Volume 39 Issue 10 Pages 2187-2190
    Published: 1966
    Released: March 27, 2006
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    The ion association of hexacyanoferrate(III) and hexacyanoferrate(II) anions with univalent or bivalent cations in aqueous solutions has been studied by the measurement of the infrared absorption band due to the C≡N stretching vibrations. All the solutions measured in which ion-pairs with hexacyanoferrates(III) predominated gave an absorption maximum at 2121 cm−1, and those in which ion-pairs with hexacyanoferrates(II) predominated, at 2020 cm−1, although hexacyanoferrates(III) and hexacyanoferrates(II) of potassium and alkaline earth metals gave different spectra from each other in solid state. No difference in absorption band obtained with different solutions was supported by the distance between two ions in ion-pair, which was estimated from the structures of hexacyanoferrate(III) and hexacyanoferrate(II) ions and the closest approach of the ion-pair; this indicates that there is no direct interaction between the complex anion and the cation, but one or more water molecules interpose between the two ions.
  • Kan Inukai, Teruo Ueda, Hiroshige Muramatsu
    1966 Volume 39 Issue 10 Pages 2191-2194
    Published: 1966
    Released: March 27, 2006
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    The addition of thiols to chlorofluoroethylenes was carried out under γ-ray irradiation; chlorofluoroethyl alkyl sulfides were thus obtained. Ghlorofluoroethyl alkyl sulfoxides and sulfones were prepared by the oxidation of the sulfides. The dehydrohalogenation of chlorofluoroethyl alkyl sulfides yielded chlorofluorovinyl alkyl sulfides, whose structure indicated that the thiyl radical attacked the difluoromethylene side of the asymmetrical dichlorodifluoroethylene. Chlorofluorovinyl sulfoxides and sulfones were also synthesized from the sulfides by oxidation with hydrogen peroxide.
  • Akira Terada
    1966 Volume 39 Issue 10 Pages 2194-2201
    Published: 1966
    Released: March 27, 2006
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    Hydrogenations of bisphenol A (I) over Raney nickel (W-1) and Urushibara nickel A and B have been carried out, and three stereoisomers of 2,2-bis(4-hydroxycyclohexyl)propane (II) and two of 2-(4-hydroxycyclohexyl)-2-(p-hydroxyphenyl)propane (III) have been isolated from the products. The configurations and the preferred conformations of the II isomers, cis-cis (m. p. 174–175°C), cis-trans (164–165.5°C) and trans-trans (188–189°C), and of the III isomers, cis (159–161°C) and trans (150.5–151.5°C), have been determined by means of the infrared and nuclear magnetic resonance spectra, inversions over sodium to the stable isomers, and other methods. When heated with purified methanol, 2,2-bis(4-ketocyclohexyl)propane prepared from the chromium trioxide oxidation of an isomeric mixture of II afforded 2,2-bis(4,4-dimethoxycyclo-hexyl)propane, m. p. 140.5–141.5°C. The recrystallization of IIIt from benzene yielded IIIt·C6H6. Treating IIIc with acetic anhydride gave 2-(3-cyclohexenyl)-2-(p-hydroxyphenyl)propane (where c: cis and t: trans).
  • Susumu Tatsumi
    1966 Volume 39 Issue 10 Pages 2202-2205
    Published: 1966
    Released: March 27, 2006
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    The assignments of the erythro-threo configuration to isomeric 2-methyltartaric acids and the-cis-trans configuration to isomeric 1,2-dihydroxycyclohexane-1,2-dicarboxylic acids were made on the basis of the infrared absorption spectra of their calcium salts. Thus, the isomer of 2-methyltartaric acid, with a m. p. of 146°C, corresponds to the erythro form, and the other isomer, with a m. p. of 161°C, to the threo form; also the one isomer of isomeric 1,2-dihydroxycyclohexane-1,2-dicarboxylic acids with a m. p. of 154°C corresponds to the cis (meso) form, and the other, with a m. p. of 180°C, to the trans (racemic) form. The configurations of the compounds are discussed in comparison with those of tartaric acid and 2,3-dimethyltartaric acid, the latter of which was recently decided by optical resolution by present author (S. Tatsumi, This Bulletin, in press.).
  • Kazuichi Tsuda, Takayuki Otsu
    1966 Volume 39 Issue 10 Pages 2206-2211
    Published: 1966
    Released: March 27, 2006
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    In order to study the effects of aromatic sulfur derivatives on radical polymerizations, dibenzoyl disulfide (DBDS) and its derivatives were prepared and used as initiators or chain transfer agents for the polymerizations of styrene and methyl methacrylate. All of these derivatives failed to act as initiators of thermal polymerizations, but they did prove effective photosensitizers. The rates of polymerizations were found not to be proportional to the square-root concentration of the initiator (DBDS) used. The sulfur radical derived from the photo-dissociation of DBDS affected not only the initiation reaction, but also the termination reaction. The chain transfer constants to DBDS derivatives in the polymerization of styrene and methyl methacrylate showed no linear relationship with Hammett’s equation (logCC0=ρσ), but a linear relationship was obtained when a modification of Hammett’s equation (logCC0=ρσ+γER) was applied. From the plot obtained by the use of logCC0=ρσ+γER, the γ value, which indicates the extent of resonance stabilization in the transition state was found to be 6.0 upon the polymerization of styrene at 60°C. Under similar conditions, however, the γ-value for benzoyl peroxide was calculated as 3.0 from the results of Cooper. This difference may be explained from an increased 3d-orbital resonance stabilization of DBDS in the transition state.
  • Yoshio Kamiya, Tadahiko Nakajima, K\={o}ichiro Sakoda
    1966 Volume 39 Issue 10 Pages 2211-2215
    Published: 1966
    Released: March 27, 2006
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    The rate of the cobalt-catalyzed autoxidation of p-xylene by adding sodium bromide reaches the steady state within several minutes and increases remarkably at high cobalt concentrations. Although p-tolualdehyde as well as water, the main oxidation products of p-xylene at the initial stage, strongly affect the rate of oxidation, the apparent rate is kept constant over a long period. When cobalt dibromide is used, a pronounced induction period can be observed at high cobalt concentrations, and the rate of oxidation starts to decrease after a short while. The effect of the ratio of sodium bromide to cobalt has shown that cobalt monobromide is an effective catalyst for the propagation step. The rate of the oxidation of p-xylene is found to be of the order of from 1.5 to 2.0 with respect to cobalt at concentrations from 10−3 to 5×10−2mol./l. and at temperatures from 65 to 95°C, and to be first-order with respect to the p-xylene concentration; these findings show excellent agreement with the theory. When cobalt is partly replaced by manganese, a strong synergistic effect can be observed.
  • Yoshio Hirabayashi, Masateru Mizuta, Tetsuro Mazume
    1966 Volume 39 Issue 10 Pages 2216-2219
    Published: 1966
    Released: March 27, 2006
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    Thiopalmitic acid, C15H31COSH (m.p. 30.8–31.3°C), and thiomyristic acid, C13H27COSH (m.p. 19.8–20.3°C), were synthesized by the reaction of sodium hydrogen sulfide in ethanol with palmitoyl and myristoyl chlorides respectively. The infrared absorption spectra of thiopalmitic and thiomyristic acids indicate that both acids assumed the thiolic acid form. Dipalmitoyl disulfide (m.p. 76.0–76.5°C) and ethyl palmitate, and dimyristoyl disulfide (m.p. 70.5–71.5°C) and ethyl myristate were isolated as by-products.
  • Yoshio Hirabayashi, Masateru Mizuta, Tetsuro Mazume
    1966 Volume 39 Issue 10 Pages 2219-2223
    Published: 1966
    Released: March 27, 2006
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    The products obtained by heating thiostearic acid in methanol, aqueous methanol, ethanol, or aqueous ethanol have been found to consist of hydrogen sulfide, distearoyl sulfide, methyl or ethyl stearate, thiostearic acid, and stearic acid, the last of which has been detected only in the case of aqueous alcohols. On the basis of the above results, the following scheme may be involved, at least in part, in the formation of carboxylic ester and hydrogen sulfide by heating the thio acid in alcohols:
    (Remark: Graphics omitted.)
  • Yoshiharu Izumi, Susumu Tatsumi, Masami Imaida
    1966 Volume 39 Issue 10 Pages 2223-2226
    Published: 1966
    Released: March 27, 2006
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    Asymmetric hydrogenation catalysts were prepared by modifying Raney nickel with aqueous solutions of D-tartaric acid, monomethyl D-tartrate, L-erythro- and D-threo-2, 3-dihydroxybutyric acid, L-malic acid, (+)-erythro- and (−)-threo-3-methylmalic acid, L-citramalic acid and L-methyl-succinic acid. Their asymmetric activities in the hydrogenation of methyl toacetate to methyl 3-hydroxybutyrate were compared with each other in order to study the effect of the chemical structure of the modifying reagent on the activity. Monomethyl D-tartrate, L-erythro- and D-threo-2, 3-dihydroxybutyric acid are less effective in asymmetric activity than D-tartaric acid. On modification with these three reagents, optimum asymmetric activities were obtained under acidic conditions. With D-tartaric acid, however, while high asymmetric activities were obtained at pH 5–9, there was a considerable decrease in activity at lower pH values. This suggests that the β-carboxyl group of tartaric acid plays an important role in the modification. (−)-threo-3-Methylmalic acid is more effective in asymmetric activity than L-malic acid, while (+)-erythro-3-methylmalic acid and L-citramalic acid are less effective. It has been suggested that these differences are related to hindrances due to the methyl groups on the α- or β-asymmetric centers, and also related to the correlations of the configurations of the asymmetric centers of 3-methylmalic acids. L-Methyl-succinic acid has little asymmetric effect on Raney nickel.
  • Akira Kasahara, Katsuyasu Uji-ie, Keiko Tanaka
    1966 Volume 39 Issue 10 Pages 2227-2229
    Published: 1966
    Released: March 27, 2006
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    The pseudo-aromatic divalent palladium acetylacetonate has been found to undergo electrophilic substitution at the central carbon of the chelate ring. The mononitro (decomp.p. 240–245°C, λmax 325 mμ) and dinitro (decomp.p. 250–255°C, λmax 324 mμ) palladium acetylacetonates were prepared by treating palladium acetylacetonate with a mixture of copper nitrate trihydrate and acetic anhydride; they were characterized by their infrared and NMR spectra. The halogenation of palladium acetylacetonate was accomplished with N-halosuccinimides in chloroform. Dichloro (decomp.p. 205–210°C, λmax 345 mμ), dibromo (decomp.p. 240–245°C, λmax 345 mμ) and diiodo (decomp.p. 195–200°C, λmax 324 mμ) derivatives were isolated and characterized by their spectra.
  • Koji Sakai, Takehiko Ito, Ken-ichi Watanabe
    1966 Volume 39 Issue 10 Pages 2230-2233
    Published: 1966
    Released: March 27, 2006
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    Styrene, mesityl oxide, benzonitrile and nitrobenzene are reduced when heated with primary alcohols, such as methanol, ethanol, 1-butanol and benzyl alcohol, in the presence of nickel catalysts. On the other hand, aldehydes are obtained by the dehydrogenation of the primary alcohols. The relative reactivity of the functional groups for the reduction is as follows: C=C>C≡N>NO2>C=O. The carbonyl group and the benzene nucleus can not be reduced under these reaction conditions. A selective reduction occurs in the reaction with mesityl oxide. The lower limit of the reaction temperature depends on the combination of the two species of the hydrogen donor (primary alcohol) and the acceptor compounds. The use of a large excess of alcohols for the reduction is effective in this redox reaction. In the reaction between styrene and benzyl alcohol, the ratio of the decreased amount of styrene to the increased amount of ethylbenzene is always 1 : 1, as determined by gas chromatographic analysis.
  • Michio Kondo, Haruhiko Aoyagi, Tetsuo Kato, Nobuo Izumiya
    1966 Volume 39 Issue 10 Pages 2234-2242
    Published: 1966
    Released: March 27, 2006
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    A cyclic decapetide dihydrochloride, cyclo-(glycyl-L-ornithyl-L-leucyl-D-phenylalanylglycyl)2·2HCl, which is an analog of gramicidin S, and a cyclic pentapetide monohydrochloride, cycloglycyl-L-ornithyl-L-leucyl-D-phenylalanylglycyl·HCl,where synthesized in order to compare their decapeptide active esters was found to yield the same cyclic bezyloxycarbonyl-substiuted decapetide: this was converted by hydrogenolysis to the cyclic decapeptide dihydrochloride mentioned above. The cyclization reaction of a linear pentapetide active ester, in which the glycines are both terminal amino acid residues, yielded a cyclic benzyloxycarbonyl-substiuted pentapetide exclusively. When another linear pentapeptide active ester and a pentapetide azide where also subjected to cyclization reaction, they afforded the same cyclic benzyloxycarbonylsubstituted pentapeptide; this was then hydrogenolyzed to the corresponding cyclic pentapeptide monohydrochloride. The effects of the two cyclic peptide hydrochlorides on the bacterial growth were tested; no retardation of growth was observed with any of the microorganisms tested.
  • Tetsuo Kato, Nobuo Izumiya
    1966 Volume 39 Issue 10 Pages 2242-2249
    Published: 1966
    Released: March 27, 2006
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    A cyclic hexapeptide, cyclo-D-phenylalanyl-D-leucyl-L-ornithyl-L-valyl-D-ornithyl-L-prolyl, was once reported to be an antibiotic gramicidin J2, and the synthesis of the compound was described also. However, the natural occurrence of gramicidin J2 was denied recently. For the purpose of comparing its antibacterial activity, if any, with gramicidin S, the synthesis of this compound was carried out. p-Methoxybenzyloxycarbonyl-D-phenylalanyl-D-leucyl-δ-benzyloxycarbonyl-L-ornithyl-L-valyl-δ-benzyloxycarbonyl-D-ornithyl-L-proline p-nitrophenyl ester was prepared, and, after the selective cleavage of p-methoxybenzyloxycarbonyl group, the hexapeptide ester was transformed to the cyclic benzyloxycarbonyl hexapeptide, which was then hydrogenated to afford the desired cyclic hexapeptide as dihydrochloride. The effects of the synthesized cyclic peptide on bacterial growth have been examined. No antibacterial activities were observed in reaction to the microorganisms utilized here.
  • Naruyoshi Obata, Ichiro Moritani
    1966 Volume 39 Issue 10 Pages 2250-2255
    Published: 1966
    Released: March 27, 2006
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    The reactions of acylcyclopropenes, such as 3-benzoyl-1,2-diphenyl- and 3-acetyl-1,2-diphenyl-cyclopropene, were investigated. These ketones gave normal hydrazones with 2,4-dinitrophenylhydrazine. With p-toluenesulfonylhydrazine, the acetyl compound gave ordinary hydrazone, but the benzoyl derivative did not give its hydrazone. The reaction with hydrazine hydrate caused the expansion of the cyclopropene ring and produced pyridazine derivatives in both the ketones. The carbenic decomposition of 3-acetyl-1,2-diphenylcyclopropene p-toluenesulfonylhydrazone with sodium methoxide in diglyme gave diphenylacetylene and 3,4-diphenyl-6-methylpyridazine. On irradiation with ultraviolet light, 3-benzoyl-1,2-diphenylcyclopropene produced 1,2,4,5-tetraphenylbenzene. In the case of 3-acetyl-1,2-diphenylcyclopropene, the same benzene derivative and 1,2,4,5-tetraphenyl-3,6-diacetyltricyclo[3,1,0,02,4]hexane were obtained. The latter material was transformed into a benzene derivative upon further irradiation. Tricyclohexane could be an intermediate in the transformation of ketones to a benzene derivative.
  • Yasuhide Yukawa, Nobuyoshi Hayashi
    1966 Volume 39 Issue 10 Pages 2255-2256
    Published: 1966
    Released: March 27, 2006
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    The reaction of p-methoxystyrene with lead tetraacetate in glacial acetic acid should proceed mainly through the rearrangement of the carbon skeleton. The possibility of the hydrogen migration can not be ruled out, but its extent should be only 7% even if it is involved.
  • Takayuki Otsu, Toshio Ito, Tomiya Fukumizu, Minoru Imoto
    1966 Volume 39 Issue 10 Pages 2257-2260
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In order to clarify the effect of the alkyl groups in alkyl acrylates (RA) on their reactivities to the attack of a radical, the copolymerization of RA (M2) with styrene (M1) has been carried out at 60°C. From the results obtained, the monomer reactivity ratios and the Q2 and e2 values were determined. It was found that the relative reactivities (1/r1) of RA to a polystyryl radical were correlated only by the polar substituent constant (σ*) of the alkyl group in RA, not by their steric substituent constant (Es) in Taft’s equation:
    log(1⁄r1)=ρ*σ*Es
    According to the above equation, the ρ* and δ values were obtained as 0.56 and 0, respectively. It was also observed that the Q2 and e2 values for RA were correlated by Taft’s σ* substituent constant.
  • Shigeru Oae, Naomichi Furukawa
    1966 Volume 39 Issue 10 Pages 2260-2263
    Published: 1966
    Released: March 27, 2006
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    Diphenylsulfone-1-14C was treated with fused potassium hydroxide at 300°C for 7 hr. in a sealed metal tube. The yield of phenol, as determined by the isotope dilution technique, was found to be almost quantitative. The distribution of 14C in the resulting phenol was determined by degradating it by the usual method. Practically all the activity of 14C in the phenol was found at the position 1, which corresponded to the originally-labeled position in the diphenylsulfone-1-14C used. This indicates that the mechanism of the alkaline fusion of diphenylsulfone proceeds thruogh a simple SN2-type mechanism, not the elimination-addition mechanism.
  • Hideki Sakurai, Akira Hosomi, Jun-ichi Nakajima, Makoto Kumada
    1966 Volume 39 Issue 10 Pages 2263-2265
    Published: 1966
    Released: March 27, 2006
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    The reactions of three hexaorganodisilanes with N-bromosuccinimide in carbon tetrachloride or in chloroform were carried out. Hexamethyldisilane afforded trimethylbromosilane (82.9–100%) and N-trimethylsilylsuccinimide (73.5–79.5%). No bromomethylpentamethyldisilane was obtained. Similarly, 1,2-diphenyltetramethyldisilane gave phenyldimethylbromosilane and a small amount of bromobenzene. The N-silyl compound could not be isolated, but succinimide was obtained as a decomposition product. Phenylpentamethyldisilane gave trimethylbromosilane and phenyldimethylbromosilane in 67.4 and 12.3% yields respectively. A possible reaction mechanism was discussed.
  • Yasuhide Yukawa, Mitsuru Sakai, Shigeo Suzuki
    1966 Volume 39 Issue 10 Pages 2266-2269
    Published: 1966
    Released: March 27, 2006
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    A detailed study of the reaction of oximes by lead tetraacetate has been made. It has beers found that the reaction gave nitrogen and the respective aldehydes or ketones in good yields.. In the reaction, which can be applied to general oximes, the order of yields was: aliphatic aldoximes >aliphatic ketoximes>alicyclic ketoximes >aromatic ketoximes>aromatic aldoximes. Some limited mechanistic implications are presented and discussed on the basis of the results obtained. Stoichiometrically, it has been found that 2 moles of oxime react with 1 mole of lead tetraacetate to produce 2 moles of aldehyde or ketone and 1 mole of nitrogen.
  • Yojiro Tsuzuki, Koko Tanabe, Kikuhiko Okamoto, Noriko Yamada
    1966 Volume 39 Issue 10 Pages 2269-2273
    Published: 1966
    Released: March 27, 2006
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    Circular dichroism has been measured of eighteen nitrates of hexoses (glucose, mannose and altrose), and its correlation with the rotatory dispersion as well as the ultraviolet absorption has been established, verifying even a number of suggestions made as regards the sign of some ambiguous Cotton effects (Tsuzuki et al., This Bulletin, 39, 1391 (1966)), which has eventually led to some significant conclusions.
  • Yasuhide Yukawa, Yuho Tsuno, Masami Sawada
    1966 Volume 39 Issue 10 Pages 2274-2286
    Published: 1966
    Released: March 27, 2006
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    A set of normal substituent constants, σ0, was derived from the rates of alkaline hydrolysis of m- and p-substituted ethyl phenylacetates in 60% (v/v) aqeuous acetone at 25.0°C. The obtained values of σ0-constants were generally identical with Taft’s values within experimental uncertainty. On the basis of the derived σ0, substituent effects on the general electrophilic reactions were correlated excellently by the equation, logkk0=ρ(σ0+\barσR+) where Δ\barσR+ corresponds to the exaltation of Brown and Okamoto’s σ+ from σ0. The similar treatment could be applied also to the nucleophilic reactions. The utility of this equation for the estimation of resonance contribution and for the consideration of reaction mechanisms are discussed.
  • Jun-ichi Oh-hashi, Kaoru Harada
    1966 Volume 39 Issue 10 Pages 2287-2289
    Published: 1966
    Released: March 27, 2006
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    DL-β-Hydroxyvaline was synthesized from sodium β,β-dimethylglycidate by aminolysis with benzylamine, followed by hydrogenolysis. N-Benzoyl-DL-β-hydroxyvaline was resolved by use of (−)-α-methylbenzylamine to yield (−)-N-benzoyl-β-hydroxyvaline. The configuration of VI was determined by converting it to methyl N-benzoyl-β-chlorovalinate (I) and subsequent hydrogenolysis of I yielded (−)methyl N-benzoylvalinate (II). From II, optically pure D-(−)-valine was obtained upon hydrolysis.
  • Harusuke Tokui, Kiroku Yamazaki
    1966 Volume 39 Issue 10 Pages 2290-2294
    Published: 1966
    Released: March 27, 2006
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    The capability of several sorts of conventional antioxidants was studied by means of the tensile and the swelling tests of the elastomers derived from the carboxy-terminated polybutadiene prepolymer. When exposed for one year, the elastomers containing no antioxidants deteriorated remarkably; they became brittle and, without exception, no longer looked like the so-called “elastomers.” Many kinds of the antioxidants worked out and were found to be effective; their capabilities were evaluated as almost the same as far as the tensile properties of the exposed material were concerned. The changes in the reciprocal value of the average chain length between cross-links, 1/Mc, in the course of the exposure, however, would be a convenient semi-quantitative measure of the induced cross-linking reaction. With this assumption, the swelling test might prove that, among the additives covered, the amine-type antioxidants were most effective in preventing the deterioration induced by the over-cross-linking reaction of the elastomer. The relationship between the amount of the sol-fraction and the cross-linking density for the exposed specimens was fitted to that of the random cross-linking and the scission of the polymer with a random distribution of chain lengths.
  • Soichi Muroi
    1966 Volume 39 Issue 10 Pages 2295-2298
    Published: 1966
    Released: March 27, 2006
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  • Gopal Narain
    1966 Volume 39 Issue 10 Pages 2298-2300
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Katsumi Tabei, Kuniomi Natou
    1966 Volume 39 Issue 10 Pages 2300-2303
    Published: 1966
    Released: March 27, 2006
    JOURNALS FREE ACCESS
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