Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 46 , Issue 1
Showing 1-50 articles out of 87 articles from the selected issue
  • Kenshi Numakura, Masakatsu Saeki, Enzo Tachikawa
    1973 Volume 46 Issue 1 Pages 1-4
    Published: 1973
    Released: March 27, 2006
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    The moderator effect of Kr on the reaction of (I.T.)-activated 80Br with CH4 has been examined, keeping the ratio of Br2/CH4 at 0.02 or 0.05. The yield of CH280BrBr shows a slight decrease at the beginning of moderation and then tends to increase with further moderation. These facts suggest an additional formation of CH2-80BrBr via a thermal ionic process in highly-moderated systems. When the concentration of Br2 is varied in the system containing 10 cmHg of CH4 and from 40 to 36 cmHg of Kr, the yield of CH280BrBr first increases and then decreases, showing a broad maximum. This dependence not only partly explains the inconsistence of the present results with those previously reported, but also suggests the competition of two types of reaction in its formation. One must be the reaction of a radioactive radical with Br2, leading to the formation of CH280BrBr:
    ·CH280Br+Br2→CH280BrBr.
    The other type of reaction is a scavenging reaction of Br2 for the reacting 80Br atom.
  • Yasuaki Okamoto, Toshinobu Imanaka, Shiichiro Teranishi
    1973 Volume 46 Issue 1 Pages 4-8
    Published: 1973
    Released: March 27, 2006
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    The isomerization of propylene oxide was carried out over silica-magnesia catalysts and metal oxides at 260–270°C using a pulse reactor. The main products of the reaction were propionaldehyde, acetone, allyl alcohol, 1-propanol, and acrolein. Propionaldehyde and acetone are produced on acidic and basic sites respectively. Allyl alcohol is formed over acid-base bifunctional catalysts. 1-Propanol and acrolein are mainly produced through hydrogen-transfer reactions between allyl alcohol and propionaldehyde and propylene oxide. As regards these reactions, acid-base bifunctional catalysts are favorable and the reaction rate depends on the electron-donating power of the hydrogen acceptor and the basic strength of the catalyst. The acid sites on silica-magnesia catalysts are attributed to the forsterite produced by the reaction of magnesium oxide and silica gel, and the basic sites, to the magnesium oxide remaining. The metal oxides, such as magnesium and calcium oxides, are considered to have very weak acid sites.
  • Takiko Fujisawa, Shigenobu Okuda, Yuzaburo Fujita
    1973 Volume 46 Issue 1 Pages 9-14
    Published: 1973
    Released: March 27, 2006
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    The triketone (6-oxohelvolic acid (IIa) or its tetrahydro-derivative (IIb)) was readily oxidized in air into the anhydride (IIIa or b) in an alkaline solution; it spontaneously turned red or deep green and then gradually lost its color. In this reaction process, the presence of a relatively stable intermediate radical was confirmed by the ESR measurement. As a result of an analysis of the well-resolved proton hyperfine structure of this radical, it was explained that the structure of helvolic acid is of the protostane type: that is, it is a distinctive structure of the trans-fusion of the A/B ring juncture and a boat form of the B-ring. A reasonable oxidation mechanism including this intermediate radical was presented.
  • Raj Deo Singh
    1973 Volume 46 Issue 1 Pages 14-16
    Published: 1973
    Released: March 27, 2006
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    Ion-solvent interaction of some partially substituted alkylammonium ions in N-methylacetamide (NMA) and N-methylpropionamide (NMP) has been investigated from the point of view of electrical conductance and the derived Walden product. From the results, it seems that like tetraalkylammonium (R4N+) ions, Me3NH+ and CeMe3N+ ions are structure breakers in these solvents while Me3PhN+ ion is neither structure breaker nor structure maker.
  • J. K. Vij, Iqbal Krishan, K. K. Srivastava
    1973 Volume 46 Issue 1 Pages 17-20
    Published: 1973
    Released: March 27, 2006
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    Measurements of relative permittivity at 1 MHz and at 9.46 GHz, the refractive index for the Sodium D-line, have been made for (a) N,N-dimethylaniline, (b) N,N-diethylaniline, (c) o-chloroaniline, (d) m-chloroaniline and (e) p-chloroaniline at temperatures of 15, 25, 35, and 45°C in dilute solutions of benzene. Dielectric relaxation times τ(1) and τ(2) have been calculated by the method recently suggested by Higasi, Koga, and Nakamura in terms of the slopes a0, a′, a″, and aD. It is remarked that τ(2) at the experimental frequency of 9.46 GHz leads to τ1 the relaxation time for overall rotation, whereas τ(1) becomes an explicit function of τ1 and τ2- These determinations suggest the presence of both molecular and intramolecular rotations in the molecules. The results for τ(2) show a systematic decrease with increase in temperature whereas for τ(1) there seems to be no observable trend. The enthalpy and entropy of activation for molecular dielectric relaxation process has been determined. The enthalpy of activation for (a) and (b) is of the same order of magnitude (i.e., 3 kcal/mol), and the same is true for the case of (d) and (e) (1.8 kcal/mol) but 6.8 kcal/mol for (c). It appears that in o-chloroaniline, there is a finite probability of H–Cl bond formation between one of the amino hydrogens and the neighbouring chlorine atom.
  • Jae Shi Choi, Bo Won Kim
    1973 Volume 46 Issue 1 Pages 21-24
    Published: 1973
    Released: March 27, 2006
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    A kinetic study on the oxidation reaction of carbon monoxide has been carried out between 260 and 350°C by means of the static method using n-type ZnO semiconductor as a catalyst under various oxygen and carbon monoxide pressure. The order of reaction between 260 and 320°C was found to be 1.5, with dPCO2dt=kPCO·PO21⁄2. The Roginsky-Zeldovitsch equation, dPCO2dt=ke-ap, fits well at 350°C. The mechanism of the reaction can be explained by the n-type character of ZnO.
  • Noriyuki Sotani, Masatomo Hasegawa
    1973 Volume 46 Issue 1 Pages 25-29
    Published: 1973
    Released: March 27, 2006
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    The reaction between thiophene and hydrogen on hydrated molybdenum oxide was studied. Structural and compositional changes in the catalyst were found during the hydrodesulfurization of thiophene. The main products of the reaction were n-butane, butenes, and hydrogen sulfide. The conversion of thiophene increased with the progress of the reaction and reached a steady value after passing through a maximum. This reaction process was distinguished into two stages. One is the “aging stage,” and the other is the “stationary stage.” At the aging stage, three reactions, that is: i) dehydration, ii) reduction, and iii) sulfurization occur. The catalyst reacts with the reactants and changes in structure and composition. Hydrated molybdenum oxide was converted to MoO3 by liberating the structural water, and MoO3 was reduced to MoO2. A part of the MoO3 was also sulfurized directly with thiophene to MoS2 during the aging stage, but MoO2 could not easily be sulfurized. At the stationary stage, no further change in the catalyst was found, and only the catalytic hydrodesulfurization of thiophene occurred. The conversion at the stationary stage, when the aging temperature was low, was larger than the conversion at a high temperature. The difference between the conversions at different reaction temperatures was assumed to result from the structural and compositional changes in the catalyst caused by the different temperatures of the aging processes. In this reaction, the dehydration at the aging stage controls the activity of the catalyst.
  • Tetsu Yamamuro, Norisuke Hata, Ikuzo Tanaka
    1973 Volume 46 Issue 1 Pages 29-34
    Published: 1973
    Released: March 27, 2006
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    Carbostyril dimerizes photochemically in an aqueous solution, in order to investigate the effect of a hydroxide ion on the primary process of the photochemical dimerization in an aqueous solution, both measurements of the quantum yields and flash spectroscopic experiments were carried out under various conditions. The experiments revealed that the photodimerization reaction proceeded through a bimolecular interaction between the triplet and the unexcited carbostyril molecules, although the triplet carbostyrilate ion was in equilibrium with the triplet carbostyril. The triplet carbostyrilate ion was proved not to be involved in the dimerization process.
  • Masaaki Ogasawara, Hidetoshi Takaoka, Koichiro Hayashi
    1973 Volume 46 Issue 1 Pages 35-37
    Published: 1973
    Released: March 27, 2006
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    The rates of homogeneous electron-transfer reactions between radical anions and neutral molecules were studied in a variety of tetracyanoethylenide systems in order to obtain information concerning the counterion effect on the electron-transfer reactions. The estimated values of the rate constants had the same order of magnitude at room temperature for all the systems, while the activation energies and the preexponential factors were markedly dependent on the natures of the counterions and the solvents. The obtained results are discussed in terms of the forms and structures of the radical anions.
  • Hiroshi Kawabe, Masaya Yanagita
    1973 Volume 46 Issue 1 Pages 38-42
    Published: 1973
    Released: March 27, 2006
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    Although the apparent second-order rate constant of the amination of chloromethylated polystyrene with n-butylamine or with 2-aminobutanol decreased or increased, respectively, during the course of the amination in dioxane, as has been reported previously, both animations as well as the aminations of benzyl chloride have been found to conform to the ordinary second-order kinetics in DMF and DMSO. The viscometric measurements have indicated that the viscosity of the reaction mixture decreased during the amination with n-butylamine and increased slightly during the amination with 2-aminobutanol, but no relation between the kinetic behavior and the viscometric changes in the reaction mixtures could be found. The magnitude of the rate constants was comparable to that of the amination of benzyl chloride, and it increased with an increase in the dielectric constant of the solvents in this order: dioxane<<DMF<DMSO. The effects of the solvents on both the kinetic behavior in the aminations of the polymer and the magnitude of the rate constants have been discussed in terms of the interactions between the solvent and the solute molecules.
  • Takayuki Sano, Tomohiro Miyazaki, Nobuhide Tatsumoto, Tatsuya Yasunaga
    1973 Volume 46 Issue 1 Pages 43-47
    Published: 1973
    Released: March 27, 2006
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    The ultrasonic absorptions were measured in aqueous solutions of acetic, propionic, butyric, valeric, and chloroacetic acids as a function of the pH over the frequency range from 1.5 to 220 MHz at 25°C. From the dependences of μ′max and fr on pH, it was deduced that the perturbation of the ionization equilibrium of acids was the cause of the excess absorptions in dilute aqueous solutions. The kinetic parameters thus calculated were compared with those obtained by other methods.
  • Takako Shinoda, Hisae Enokido, Yoji Maeda, Hiroshi Tomita, Yo-ichiro M ...
    1973 Volume 46 Issue 1 Pages 48-52
    Published: 1973
    Released: March 27, 2006
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    The heat capacity of tetramethylsilane was measured at temperatures from 2 to 26 K and in the premelting temperature range for two crystalline forms. There are two crystalline forms in solid tetramethylsilane. The heat of fusion and triple point temperature of a stable form were found to be 1611.2±0.9 cal/mol and 174.049 K, while those of a metastable form to be 1396.0±0.8 cal/mol and 170.981 K. Tetramethylsilane was highly purified by preparative gas chromatography. The amount of impurity in the specimen of Si(CH3)4 was estimated to be 0.0046 mol% from measurement of the melting point range for two crystalline forms. The Debye characteristic temperature at 0 K, θD(0), was derived from low temperature heat capacity data, and the θD(T)⁄θD(0) curve was compared with those for C(CH3)4 and CF4. Despite high purity, Cp values for two crystalline forms in the region below melting points increases abnormally with the rise of temperature. The phenomena were interpreted as due to effects of formation of vacancies in the crystals and of melting accompanied by molecular orientation transition; analysis of heat capacity curves for the two crystalline forms was made in the region befow the melting point.
  • Takemi Kawaguchi, Masaya Hijikigawa, Yoshinori Hayafuji, Masashi Ikeda ...
    1973 Volume 46 Issue 1 Pages 53-56
    Published: 1973
    Released: March 27, 2006
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    The crystal structures of methyl bromide and methyl iodide have been determined by the X-ray diffraction method at about −120°C and about −80°C respectively. Both the crystals are isomorphous, with orthorhombic space group D2h16Pnma. Unit cells containing four molecules have the dimensions: a=4.474(1), b=6.420(2), and c=9.150(1) Å for methyl bromide, and: a=4.597(2), b=6.987(1), and c=10.117(1) Å for methyl iodide. These structures are quite different from that of methyl chloride, which has a symmetry of C2v12Cmc21. In the three crystals, all the molecules are found on the mirror planes; the difference lies in the mutual orientations of the molecules.
  • Takemi Kawaguchi, Akira Wakabayashi, Mitsuhiro Matsumoto, Toru Takeuch ...
    1973 Volume 46 Issue 1 Pages 57-61
    Published: 1973
    Released: March 27, 2006
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    The crystal structures of methylene dibromide and methylene diiodide (Form II) have been determined by the X-ray diffraction method at about −90°C and about −20°C respectively. Both the crystals are isomorphous, with monoclinic space group C2h6C2/c. Unit cells containing eight molecules have these dimensions: a=12.239(12), b=4.459(15), c=15.212(16) Å, and β=113.54(7)° for methylene dibromide, and a=13.346(3), b=4.720(90), c=16.479(5) Å, and β=114.48(8)° for methylene diiodide. The orientations of the methylene groups have been obtained by lattice-energy calculations.
  • Takemi Kawaguchi, Kazuo Tanaka, Toru Takeuchi, Tokunosuké Watan ...
    1973 Volume 46 Issue 1 Pages 62-66
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of methylene dichloride has been determined by the X-ray diffraction method at about −120°C. The structure has a symmetry D2h14Pbcn, and its orthorhombic tetramolecular cell has these dimensions: a=4.249±0.001, b=8.138±0.020, and c=9.492±0.002 Å. The positional parameters of the chlorine and carbon atoms are obtained by a three-dimensional Patterson function, followed by a least-squares refinement including the hydrogen atom. The structure thus obtained is in excellent agreement with the results of lattice-energy calculations. The crystal structure is quite different from that of methylene dibromide (and of methylene diiodide).
  • Vadim I. Pitchoozhkin, Hideo Yamazaki, Shoji Shida
    1973 Volume 46 Issue 1 Pages 67-70
    Published: 1973
    Released: March 27, 2006
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    The photolysis of liquid n-hexane has been studied at room temperature and at −78°C by using the resonance lines of Xe and Kr. The main process is hydrogen detachment, giving the same amount of hydrogen and of hexenes; relatively small amounts of the decomposition and dimer products were also formed. Upon the addition of SF6, the yield of the hydrogen detachment decreased strongly with an increase in the concentration of SF6, and then approached a constant value of 0.65 relative to that in pure n-hexane. The total amount of fluorinecontaining products detected in the presence of SF6 was relatively small compared with the amount of the decrease in the hydrogen detachment. As another electron scavenger, C6H13F was also tested; here, the decrease in the hydrogen detachment was quite small.
  • Tetsuo Miyazaki, Yoshiyuki Saitake, Zen-ichiro Kuri, Shigenori Sakai
    1973 Volume 46 Issue 1 Pages 70-74
    Published: 1973
    Released: March 27, 2006
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    The luminescence from 2,3-dimethylbutane(2,3DMB) containing toluene in the solid phase has been measured at 77°K during γ-irradiation. The emission consists of fluorescence and phosphorescence from toluene. Since the emission becomes zero upon the removal of a γ-ray source, it cannot be due to a post-irradiation effect. It is concluded from the dependency of the intensity on the concentration of toluene that the luminescence is due to an intermolecular energy transfer from 2,3DMB to toluene during γ-irradiation. ESR studies of γ-irradiated 2,3DMB containing toluene have also been undertaken at 77°K in order to obtain some information on the intermolecular energy transfer. The toluene anion is formed in the γ-irradiated 2,3DMB containing toluene. The dimer cation of toluene is formed in the γ-irradiated 2,3DMB containing toluene and an electron scavenger. The luminescence from toluene in the 2,3DMB matrix decreases upon the pre-irradiation of the sample at 77°K. When the pre-irradiated sample is illuminated by the light from a tungsten lamp to photobleach the toluene anion, the luminescence during γ-irradiation is recovered. Since the intensity of the luminescence does not correspond at all to the amount of toluene anions, the luminescence from toluene in the 2,3DMB matrix during γ-irradiation must not be due to a neutralization reaction between a toluene anion and a migrating hole. It is suggested that the migration of energy from the irradiated 2,3DMB to toluene may occur via an excitation transfer reaction.
  • Sachio Murakami, G. C. Benson
    1973 Volume 46 Issue 1 Pages 74-79
    Published: 1973
    Released: March 27, 2006
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    Molar excess enthalpies and molar excess volumes are reported for binary mixtures of n-butyl alcohol with isobutyl alcohol, sec-butyl alcohol, and t-butyl alcohol. All of the measurements were carried out at 25°C except for the excess enthalpies of n-butyl alcohol–t-butyl alcohol which were determined at 26°C. Interpretation of the results in terms of a lattice model was investigated.
  • Toshio Ichida
    1973 Volume 46 Issue 1 Pages 79-82
    Published: 1973
    Released: March 27, 2006
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    The thermal decomposition process of a hexavalent iron compound, K2FeO4, was studied by means of the Mössbauer effect. The compound began to decompose in air at about 170°C, and an amorphous product was obtained by the decomposition below 200°C. The product showed a paramagnetic Mössbauer spectrum at 293°K, with an isomer shift and quadrupole splitting of +0.40±0.02 mm/sec and 0.64±0.02 mm/sec respectively; it also showed a magnetically-split six-line spectrum at 4.2°K, with an internal magnetic field of 480±5 kOe. These Mössbauer parameters are characteristic of the Fe3+ state. The intermediate valence states, Fe5+ or Fe4+, were not observed during the decomposition process, and so it was concluded that the Fe6+ ions in K2FeO4 were reduced directly to Fe3+ ions. KFeO2 was formed in air above 250°C, and the temperature dependence of the internal magnetic field showed the Néel temperature of KFeO2 to be very high, 983±10°K.
  • Shigeru Tsunashima, Osamu Ohsawa, Chiharu Takahashi, Shin Sato
    1973 Volume 46 Issue 1 Pages 83-86
    Published: 1973
    Released: March 27, 2006
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    The 326.1 nm direct photolysis and the cadmium-photosensitized reactions of cyclopentanone have been compared in order to clarify the role of the triplet state of cyclopentanone in the photolysis. The products observed in the both photolyses were carbon monoxide, ethylene, cyclobutane, and 4-pentenal. The results obtained in the direct photolysis were very similar to those obtained in the cadmium photosensitization. The ethylene/cyclobutane ratio was not affected by the pressure and temperature changes. The 4-pentenal/CO ratio increased with a decrease in the temperature. These similarities suggest that the decomposition of cyclopentanone takes place through the lowest triplet state in both the photolyses. The efficiency of cyclopentanone in quenching triplet cadmium was found to be about 0.8 times that of cis-2-butene.
  • Tsunetake Fujiyama
    1973 Volume 46 Issue 1 Pages 87-89
    Published: 1973
    Released: March 27, 2006
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    The relative intensities of the 996 cm−1 line of liquid benzene and the 367 cm−1 line of liquid chloroform were observed at various temperatures with a high accuracy. The apparent intensity change due to the temperature was explained completely in terms of the local field effect, the density change, and the statistical distribution. The validity of Eckardt’s correction factor was strongly supported. In the case of liquid chloroform, an intensity change due to intermolecular interaction was observed after the elimination of the above three factors. The reliability of the relative intensity measurements of Raman lines was discussed.
  • Masahiro Yamaji, Yuzo Fujiwara, Ryuzo Asano, Shiichiro Teranishi
    1973 Volume 46 Issue 1 Pages 90-93
    Published: 1973
    Released: March 27, 2006
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    The reaction of dihaloethylenes with acetate anions in the presence of palladium(II) salts gave trans-diacetoxyethylenes catalytically. It was found that the system, PdCl2–NaOAc–CH3CN is the best for the diacetoxylation of dihaloethylenes, and that palladium(II) salts catalyze the isomerization of trans-diacetoxyethylene to its 1,1-diacetoxy derivative. The mechanism was also discussed.
  • Hideaki Chihara, Nobuo Nakamura
    1973 Volume 46 Issue 1 Pages 94-96
    Published: 1973
    Released: March 27, 2006
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    Chlorine-35 nuclear quadrupole resonance frequencies in the ionic crystal PCl4+·PCl6 were redetermined. Ten resonance lines were found and their temperature dependences were measured below the second order phase transition point at 102 K. The splitting Δvi in the resonance lines in the low temperature phase showed a similar temperature dependence as the order parameter. This was accounted for by a librational soft mode theory based on an anharmonic coupling between molecular or ionic librational modes in the crystal.
  • Hideaki Chihara, Minoru Nakamura, Kazuyuki Masukane
    1973 Volume 46 Issue 1 Pages 97-100
    Published: 1973
    Released: March 27, 2006
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    Molar heat capacity of solid P2Cl10 was measured between 4 and 150 K with an adiabatic calorimeter, with particular attention to the phase transition at 102.0±0.2 K. The heat and entropy of the transition were 148±3 Jmol−1 and 1.67±0.03 JK−1mol−1. Shape and magnitude of the anomalous heat capacity depend on the method of preparation. Anomaly in the heat capacity begins at about 75 K, rises gradually to a maximum of 9.12±0.08 JK−1mol−1 at 102.0 K and tails off at about 110 K. The shape of the excess heat capacity curve can be explained satisfactorily by the librational soft-mode theory which assumes that PCl6 anions tend to change equilibrium orientation with temperature.
  • Yukio Kubota, Michiko Kodama, Masaji Miura
    1973 Volume 46 Issue 1 Pages 100-103
    Published: 1973
    Released: March 27, 2006
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    The depolarization of the fluorescence emitted from a dye solubilized in the micelle was measured over a wide concentration range of sodium dodecyl sulfate (SDS). The polarization of the fluorescence showed an abrupt increase at the 1st CMC and at about 70 mM of SDS; the latter agrees very closely with the 2nd CMC revealed by conductivity and viscosity measurements. This phenomenon implies that there is a certain change in the micelle structure at the 2nd CMC. The micellar size was calculated from the fluorescence depolarization data using Perrin’s equation. The results showed that: (1) the micellar volume below the 2nd CMC is in good agreement with that determined by light-scattering, (2) the micellar volume gradually increases with an increase in the concentration of SDS, and (3) the micellar volume increases abruptly at the 2nd CMC.
  • Yoshio Miyazaki, Mitsuo Ito
    1973 Volume 46 Issue 1 Pages 103-106
    Published: 1973
    Released: March 27, 2006
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    The low-frequency Raman active lattice vibrations of the 9,10-anthraquinone single crystal were measured at various temperatures from 26°C to −190°C, and the symmetry species of the observed Raman bands were determined by polarization measurements. From a comparison between the observed and calculated frequencies, it seems that Dashevsky’s potential expresses well the intermolecular potential of the 9,10-anthraquinone crystal. It was also found that the temperature dependence of lattice vibrations can be explained reasonably with this potential.
  • Shunzo Katayama
    1973 Volume 46 Issue 1 Pages 106-109
    Published: 1973
    Released: March 27, 2006
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    Thermodynamic equilibrium constants for the ion-association in aqueous solutions of magnesium and nickel sulfates were determined by electrical conductivity measurements at various temperatures between 0°C and 45°C. The standard Gibbs energy and the enthalpy and entropy for the reaction M2++SO42−\ ightleftharpoonsM2+·SO42− (M: Mg or Ni) were then calculated from the temperature-dependence of the ion-association constants. The values obtained are as follows: ΔG°298=−2.91 kcal mol−1, ΔH°=2.04 kcal mol−1, and ΔS°298=16.6 cal deg−1 mol−1 for Mg2·SO42−; and ΔG°298=−3.10 kcal mol−1, ΔH°=1.27 kcal mol−1, and ΔS°298=14.7 cal deg−1 mol−1 for Ni2+·SO42−.
  • Hisao Negita, Kaoru Shibata, Tsuneo Kubo
    1973 Volume 46 Issue 1 Pages 110-113
    Published: 1973
    Released: March 27, 2006
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    Four nuclear quadrupole resonance (NQR) lines due to 14N nuclei of the ring nitrogens in 2-aminopyrimidine were paired for the powder sample by use of a frequency-modulated spectrometer and a Helmholtz coil for the Zeeman field (H). NQR parameters e2Qq=3707.2 kHz and η=0.0646 were obtained for one nitrogen, and e2Qq=3759.6 kHz and η=0.0329 for the other. Moreover, the frequency of the lower line of a pair of lines for the amino nitrogen was predicted from the shift of the higher line subjected to the Zeeman field in a single crystal. The region around the expected position was carefully swept and a very weak line was found at 2357.8 kHz. Thus e2Qq=3428.0 kHz and η=0.2488 were deduced for the amino nitrogen. The quadrupole coupling constant for the amino nitrogen in 2-aminopyrimidine was smaller than that for the amino nitrogen in 2-aminopyridine. The asymmetry parameter for the amino nitrogen in 2-aminopyrimidine was smaller than that for the amino nitrogen in 2-aminopyridine and roughly equal to that for the amino nitrogen in aniline.
  • Kie Hishinuma, Hideo \={O}ki, Y\={o}ichi Kurokawa, Norio Yui
    1973 Volume 46 Issue 1 Pages 113-115
    Published: 1973
    Released: March 27, 2006
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    The salting-out adsorption of isomeric butyl alcohols on Amberlite (200) type designated as the macroreticular ion-exchange resin (MR type) was studied. On the basis of the difference in the salting-out effect of isomers, the separation of the isomer mixture in a dilute aqueous solution was attempted by using an aqueous ammonium sulfate solution as an eluent and the MR resin as a stationary phase. It seems that MR resin as the stationary phase is inadequate for the salting-out chromatography of isomeric butyl alcohols.
  • Masuo Aizawa, Shuichi Suzuki, Teruo Suzuki, Hiroshi Toyama
    1973 Volume 46 Issue 1 Pages 116-119
    Published: 1973
    Released: March 27, 2006
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    The line-width of the nuclear magnetic resonance (NMR) signal gets narrow, in general, with an increase in the temperature. In contrast, the NMR line-width of the water proton in agarose gels was found to increase with an increase in the temperature up to about 30°C. As for the other polysaccharide gels, such as curdlan-type polysaccharide, and κ-and λ-carrageenan gels, the NMR line-width of water increases with an increase in the temperature. The anomalous temperature dependence of the line-width was most marked in agarose gels than in other polysaccharide gels. The close relationship between the gel network, which consists of small cavities (microspace) of the micelle, and the magnitude of the anomality was revealed, this anomalous effect was named the “Micro-Space Effect.”
  • Takeshi Kawakami, Akira Usui, Yoshisada Ogino
    1973 Volume 46 Issue 1 Pages 120-126
    Published: 1973
    Released: March 27, 2006
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    In order to clarify the mechanism of the acidity change due to compression, zinc sulfate was compressed under various pressures, ranging from 0 to 7000 kg/cm2, and the surface acidity was measured and compared with the data of the structural change in the sample. According to the experimental results, the surface acidity varied on compression. At lower compacting pressures (P∼2500 kg/cm2), the content of weak acid (H0=1.5–3.3) was high and that of the strong acid was poor. These facts were explained by the higher content of anion-water, or heptahydrate, in the sample. In the pressure region of P=2500<5500 kg/cm2, the acidity-pressure curve showed a maximum at 4500 kg/cm2. Further, in this pressure range, the acidity-pressure curve paralleled well the respective curves of the X-ray peak width of hexahydrate pressure, the relative intensity of the IR v1(SO42−)-pressure, and the half width of the IR v3(SO42−)-pressure. It was considered that the acidity change in this pressure range is caused by the change in the content of the distorted structural unit of hexahydrate in the sample. In the highest pressure range, the content of weak acid was found to increase, whereas the content of strong acid was found to decrease. These results were discussed by considering the increased inclusion of tetrahydrate in the sample.
  • Shoe Baba, Yoshisada Ogino
    1973 Volume 46 Issue 1 Pages 127-133
    Published: 1973
    Released: March 27, 2006
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    In order to investigate the effect of the compacting pressure on the surface basicities of solids, experiments were carried out by employing various carbonates, hydroxides, and oxides of alkali metals and alkaline earth metals as samples. That is, compacting pressures ranging from 0 to 15000 kg/cm2 were applied to these samples, and the changes in the surface basicities were observed using an indicator method. It was observed that the surface basicities of various solid vary on compression. Further, the respective basicity change in cadmium carbonate, calcite, and aragonite could be explained by the change in the surface area of each of these samples. On the other hand, the basicity changes of both strontium carbonate and barium carbonate could be explained thus only with difficulty. From the results of the X-ray-diffraction study and the electron-diffraction study, the changes in the crystal structures of these samples were suspected of causing the basicity changes due to compressions. According to the results of infrared spectroscopic studies, changes in the symmetry around carbonate ions in the sample crystals were considered to be the cause of the basicity changes in strontium cabonate and barium carbonate.
  • Takeshi Kawakami, Hiroyoshi Banba, Yoshisada Ogino
    1973 Volume 46 Issue 1 Pages 133-139
    Published: 1973
    Released: March 27, 2006
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    In order to clarify the mechanism of the acidity change due to compression, magnesium sulfate was compressed under various pressures ranging from 0 to 12000 kg/cm2, the surface acidities, the powder X-ray diffraction patterns, the DTA data, and infrared spectra of the compressed samples were thus obtained. According to the experimental results, the surface acidity of the sample did not vary upon the compression of low pressures (0–6000 kg/cm2), and a further increase in the compacting pressure resulted in an increase in the surface acidity. From the results of the X-ray diffraction studies, infrared, and far infrared absorption studies and the DTA studies, the relations between the acidity change and the structural changes of the samples were discussed. As a result of this work, the observed acidity change was explained in terms of the distortion of the structural unit of magnesium sulfate.
  • Kazuhiko Ishizu, Fujito Nemoto, Hideo Hasegawa, Koji Yamamoto, Masao N ...
    1973 Volume 46 Issue 1 Pages 140-143
    Published: 1973
    Released: March 27, 2006
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    The electron spin resonance has been observed for anion radicals of 4,4′-polymethylene bridged biphenyls which have various lengths of the polymethylene chain, from the carbon number of n=11 to that of n=16. The relation between the chain length of the methylene bridge and the ring-proton splitting were studied in order to see how the polymethylene span brings on a strain in the biphenyl ring. The geometrical structures of the sp3-hybrid bond of the β-carbons were investigated on the basis of the observed values of the β-proton splitting in each derivative. In the cases of both pentadeca and hexadeca derivatives, the magnitude of both the ortho- and the meta-ring proton splitting are comparable with those of the 4,4′-diethylbiphenyl anion radical, the open-chain model of the present derivatives. A rotation of the β-methylene sp3-bond is forbidden in this case, however, and the coupling constants of the β-methylene protons no longer exhibit an equivalent value; that is, two of these C–H bonds are placed on a coplanar biphenyl plane, but the others are twisted out by about 30° from the 2pz axis of the ring-carbon atom. When the number of the methylene groups is reduced from thirteen to twelve, the magnitude of the ortho-ring proton coupling constant is greatly reduced. The HMO calculations of the spin density were carried out. The observed tendency of the ring-proton splitting can be qualitatively understood on the assumption that the coplanar biphenyl ring may be modified by twisting the phenyl groups about the central 1-1′ bond rather than by slanting them together against the original aromatic plane. A strong beam of the polymethylene chain also causes a modification of the geometrical structure of the β-methylene sp3 bond and results in a reduction of the β-proton coupling constant to a large extent.
  • Kenzo Nagase
    1973 Volume 46 Issue 1 Pages 144-146
    Published: 1973
    Released: March 27, 2006
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    The thermal decomposition reactions of a number of metal oxalato complexes in the solid state were studied by an EGA method in a helium atmosphere. As regards the decomposition stage of an anhydrous complex, the complexes investigated could be divided into three groups: the complexes of Mn(III), Fe(III), Co(III), Rh(III), Cu(II), Pd(II), and Pt(II), this first group giving only CO2 as a gaseous product, decomposed by electron transfer from an oxalato ligand to a central metal ion; the complexes of Al(III) and Zn(II), this second group giving CO and CO2 in the molar ratio of 1:1, decomposed by C–O bond breaking to form a metal oxide with no change in the oxidation number of a central metal; and the complexes of V(III) and Cr(III), this third group giving CO2and a smaller amount of CO, decomposed through both the processes, electron transfer and C–O bond breaking. The subsequent decomposition reactions of the bivalent metal oxalato complexes formed upon heating the corresponding trivalent metal oxalato complexes were divided into two types: one is associated with further reduction of a central metal ion, while the other is associated with C–O bond breaking.
  • Yoshihisa Matsui, Yukio Kurosaki, Yoshio Date
    1973 Volume 46 Issue 1 Pages 147-152
    Published: 1973
    Released: March 27, 2006
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    The behavior of ammonia and several amines at the dropping mercury electrode was studied in N,N-di-methylformamide containing 0.10M Et4NClO4 by means of DC polarography and amperometric titration. Ammonia gave a diffusion-controlled anodic wave, which was attributed to the reversible oxidation of mercury to the 1:2 complex of mercury(II) with ammonia. A dilute solution of methylamine or dimethylamine gave a diffusion-controlled anodic wave similar to that of ammonia. A concentrated solution of each amine gave a prewave due to the adsorption of the electrolysis product, Hg(am)22+, on the electrode surface. Trimethylamine also gave an anodic wave, but it was attributed to the oxidation of the amine itself to the corresponding cation radical. Ethylenediamine and 1,2-diaminopropane each gave a well-defined anodic wave over the concentration range examined. The wave was diffusion-controlled and was attributed to the reversible oxidation of mercury to the chelate compound of the Hg(diam)22+ type. No adsorption phenomena were observed in this case. Aromatic amines such as aniline and β-naphthylamine gave no anodic waves. The overall stability constants of the 1:2 complexes of mercury(II) with ammonia, methylamine, dimethylamine, ethylenediamine, and 1,2-diaminopropane were evaluated by the analyses of the waves to be 1016.9, 1017.1, 1015.0, 1023.5, and 1024.0M−1 respectively.
  • Kozo Nagashima, Hisanobu Wakita, Akihiko Mochizuki
    1973 Volume 46 Issue 1 Pages 152-156
    Published: 1973
    Released: March 27, 2006
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    The factors which influence the crystallization of rare earth carbonates were studied. Crystalline rare earth carbonates were precipitated at various temperatures from aqueous solutions by using sodium carbonate, sodium bicarbonate, trichloroacetic acid, and urea as precipitants. The crystal parameters, compositions, and factors concerning the formations of various carbonates, such as lanthanite-type Ln2(CO3)3·8H2O(Ln=La, Ce), tengeritetype Ln2(CO3)3·nH2O(Ln=Nd, Sm, Gd, Dy, Ho, Er, and Y, n=2–3), monoxocarbonate-type Ln2O(CO3)2·nH2O(Ln=La, Ce, Nd, and Sm, n=1–2) and a hydrated double carbonate of rare earth and sodium (rare earth= La, Ce, Nd, Sm, Gd, Dy, and Y) were determined by chemical analysis and X-ray powder diffractometry.
  • Kiyoshi Mizutani, Motoo Yasuda
    1973 Volume 46 Issue 1 Pages 157-159
    Published: 1973
    Released: March 27, 2006
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    The viscosities of aqueous solutions containing a metal chelate formed with iminodiacetic acid (H2ida) or N-methyliminodiacetic acid (H2mida) were measured with Cannon-Fenske capillary viscometers. Measurements were made in a Shibata viscosity bath maintained at 25±0.01°C. The Jones-Dole viscosity B-coefficient of each bis-ida chelate is lower than that of the corresponding bis-mida chelate, as may be expected. The B-coefficients for the mono-ida and mono-mida chelates were not determined accurately and will not be reported here. The B-value of cisN-[Co(ida)2] is higher than that of the trans-isomer. This is probably associated with the fact that the cis-isomer interacts with the solvent more strongly than the trans-isomer.
  • Tadashi Aoki, Keiji Matsumoto, Shun’ichiro Ooi, Hisao Kuroya
    1973 Volume 46 Issue 1 Pages 159-162
    Published: 1973
    Released: March 27, 2006
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    The absolute configuration of (−)589-[Co ox en2]+ has been determined by the X-ray diffraction method. The crystals of (−)589-[Co ox en2]Br·H2O are orthorhombic, with the space group P212121, and the unit cell dimensions are: a=16.67(1)Å, b=12.40(1)Å, c=6.183(7)Å, and Z=4. The crystal structure was solved by the conventional Patterson and Fourier methods, and refined by the least-squares procedure to an R factor of 9.97%. The cobalt atom has an octahedral coordination, being chelated by an oxalate anion and two ethylenediamine molecules which are of the ob-lel conformation. The absolute configuration of the complex cation can be denoted as Δ(δλ).
  • Akira Ohyoshi, Tsuneo Kawamura
    1973 Volume 46 Issue 1 Pages 162-165
    Published: 1973
    Released: March 27, 2006
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    The distribution study of neptunium ions in an aqueous solution containing Np(IV) and Np(V) was made using the metal chelate extraction system, TTA-benzene, or HDEHP-benzene at room temperature. The results obtained by this method were then compared with those obtained by spectrophotometry. In each system, a linear relationship was obtained between the fraction of the Np(V) ion and 1/(D+1), where D is the distribution ratio of neptunium. This analysis was performed with an accuracy of ±5% and was established within one minute in the case of the HDEHP-benzene system. The results obtained by this method were in good agreement with those obtained by spectrophotometry.
  • Kiyoshi Isobe, Yukio Nakamura, Shinichi Kawaguchi
    1973 Volume 46 Issue 1 Pages 166-169
    Published: 1973
    Released: March 27, 2006
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    The ultraviolet spectrum of Ni(acac)2 in dichloromethane shows two maxima, at 265 and at 300 nm. The intensity ratio of these two bands is very sensitive to the water content of the solvent, the high-energy band decreasing and the low-energy band increasing with the water content. It is thus suggested that the trimeric Ni(acac)2might have only one absorption band, at 265 nm, in dichloromethane completely free from donor impurities. The UV spectrum of Ni(acac)2 in dichloromethane changes with time due to the hydrolytic reaction. Even in the solvent containing 4.54×10−3M water, acetylacetone was freed from the complex in the yield of 34.4% after 48 hours’ standing. A minute amount of the residual complex was isolated; its tetrameric structure is suggested on the basis of its UV spectrum in methanol.
  • Ryokichi Tsuchiya, Shigeo Nakagawa, Akira Uehara, Eishin Kyuno
    1973 Volume 46 Issue 1 Pages 169-175
    Published: 1973
    Released: March 27, 2006
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    It was found by derivatography and spectral measurements that the double complex salts, [Co(H2O)2N4] [Co(CN)6nH2O, where N4 is 4NH3, two moles of ethylenediamine (en) or one mole of triethylenetetramine (trien), [Co(NH3)2trien][Co(CN)6]·2H2O, [Co(NH3)tepa][Co(CN)6].2H2O, where tepa is tetraethylenepent-amine, and [Co(H2O)2trien][Cr(CN)6]·2H2O underwent deaquation-or deammonation-CN-bridging formation reaction upon heating. The general tendency was observed to be as follows: the more stable the structural configuration of the coordination sphere, the higher the activation energy. In the case of the complex containing hexacyanochromate(III) as an anion, the activation energy for the bridging formation reaction is especially high as a result of possible flipping in CN bridging groups.
  • Makoto Aihara, Seizo Misumi
    1973 Volume 46 Issue 1 Pages 175-178
    Published: 1973
    Released: March 27, 2006
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    Polarographic behaviour of some lanthanoids(III) has been studied in N,N-dimethylacetamide. La(III), Pr(III), and Nd(III) showed irreversible, three-electron reduction wave and the other lanthanoids(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), and Lu(III) except Sm(III), Eu(III), and Yb(III), gave irreversible, three-electron reduction wave with a pre-wave. The kinetic parameters for La(III), Pr(III), and Nd(III) were determined by means of Koutecky’s method. Sm(III), Eu(III), and Yb(III) showed two-step reduction waves, the first wave being a reversible, one-electron reduction wave. These solvated lanthanoids(III) were investigated also by cyclic voltammetry.
  • Hiroshi Ogino, Masatake Takahashi, Nobuyuki Tanaka
    1973 Volume 46 Issue 1 Pages 178-183
    Published: 1973
    Released: March 27, 2006
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    The kinetics of racemization reactions of ethylenediaminetetraacetatocobaltate(III), CoIIIedta, and trimethylenediaminetetraacetatocobaltate(III), CoIIItrdta, were investigated in acid solutions. The rate law for the racemization of (+)546CoIIIedta is:
    \fracd[(+)546CoIIIedta]dt=−2\frackr1Ka+kr2[H+]Ka+[H+][(+)546CoIIIedta]
    where Ka is the equilibrium constant of the reaction:
    (+)546CoIII(H2O)Hedta\ ightleftarrows(+)546CoIIIedta+H+
    The values of kr1 and kr2 at 120°C and at an ionic strength of 0.53 are 2.0×10−5 sec−1 and 5.6×10−4 sec−1 respectively. The rate law for the racemization of (+)589CoIIItrdta is:
    \fracd[(+)589CoIIItrdta]dt=−2kr2[H+][(+)589CoIIItrdta]
    The value of kr2 at 120°C and at an ionic strength of 0.53 is 1.9×10−5 l mol−1 sec−1. It is known that the rate of the racemization reaction of optically-active CoIIedta2− is accelerated by the presence of CoIIedta2− because of the electron-exchange reaction between these two species. In this paper, the electron-exchange reaction between CoIIItrdta and CoIItrdta2− is also investigated by the utilization of the optical activity. This reaction proceeds faster than the reaction between CoIIIedta and CoIIedta2−.
  • Etsuro Kobayashi
    1973 Volume 46 Issue 1 Pages 183-186
    Published: 1973
    Released: March 27, 2006
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    In order to develop fireproof materials, a new compound, phosphoric aniline diamide, was prepared by employing phosphorus oxychloride, aniline, and ammonia as the starting materials. The conditions for the synthesis and the characteristics of the product have been investigated. Phosphoric aniline diamide can be prepared in the following way: 2 moles of aniline are added to 1 mole of phosphorus oxychloride diluted with chloroform, and the precipitate of aniline hydrochloride, a by-product, is separated from the solvent by filtration. A mixture of phosphoric amide and ammonium chloride is formed by the reaction between an excess of gaseous ammonia and the above filtrate at −10–20°C, and is then separated from the mother liquor. Crude phosphoric amide is extracted from the mixture with ethanol, and subsequent re-extraction with acetone yields the pure product with the formula PONHC6H5(NH2)2. The product thus obtained is composed of a white crystalline powder, soluble in water, ethanol and acetone but insoluble in various organic solvents. The compound shows its own characteristic X-ray diffraction pattern and IR absorption bands. Upon heating, the product melts at about 140°C; condensation occurs by de-ammoniation above 170°C, and conversion into insoluble condensed amidophosphates takes place.
  • Yasuo Nakao, Akitsugu Nakahara
    1973 Volume 46 Issue 1 Pages 187-190
    Published: 1973
    Released: March 27, 2006
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    Copper(II) and nickel(II) complexes of Schiff bases derived from salicylaldehyde(Sal) and dipeptides containing glycine and/or β-alanine have been prepared. It has been found that Schiff base ligands containing glycylglycine (Gly·Gly), glycyl-β-alanine (Gly·β-Ala) or β-alanylglycine (β-Ala·Gly) as the peptide moieties give rise to square-planar, quadridentate copper(II)- and nickel(II)-chelates, while the N-salicylidene-β-alanyl-β-alanine (Sal=β-Ala·β-Ala) does not form the same type of copper(II)- or nickel(II)-chelate. It is concluded on the basis of spectrophotometric, polarographic and other measurements that the stability decreases in the order 6-5-5-([Cu(Sal=Gly·Gly)])≥6-5-6-([Cu(Sal=Gly·β-Ala)])≥6-6-5-([Cu(Sal=β-Ala·Gly)])>>6-6-6-([Cu(Sal=β-Ala·β-Ala)])fused-ring system.
  • Kaoru Harada, Tadashi Okawara
    1973 Volume 46 Issue 1 Pages 191-193
    Published: 1973
    Released: March 27, 2006
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    The addition reactions of benzoyl cyanide to the Schiff’s bases prepared from several aliphatic aldehydes with optically active benzylic amines were studied. The adioditn products were hydrolyzed and hydrogenolyzed to form optically active amino acids. The synthetic yields of optically active amino acids were in a range 15 to 57% and the optical purities were in a range 15–37%. When S-α-alkylbenzylamines were used, S-amino acids were obtained.
  • Shunzo Yamamoto, Norio Nishimura, Shigeo Hasegawa
    1973 Volume 46 Issue 1 Pages 194-198
    Published: 1973
    Released: March 27, 2006
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    The tautomeric equilibrium constants, Kt=[ammonium ion]/[azonium ion], of the first conjugate acids of 4-dialkylaminoazobenzene derivatives were estimated by the spectrophotometric method. The Kt values increase in this order: pyrrolidino- <dimethylamino- <diethylaminoazobenzenes. The effects of N-alkyl groups on the base strength of the amino and azo nitrogens were examined in order to explain the effects on the tautomeric equilibrium. The base strength of azo nitrogens is governed by the degree of the resonance interaction between the amino group and the rest of the molecule. For dimethylamino- and pyrrolidinoazobenzenes, the base strength of the amino nitrogen can also be explained in terms of the resonance effects, but the amino nitrogen of diethylaminoazobenzenes exhibits an anomalously high base strength, arising from the steric inhibition of the hydrogen bonding in the free base. The above order of Kt can be explained in terms of these cumulative resonance and steric effects.
  • Kimiaki Imafuku, Hisashi Matsumura
    1973 Volume 46 Issue 1 Pages 199-203
    Published: 1973
    Released: March 27, 2006
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    The methylation of 4-styryltropolones with diazomethane afforded two isomers, 2-methoxy-4-styryltropones and 2-methoxy-6-styryltropones. Their reactions with ammonia gave the corresponding 2-amino-4-styryltropones and 2-amino-6-styryltropones, respectively, by normal nucleophilic substitution. Infrared and ultraviolet absorption spectra were measured. The halochromism of 2-aminotropones was also examined, the halochromic shifts being found to be linearly correlated with the Hammett substituent constants.
  • Yoshiaki Kusuyama, Yoshitsugu Ikeda
    1973 Volume 46 Issue 1 Pages 204-209
    Published: 1973
    Released: March 27, 2006
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    The normal substituent constant, σ0, and the resonance substituent constant, Δ\barσR+, in the Yukawa and Tsuno treatment of cyclopropyl and 2,2-dichlorocyclopropyl were determined by the ionization of m-, p-substituted phenylacetic acids in 50% aqueous ethanol and by the solvolysis of α-(m-, p-substituted phenyl) ethyl chlorides in 80% aqueous acetone. For cyclopropyl, the obtained σ0 value indicates an inductive electron-attracting behavior, while the Δ\barσR+ value indicates a marked enhancement of the electron-releasing resonance effect on the electron deficient reaction center compared with alkyl groups. A minor resonance contribution was observed for the 2,2-dichlorocyclopropyl group.
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