Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 2
Showing 1-50 articles out of 55 articles from the selected issue
  • Tanekazu Kubota, Hiroshi Miyazaki, Yutaka Mori
    1967 Volume 40 Issue 2 Pages 245-251
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Polarograms and half-wave potentials (E1⁄2’s) of sixteen substituted benzylidenementhylamine N-oxides were extensively measured in various pH solutions. The half-wave potential, E1⁄2, was expressed in the form: E1⁄2=a·pH+b. It was always observed that the four-electron wave due to the reduction of the C=N→O group decreases in wave height in an alkaline medium, and at the same time another wave appears in a more negative potential. The former behavior was similar to that found for pyridine N-oxide and its derivatives. The plot of the Hammett σ values of the substituents against the E1⁄2 values of nitrones satisfied a linear relation very well, ρ being positive but smaller than that obtained previously for the system of substituted pyridine N-oxides. Controlled-potential electrolysis was carried out in order to compare the results with the polarographic results.
  • Tatsuya Sekine, Ichiro Sakamoto, Tatsuo Sato, Tomoe Taira, Yuko Hasega ...
    1967 Volume 40 Issue 2 Pages 251-254
    Published: 1967
    Released: March 27, 2006
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    The complex formation of europium(III) with nitrate and chloride ions in 4 M H(ClO4) and 4 M Na(ClO4) was studied at 25 °C, using radioactive tracers at very low concentrations and in conjunction with cation exchange resin. The stability constants were determined graphically by a “curve-fitting” method. The stability constants obtained were as follows:
    (Remark: Graphics omitted.)
    It was concluded that the stability of the nitrate complexes is nearly comparable with that of the chloride complexes.
  • Kazuo Shimokoshi, Yuji Mori, Ikuzo Tanaka
    1967 Volume 40 Issue 2 Pages 254-260
    Published: 1967
    Released: March 27, 2006
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    The ESR technique has been applied to a study of the mercury-photosensitized reaction of H2+O2 mixtures in the PO2=10–200 μHg and PH2=0.2–4 mmHg regions. For the determination of this reaction, the concentration (ESR signal amplitude) of H atoms was followed with time throughout the reaction. The concentration of H atoms varied with time; its maximum was determined. The time (Tm) at which the H atom concentration reached a maximum depended on oxygen and hydrogen pressures. From the variations in Tm and some kinetic considerations, it was concluded that oxygen played an important role in this reaction in increasing the stationary concentrations of H atoms in the system. In this experiment, I0=2.4×1015 molecules/sec, the rate of the production of H atoms in Reaction (1), was determined from the variations in Tm with the initial oxygen pressure:
    (Remark: Graphics omitted.)
    The pressure of oxygen at the maximum concentration of H atoms was found to be little dependent on the PH2 used in this experiment; 5 μHg was found to be this pressure.
  • Tatsuya Sekine, Mitsuo Sakairi
    1967 Volume 40 Issue 2 Pages 261-264
    Published: 1967
    Released: March 27, 2006
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    The complex formation of beryllium (II) with sulfate and oxalate ions in 1 M Na(ClO4) at 25°C has been studied by a liquid-liquid distribution method. The radioactive tracer beryllium-7 at very low concentration was used in conjunction with thenoyltrifluoroacetone in methylisobutylketone. The stability constants of the beryllium complexes were determined graphically from the distribution data by a curve-fitting method. The data seemed to be explained by the formation of the following complex species;
    βn=[BeLn2–2n]⁄[Be2+][L2−]n,
    where logβ2=1.78 and logβ3=2.08 for sulfate and logβ1=3.55 and logβ2=5.40 for oxalate. The formation of the primary sulfate complex, BeSO4, or the tertiary oxalate complex, Be(C2O42−)34−, was not concluded within the ligand concentration region studied.
  • Noritake Yasuoka, Tadanao Ando, Shunsuke Kuribayashi
    1967 Volume 40 Issue 2 Pages 265-269
    Published: 1967
    Released: March 27, 2006
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    Crystals of p, p’-dichlorodiphenoxy-1,2-ethane are monoclinic; their space group is P2/c, and they have 4 molecules in the cell with dimensions of:
    a=12.79, b=9.89, c=10.37Å; β=98.2°
    Two crystallographically-independent molecules, which are slightly different in conformation, are located on the two-fold axis of the crystal. The OCH2CH2O groups are of the gauche form.
  • Noritake Yasuoka, Tadanao Ando, Shunsuke Kuriyabashi
    1967 Volume 40 Issue 2 Pages 270-273
    Published: 1967
    Released: March 27, 2006
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    1,2-Diphenoxyethane crystallizes in two forms, flake-shaped and prismatic. The crystal and molecular structures of the prismatic crystals were determined and described. The orthorhombic unit cell dimensions are: a=34.74, b=12.04, and c=5.58 Å. The space group is Fdd2. The molecule has the symmetry of a two-fold axis, and the OCH2CH2O group exists in a gauche conformation with an internal rotation angle of 66.9°.
  • Yuko Shimura
    1967 Volume 40 Issue 2 Pages 273-279
    Published: 1967
    Released: March 27, 2006
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    Short-range interactions between chain units of random copolymers in solution may be influenced by the characters of the pendant side groupes or, more precisely, by the dipole moment of the substituent. In those experiments the steric factor was derived for a random copolymer composed of methyl methacrylate and acrylonitrile from the relation between the limiting viscosity number and the molecular weight. Mark-Houwink relations were obtained in N,N′-dimethylformamide (DMF) and in methyl ethyl ketone (MEK) at 30°C for the copolymer containing 0.48 mol fraction of acrylonitrile, and for polymethyl methacrylate (PMMA) for the sake of comparison:
    [η]=4.61×10−4M0.65 for the copolymer in DMF
    [η]=1.70×10−4M0.65 for PMMA in DMF
    [η]=1.26×10−3M0.52 for the copolymer in MEK
    With the Stockmayer-Fixman expression, these correlations become, respectively:
    [η]=213×10−5M1⁄2+12.4×10−7M
    [η]=78.2×10−5M1⁄2+5.05×10−7M
    [η]=163×10−5M1⁄2+1.05×10−7M
    The unperturbed mean square end-to-end distance, ⟨L20, determined from the first term of the latter expressions, together with the ⟨L20f value calculated by assuming the completely free rotation, gives the steric factor of σ=(⟨L20⁄⟨L20f)1⁄2 2.59±0.01 from the DMF solution; this factor is larger than that for polymethyl methacrylate (2.11±0.08),, and that for polyacrylonitrile (2.20+0.05). The steric parameter derived from the MEK solution is 2.37±0.05 for this co-polymer; this value does not agree with the value obtained from the DMF solution. In both cases, it may be concluded that the dimensions of the copolymer between acrylonitrile and methyl methacrylate are influenced by the electrostatic interactions between nitrile groups of acrylonitrile units and methoxy-carbonile and/or methyl groups of methyl methacrylate units. The second virial coefficient in MEK obtained from the light scattering measurements also has a larger value for this copolymer than for polymethyl methacrylate. This tendency of copolymers to show a larger second virial coefficient seems to be an essential characteristic of some copolymers.
  • Tohru Azumi, Hiroshi Azumi
    1967 Volume 40 Issue 2 Pages 279-284
    Published: 1967
    Released: March 27, 2006
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    The energy of the excimer luminescence is interpreted in terms of a simple Hückel-type dimer orbitals, which are constructed by treating the excimer as one species. The present model of the excimer yields results quite similar to those of the complicated ASMO CI treatment as developed earlier; further, it is capable of explaining various characteristics of the excimer, including the 6000 cm−1 rule.
  • Hisaharu Hayashi, Koichi Itoh, Saburo Nagakura
    1967 Volume 40 Issue 2 Pages 284-293
    Published: 1967
    Released: March 27, 2006
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    ESR studies have been made with single crystals of sodium 1-oximinopropionate irradiated at −196°C and at room temperature. The principal values and axes of the g and hyperfine tensors of the trapped radicals have been determined. The analysis of the observed data has indicated that the σ-electron radicals CH3C(COO)=NO are trapped at −196°C and at room temperature. It has been found that the electronic structures of the trapped radicals at these two temperatures are essentially the same, but that the environments of the radicals are very different from each other. After the crystal had been heated at 50°C for a week, the σ-electron radical vanished and the π-electron radicals, CH3C(OH)(COO)NHO· and CH3CR’-(COO)NRO·, appeared. The former may be formed in the solid state by adding a crystal water molecule to the unsaturated radical. The trapped radicals in irradiated single crystals of potassium 1-oximinopropionate were also studied at room temperature and after having been heated at 50°C. They are the σ-electron radical and the π-electron radical respectively, with structures similar to those of the sodium salt. The radical pairs have been observed in irradiated single crystals of the sodium salt at −196°C.
  • Akira Yokohata, Satoru Tsuda
    1967 Volume 40 Issue 2 Pages 294-297
    Published: 1967
    Released: March 27, 2006
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    In this series of studies of silent discharge reactions, the G values of the hydrogen atom,, the hydroxyl radical and hydrogen peroxide have successfully been determined in terms of the radiolysis of water by slow electrons: G(H)=1.1, G(OH)=1.6, and G(H2O2)=1.0 in helium, and G(H)=0.6, G(OH)=0.7 and G(H2O2)=1.5 in argon. Also, the absorbed dose has been estimated. In order to obtain further information regarding the nature of these radicals and the adequacy of these G values, the ferrous-cupric ions system and ceric-thallous ions system in atmospheres of helium and argon have now been investigated. The experimental results show that Gobs(Fe3+) in a ferrous-cupric ion system and Gobs(Ce3+) in a ceric-thallous ion system almost coincide with Gcalc(Fe3+) (=2G(H2O2)+G(OH)–G(H)) and Gcalc(Ce3+) (=2G(H2O2)+G(OH)+G(H)), as was to be expected from the previously determined G values. These findings suggest that the silent discharge reaction in these systems can be well interpreted in terms of the scavenging effect of cupric ions and thallous ions on the hydrogen atom and the hydroxyl radical, as in the case of radiation chemistry. Further, the present study has confirmed that the G values determined in the earlier experiment are reliable.
  • Toshio Sato, Yoshihito Takahashi, Katsumasa Yabe
    1967 Volume 40 Issue 2 Pages 298-301
    Published: 1967
    Released: March 27, 2006
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    The energy shifts of the SKα doublet have been measured in fifty sulfur compounds in solid or liquid states, using rhombic sulfur as a standard. The values were the same as those obtained by Faessler and Goehring, although a slight discrepancy was observed on sulfites and sulfates. The mean number of the valence electrons, N, associated with the sulfur atom in compounds has then been calculated from the shifts according to a theoretical correlation presented by Coulson and Zauli. The values of N have been found to be 6.7, 6.3, 5.2, 4.7, 4.7, and 4.3 for inorganic sulfides, organic sulfides, sulfoxides, sulfites, sulfones and sulfates respectively, assuming that N=6.0 for rhombic sulfur. The dipole moments evaluated from the values of N and structural data were 4.9, 4.8 and 5.2D, for dimethyl sulfoxide, dimethyl sulfone and diphenyl sulfone, respectively; these values were almost compatible with the experimental values of 3.9, 4.41 and 5.14D. respectively.
  • Kazuo Shimokoshi, Yuji Mori, Ikuzo Tanaka
    1967 Volume 40 Issue 2 Pages 302-306
    Published: 1967
    Released: March 27, 2006
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    ESR techniques were used to examine the photosensitized decomposition of solvents in a system composed of α-naphthol and its derivatives, diphenylamine, tetraphenyl hydrazine, and diphenyl methane in methanol, EPA, and ethanol at 77°K. The effects of intermittent irradiation and incident light intensity were investigated mainly in the system composed of α-naphthol in methanol at 77°K. The lifetime of the lowest triplet state of α-naphthol was determined by the intermittent irradiation, with some kinetic considerations; it agreed reasonably well with the values obtained by the direct measurement of the phosphorescence. The rate of the radical formation was found to be nearly proportional to the square of the light intensity. From these results, it was concluded that T-T* absorption in these sensitizers played an important role in forming the radicals from alcohols. The inter-molecular triplet-triplet energy transfer process was also confirmed in a system composed of a mixed alcoholic solution of phenanthrene and naphthalene at 77°K.
  • Teijiro Yonezawa, Hiroshi Kato, Osamu Yamamoto
    1967 Volume 40 Issue 2 Pages 307-311
    Published: 1967
    Released: March 27, 2006
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    The electronic structures of several alkyl peroxides including the carbonyl group, i. e., performic acid, peracetic acid and their methyl esters, are investigated by the extended Hiickel method proposed by Hoffmann. The structure of the bond between peroxy oxygens, the intramolecular hydrogen bonding in peracid, the pyrolysis of peracid which is caused by the fact that the bond strength between peroxy oxygen atoms is weakened by an intramolecular hydrogen bonding, and the reaction mechanism of both the epoxidation of olefin by peracid and the ionic decomposition of peresters by basic catalysts can be successfully explained on the basis of the calculated results.
  • Hiromichi Arai, Yasukazu Saito, Yukio Yoneda
    1967 Volume 40 Issue 2 Pages 312-321
    Published: 1967
    Released: March 27, 2006
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    The electronic spectra of adsorbed triphenylmethane have been observed through a study of disk samples made by the compression method from ordinary powder catalysts. Three kinds of adsorbed species of triphenylmethane were obtained for silica-alumina. The band at 265 mμ was due to a physically adsorbed species (Ph3CH). A new band at 340 mμ was assigned to the triphenylmethyl radical (Ph3C·), formed in the absence of air, with a sharp spectrum (g=2.004) observed in the electron spin resonance. The species of the bands at 408 and 435mμ was identified as triphenylcarbonium ion (Ph3C+), the amount of which increased with the light and temperature exposure period. Types of acid present on silica-alumina, alumina, silica, and other catalysts were discussed.
  • Hisao Imai, Hiroshi Uchida
    1967 Volume 40 Issue 2 Pages 321-326
    Published: 1967
    Released: March 27, 2006
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    The oxidation of carbon monoxide and magnetic susceptibility measurements have been carried out with a series of nickel oxide-silica-alumina catalysts, all of which are the same in aluminum content but which are different in nickel content. The kinetic data of the oxidation followed an Elovich rate equation, and the initial activity per unit of surface area of the catalyst increased as the nickel content increased from 0 to 8.0 atom%. The apparent activation energy was found to be 8±2 kcal/mol. The magnetic susceptibility vs. temperature curves followed the Curie-Weiss relationship in the temperature range between 240 and 723°K, and the effective Bohr magneton number increased to an approximately constant value of 3.7 Bohr magnetons as the nickel content decreased. The structure of the nickel oxide-silica-alumina catalysts has been discussed on the basis of the results obtained, and the Thomas model of the nickel acid site previously proposed for the active site of the ethylene polymerization (H. Uchida and H. Imai, Bull. Chem. Soc. Japan, 35, 995 (1962)) has been confirmed.
  • Kenji Bansho, Yoshimi Umezaki
    1967 Volume 40 Issue 2 Pages 326-329
    Published: 1967
    Released: March 27, 2006
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    A rapid method for the spectrophotometric determination of microgram amount of gallium with 4-(2-pyridylazo)-resorcinol (PAR) in the organic phase after the extraction of gallium from a hydrochloric acid solution with isopropyl ether and butyl acetate will be described. A red color is formed in an aliquot of the organic extract by the addition of PAR, pyridine, and sodium acetate in methanol. The complex formed in the organic phase has a maximum absorbance at 510 mμ. The color reaction conforms to Beer’s law, and the molar absorptivity of the complex is estimated to be approximately 100000. The coefficient of the variation of the absorbance measurements on a standard gallium solution at 510 mμ was about 0.8%. A study of the effect of diverse ions showed the method to be highly selective.
  • Nobuyuki Tanaka, Michio Nanjo
    1967 Volume 40 Issue 2 Pages 330-333
    Published: 1967
    Released: March 27, 2006
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    The thermal decomposition of trioxalato complexes of cobalt(III), iron(III) and chromium-(III) has been investigated by the thermogravimetric, the polarographic and the infrared spectroscopic method. The results indicate that, in the case of the iron(III) and the cobalt(III) complexes, the decomposition reaction is initiated by the electron transfer from the coordinated oxalate ion to the central metal ion. In the case of oxalatoamminecobalt(III) complexes, the oxalate ion is considered to be an electron donor; the more oxalate ions are coordinated, the complexes are thermally less stable.
  • Reita Tamamushi, Toshiaki Isono, Shunzo Katayama
    1967 Volume 40 Issue 2 Pages 334-337
    Published: 1967
    Released: March 27, 2006
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    The ionic equivalent conductivities at infinite dilution, viscosity B-coefficients, partial molal volumes, and ionic radii of nitroamminecobalt(III) complex ions have been determined in aqueous solutions at 25 °C. From the conductivity data, the thermodynarnic association constants of the polyvalent complex cations with chloride ions have been calculated. The log K values at 25°C are 1.5 for [Co(NH3)6]3+–Cl and 1.3 for [Co(NO2)(NH3)5]2+–Cl respectively. Some factors, which will determine the B-coefficients of complex ions, have been briefly discussed.
  • Tamotsu Fujisawa, Teruaki Mukaiyama
    1967 Volume 40 Issue 2 Pages 337-339
    Published: 1967
    Released: March 27, 2006
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    The reactions of diethyl N-phenyliminocarbonate with alkyl halide, acid chloride, lactone, and acid anhydride were studied in order to examine the nucleophilicity of the imino group. These reactions gave the corresponding carbamates at elevated temperatures, much as in the previously reported reactions of iminocarbonates with acids. On the other hand, from the reaction of the iminocarbonate with ethylene carbonate or ethylene sulfite, 3-phenyloxazolidone-2 was obtained along with the evolution of carbon dioxide or sulfur dioxide, respectively.
  • Shuzo Akiyama, Masazumi Nakagawa
    1967 Volume 40 Issue 2 Pages 340-345
    Published: 1967
    Released: March 27, 2006
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    The synthesis of 1, 1′-dianthryldi- and tetra-acetylenes has been reported previously by the present authors. Now, 1, 1′-dianthryltri-, penta- and hexa-acetylenes have been synthesized in order to complete the series of 1, 1′-dianthrylpoly-ynes. It is well known that the square of the wavelength of the longest absorption maxima, λmax in the electronic spectra of some series of poly-enes and poly-ynes varies linearly with the number of the multiple bonds, nmax2n). It was anticipated that the dianthrylpoly-ynes would exhibit analogous spectral behavior. Unexpectedly, however, it was observed that the λmax of the dianthrylpolyacetylenes varied linearly with the square of the number of the triple bonds, nmaxn2).
  • Noboru Sugiyama, Choji Kashima, Makoto Yamamoto, Ryotaro Mohri
    1967 Volume 40 Issue 2 Pages 345-346
    Published: 1967
    Released: March 27, 2006
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    Ethyl 5-hydroxy-5-(1-hydroxyethyl)-4-oxotetrahydrofuroate was synthesized and was identified with altenin.
  • Noboru Sugiyama, Masamoto Akutagawa, Taketoshi Gasha, Yo Saiga, Hirosh ...
    1967 Volume 40 Issue 2 Pages 347-350
    Published: 1967
    Released: March 27, 2006
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    The chemiluminescence of forty-one indole derivatives has been investigated by using two types of reaction mixtures: (A) the EtOH-KOH-H2O2-K3Fe(CN)6-Sample and (B) the DMSO-KOH-Sample. In both systems the reactions were carried out in the presence of air. The light intensity of chemiluminescence was measured by the deflection of the microammeter of the photometer or recorded by a connected automatic recorder. The relative light intensity (RLI), the ratio of the maximum intensity of the chemiluminescence of the sample to that of indole, was also measured. The electron-repelling group, such as hydroxyl and substituted aminovinyl group, at the 3- or 5-position enhanced the RLI, but alkyl, acetyl, formyl groups or chlorine at the various positions had little effect or a negative effect on the RLI. Some of the compounds showed a maximum intensity soon after the reagents were mixed, while some others slowly showed a maximum, which then decayed slowly.
  • Akira Kasahara, Keiko Tanaka, Kazunori Asamiya
    1967 Volume 40 Issue 2 Pages 351-355
    Published: 1967
    Released: March 27, 2006
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    The chloro-bridged π-allylic palladium complex has been prepared from cyclohexenone and sodium chloropalladite. 6-Oxo-4, 4-dimethylcyclohex-2-enyl, 1,2-(4-oxo-2, 2-dimethylbutano)-π-allyl and 1, 2-(1-oxo-butano)-3-phenyl-π-allyl palladium complexes have also been prepared from the corresponding cyclic α, β-unsaturated ketones. The structures of all these compounds have been confirmed by a study of their absorption spectra and of the NMR spectra.
  • Katsuo Kikuchi
    1967 Volume 40 Issue 2 Pages 355-358
    Published: 1967
    Released: March 27, 2006
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    The positions of the double bonds in 1-phenylcyclohexadiene-1,2-dicarboxylic acid, which had been obtained previously by the alkaline rearrangement of 2-phenyltropone-7-carboxylic acid, were elucidated from the spectral data. A similar rearrangement of tropone derivatives to dihydrobenzene derivatives was also observed. Tropone-2-carboxylic acid gave 2,5-cyclohexadiene-1,2-dicarboxylic acid, while 2-phenyltropone-5-carboxylic acid afforded 1-phenyl-2,4-cyclohexadiene-1,4-dicarboxylic acid. 2-Phenyltropone was also rearranged by alkali to 2-phenyl-2,5-cyclohexadiene-1-carboxylic acid.
  • Fuminori Akiyama, Keiichi Sugino, Niichiro Tokura
    1967 Volume 40 Issue 2 Pages 359-362
    Published: 1967
    Released: March 27, 2006
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    Esterifications of l- and d, l-menthols were undertaked in various solvents, such as chloroform, benzene, n-hexane, acetonitrile, methyl ethyl ketone, and liquid sulfur dioxide, in order to obtain some information on the solvent effect of the resolution of epimers by a kinetical method. The rate ratios, kdl/kll (generally larger than unity except in the case of sulfur dioxide), are in the following order: chloroform, benzene, n-hexane, acetonitrile, methyl ethyl ketone, and liquid sulfur dioxide, indicating higher kdl/kll ratios, in the less specific solvating solvents. The possibility of kinetical resolution in a non-specific solvating solvent is suggested, and the reason for it is discussed.
  • Takashi Ando, Masazumi Nakagawa
    1967 Volume 40 Issue 2 Pages 363-370
    Published: 1967
    Released: March 27, 2006
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    A cyclic diacetylene (XIa) has been synthesized by the oxidative coupling of 1, 5-bis(propargyloxymethyl)naphthalene (X) with a cyclic dimer (XIb) and a cyclic trimer (XIc). The electronic spectra of XIb and XIc have been found to be almost identical with that of naphthalene with respect to the location of the absorption maxima and the intensities. On the other hand, a marked decrease in the absorption intensities has been observed in the spectrum of the cyclic monomer (XIa). An inspection of the Dreiding model of XIa indicates that the two conformations (A and B) can retain the maximum distance between the dyine unit and the naphthalene nucleus. On the basis of the molecular model, the distance between the two chromophores and the angle between the short axis of the nucleus and the bridging chain have been estimated to be 2.26 Å, 21° for A and 2.12 Åand 38° for B. Employing these data, the hypochromic effect exerted by the diyne chromophore on the absorption of the naphthalene nucleus has been calculated according to the theory of Tinoco and Rhodes, resulting in a fairly good agreement with the observed values. Inversely, the calculation of the distance and the angle between the two chromophoric groups using the observed hypochromic effect has also given reasonable values. Therefore, the hypochromism observed in the cyclic diacetylene (XIa) has been attributed to the operation of dispersion-force interaction between diyne unit and the naphthalene chromophore.
  • Toshio Fukuda, Takahiko Tsuyuki, Yoshiaki Tanahashi, Takeyoshi Takahas ...
    1967 Volume 40 Issue 2 Pages 370-373
    Published: 1967
    Released: March 27, 2006
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    3β-Friedelanol (V, R=H) and 3β-shionanol (VIII, R=H) have been converted into γ-lactones, (VI) and (IX) respectively, either by lead tetraacetate-iodine oxidation followed by Jones’ oxidation or by photolysis of their nitrites (V, R=NO and VIII, R=NO) followed by Jones’ oxidation. These results confirm the presence of an axial methyl group at C-5 in friedelin (II) and shionone (I).
  • Junichi Oda, Tsutomu Nakagawa, Yuzo Inouye
    1967 Volume 40 Issue 2 Pages 373-378
    Published: 1967
    Released: March 27, 2006
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    The methoxy-mercuration of (−)-menthyl crotonate, cinnamate, and β-methylcinnamate resulted in partial asymmetric syntheses of the corresponding β-methoxylated derivatives, (−)-R-β-methoxybutyric acid, (−)-S-β-methoxy-β-phenylpropyl alcohol, and (−)-S-β-methoxy-β-phenylbutyl alcohol. The results suggested an ionic mechanism involving a cyclic mercurinium ion as an intermediate, formed by the electrophilic attack of mercuric acetate from the least-hindered side of the double bond in the Cram-Prelog model of the systems, followed by the attack of the methoxy anion from the opposite side. The reaction mechanism leading to the predominant enantiomers was discussed.
  • Siro Senoh, Yoshiko Maeno, Shoji Imamoto, Atsushi Komamine, Shizuo Hat ...
    1967 Volume 40 Issue 2 Pages 379-384
    Published: 1967
    Released: March 27, 2006
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    The optical resolution of three isomers of DL-β-(6-carboxy-α′-pyronyl)alanine was carried out by chemical as well as enzymatic methods and six optically active isomers were obtained. The configuration of each aspartic acid, derived from the ozonolysis of these optical isomers in aqueous solution, was analyzed enzymatically using glutamic-oxaloacetic transaminase and malate dehydrogenase. By the same procedure, the configuration of the two natural amino acids, stizolobic acid and stizolobinic acid, was confirmed and both were assigned the L-form. Thus the absolute configuration of six optical active isomers of β-(6-carboxy-α′-pyronyl)alanine and the two natural amino acids is assigned unequivocally, and the relationship between the synthetic and the natural amino acids is established.
  • Katsuo Kikuchi
    1967 Volume 40 Issue 2 Pages 385-388
    Published: 1967
    Released: March 27, 2006
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    The reaction of tropone and potassium hydroxide in the presence of potassium ferricyanide gave tropolone, salicylaldehyde, and p-hydroxybenzaldehyde, while in the presence of the copper ammine complex it afforded 2-aminotropone and salicylonitrile. Similarly, when tropone was reacted with aqueous ammonia, methylamine, or dimethylamine, 2-aminotropone and its N-methyl derivatives were formed. The reaction of 2-phenyltropone with ammonia and methylamine, and the reaction of 2-α-naphthyltropone and 4-bromo-2-phenyltropone with methylamine in the presence of copper salt, also afforded 2-aminotropone derivatives and/or salicylaldehyde derivatives.
  • Tokiko Hoshino, Takahiko Tsuyuki, Takeyoshi Takahashi
    1967 Volume 40 Issue 2 Pages 389-390
    Published: 1967
    Released: March 27, 2006
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    24-Oximinofriedelan-3β-ol (V) was converted via either lactone (VI) or hemiacetal (VIII) into diol (VII). Monoacetylation of the diol gave 24-acetoxyfriedelan-3β-ol (X), which was oxidized to keto acetate (XI). Hydrolysis of XI afforded the corresponding keto alcohol, followed by Jones’ oxidation giving rise to friedelan-3-on-24-al (I), mp 248—249°C, [α]578 +66°. The physical constants of I are not identical with those of friedelan-3-on-y-al, isolated by Courtney et al. from Siphonodon australe Bent. This furnishes a further evidence that friedelan-3-on-y-al is not friedelan-3-on-24-al (I), but friedelan-3-on-25-al, confirming the recent Courtney’s proposal.
  • Takeo Sato, Yoshitaka Saito, Masatsune Kainosho, Kazuo Hata
    1967 Volume 40 Issue 2 Pages 391-394
    Published: 1967
    Released: March 27, 2006
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    Dimethyl sulfoxide (DMSO), under acidic conditions, is known to yield formaldehyde as one of its decomposition products. A new method of synthesizing dialkoxymethanes, which consists of the treatment of alcohols with a DMSO-PPA (polyphosphoric acid) mixture, has been shown to be convenient and also generally applicable. Under mild conditions, five primary alcohols and four secondary alcohols are converted to the corresponding formals in 50—80 and 30—40% yields respectively. Dimethyl disulfide, bis(methylthio) methane and methylthiomethyl ether and an oxidation product of the alcohol have been shown to be the main by-products in this reaction. The examination of the NMR spectra has revealed that the acetal methylene protons of dialkoxymethanes made from (±)-secondary alcohols are observed as an AB quartet and as a singlet, each arising from meso and racemic compounds, respectively.
  • Sumio Umezawa, Tsutomu Tsuchiya, Saburo Nakada, Kuniaki Tatsuta
    1967 Volume 40 Issue 2 Pages 395-401
    Published: 1967
    Released: March 27, 2006
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    Several aminodisaccharides have been synthesized for the investigation of the relationship between the structural and biochemical characteristics of aminoglycosides. The preferential tosylation of maltose, followed by acetylation and bromination, yielded 2,2′,3,3′,4′-penta-O-acetyl-6,6′-di-O-tosylmaltosyl bromide, of which the bromine atom and the two tosyloxy groups were replaced by azido groups. The removal of acetyl groups and the catalytic hydrogenation of the azido groups gave 6,6′-diamino-6,6′-dideoxymaltosylamine. By an analogous procedure, 1′,6,6′-triamino-1′,6,6′-trideoxysucrose was prepared from sucrose via 2,2′,3,3′, 4,4′-penta-O-acetyl-1′,6,6′-triazido-1’,6,6′-trideoxysucrose. 6,6′-Diamino-6,6′-dideoxytrehalose was obtained by the ammonolysis of 2,2′,3,3′,4,4′-hexa-O-acetyl-6,6′-di-O-tosyltrehalose.
  • Katsuhiko Wakabayashi, Yoshio Kamiya
    1967 Volume 40 Issue 2 Pages 401-406
    Published: 1967
    Released: March 27, 2006
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    The oxidation of propylene with a large amount of propylene has been studied over vanadium and molecule oxide catalysts in a flow system. The relation temperature was 470°C; the partial pressure of oxygen was kept at 0.1 atm, while that of propylene was varied from 0.1 to 0.8 atm. The main oxidation products were carbon monoxide, carbon dioxide, and acrrolein. In the oxidation with a pure vanadium oxide catalyst, the yield of acrolein increased with the proplene partial pressure, and the selectivity to acrolein was about 30% at the propylene partial pressure, and the selectivity values of the selectivity to various reaction products at the contact time of 0 sec did not change even though the propylene partial pressure was changed from 0.1 to 0.8 atm. X-ray patterns of the catlyst used (free of carriers) show the presence (of V2O4 or a mixture) of V2O4and V2O3 according to the partial pressure of propylene. It is concluded that acrolein undergoes a secondary reaction more severly when a vanadium oxide catalyst is in the higher oxidative state, that is, when it is richer in V2O4. In the system of vanadium-molybedenum oxides, the three mixed catalysts, containing 10, 18 and 30 mol% moO3, acted in a similar way and raised the selectivity to acroline to some extent in coparison with a pure vanadium oxide catalyst, whatever was partial pressure of propylene. In the mixtures containing more than 50 mol% MnO3, MoO3 had a dilution effect on the catalytic activity. A pure molybenum oxide catalyst scarcely oxidized propylene at all 470°C. It has thus been found that the catalytic cativity of this system is closely related with the formation of solid solutions MoO3 in V2O5.
  • Seigo Kamiya, Masayoshi Tokutomi, Yukiko Matsuda
    1967 Volume 40 Issue 2 Pages 407-408
    Published: 1967
    Released: March 27, 2006
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  • Toshikazu Nagai, Katsuhiko Yamamoto, Niichiro Tokura
    1967 Volume 40 Issue 2 Pages 408-409
    Published: 1967
    Released: March 27, 2006
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  • Hiroyasu Sato
    1967 Volume 40 Issue 2 Pages 410
    Published: 1967
    Released: March 27, 2006
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  • Masao Iwamoto, Sadao Yuguchi
    1967 Volume 40 Issue 2 Pages 411-412
    Published: 1967
    Released: March 27, 2006
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  • Minoru Imoto, Kiichi Takemoto, Hiroyuki Sutoh
    1967 Volume 40 Issue 2 Pages 413-414
    Published: 1967
    Released: March 27, 2006
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  • Kenichi Murata, Akira Terada
    1967 Volume 40 Issue 2 Pages 414-416
    Published: 1967
    Released: March 27, 2006
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  • Sigeru Torii
    1967 Volume 40 Issue 2 Pages 417
    Published: 1967
    Released: March 27, 2006
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  • Suketaka Ito, Toshio Oya
    1967 Volume 40 Issue 2 Pages 418-419
    Published: 1967
    Released: March 27, 2006
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  • Ken-ichi Tanaka, Atsumu Ozaki
    1967 Volume 40 Issue 2 Pages 420-421
    Published: 1967
    Released: March 27, 2006
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  • Katsuji Ueno, Akihiro Shinkawa, Koichiro Hayashi, Seizo Okamura
    1967 Volume 40 Issue 2 Pages 421-422
    Published: 1967
    Released: March 27, 2006
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  • Yonezo Morino, Kozo Kuchitsu, Tsutomu Fukuyama
    1967 Volume 40 Issue 2 Pages 423-424
    Published: 1967
    Released: March 27, 2006
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  • Hisao Yamamoto
    1967 Volume 40 Issue 2 Pages 425
    Published: 1967
    Released: March 27, 2006
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  • Hiroyuki Utsumi, Kazutoshi Fujii, Hideo Irie, Akio Furusaki, Isamu Nit ...
    1967 Volume 40 Issue 2 Pages 426
    Published: 1967
    Released: March 27, 2006
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  • Aira Misono, Tetsuo Osa, Takamichi Yamagishi
    1967 Volume 40 Issue 2 Pages 427
    Published: 1967
    Released: March 27, 2006
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  • Yoshikane Kawasaki, Rokuro Okawara
    1967 Volume 40 Issue 2 Pages 428
    Published: 1967
    Released: March 27, 2006
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  • Takahiro Kumamaru, Yuzuru Otani, Yuroku Yamamoto
    1967 Volume 40 Issue 2 Pages 429
    Published: 1967
    Released: March 27, 2006
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