Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 8
Showing 1-50 articles out of 80 articles from the selected issue
  • Koichi Katoh, G. M. Schmid
    1971 Volume 44 Issue 8 Pages 2007-2009
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The adsorption of benzoic acid from solutions of 10−2 to 10−5 M on gold electrode surface in perchlorate solutions of pH 1–4 was studied from differential capacity data obtained by a single pulse method. Strong adsorption is observed in the more acidic solutions. This points to predominant adsorption of benzoic acid molecule, rather than benzoate anions, possibly due to the π-electron interaction. At pH 1, benzoic acid replaces four water molecules. This interprets the flat adsorption of benzoic acid molecule on the gold electrode and the π-electron interaction with free electron of the metal surface. The standard free energy of adsorption Δ\barG° is −10.4 kcal/mol.
  • Hiroshi Nakatsuji, Isao Morishima, Hiroshi Kato, Teijiro Yonezawa
    1971 Volume 44 Issue 8 Pages 2010-2017
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Anisotropy of the indirect nuclear spin-spin coupling constant was studied theoretically. All the contributions to the coupling tensors were calculated for various molecules by using the INDO molecular orbitals. As shown in part I of this series, the calculated 13C–H coupling anisotropy of 13CH3F is too small to be compared with the value obtained experimentally by Krugh and Bernheim. Thus we examined the substituent effect on the anisotropy in the 13CH3X series. It is concluded that the experimentally estimated value of the 13C–H coupling anisotropy in 13CH3F as large as 1890 Hz is erroneous and that it contains some other effects which are more important than electronic effect. We believe that the change in molecular geometry from gas state to the solute state in a nematic solvent is the most probable origin for the differences between theories and experiments. For the directly bonded C–X couplings (X is C, N or F), their anisotropies are in the same order of magnitude as their isotropic couplings. For the non-bonded C–X nuclei, they seem negligible in magnitude. For the F–F couplings, their anisotropies are exceptionally large and the orbital term is a very important source of anisotropy. Furthermore, even for the isotropic F–F couplings, the orbital and spin dipolar terms are very important and sometimes make decisive contributions exceeding the Fermi contact term.
  • Shunzo Yamamoto, Norio Nishimura, Shigeo Hasegawa
    1971 Volume 44 Issue 8 Pages 2018-2025
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electric dipole moments of trans-4-N,N-dimethylaminoazobenzene and its derivatives, and the absorption spectra of azobenzene derivatives and their conjugate acids have been measured. The dipole moment and the intensity of the π–π* band are clearly reduced by introduction of methyl groups into ortho positions to azo group. The twisting angle of the benzene rings with respect to the azo group has been estimated for 2,2′-disubstituted azobenzenes and their conjugate acids by means of the Braude equation. From the spectral intensity and transition energy, it was concluded that the conjugate acids are generally more susceptible than the bases to the steric effect.
  • Katsutoshi Ohkubo, Hidetoshi Shimada, Masahide Okada
    1971 Volume 44 Issue 8 Pages 2025-2030
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electronic states of the group I, II, and III methyl compounds were investigated using the extended Hückel method, with particular reference to the nature of the bond of metal-carbon. First, the monomers of the group I methyl compounds indicated remarkable electron-localizations on the carbon atom in CH3. (CH3Li)4 was found to be a possible tetramer, its total energy being lower by 0.34 eV per CH3Li unit than that of the CH3Li-monomer in spite of the unstability of (CH3Li)2. Second, (CH3)4Be2 was more stable than (CH3)2Be by ca. 4.04 eV per (CH3)2Be unit. Third, the stability of (CH3)3B in the form of a monomer was understood well by the fact that its π-bond nature is so much in comparison with that of (CH3)3Al. Finally, the reactivities in a series of the groups were discussed briefly in connection with the electronic states.
  • V. N. Verma, K. P. R. Nair, D. K. Rai
    1971 Volume 44 Issue 8 Pages 2031-2035
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The near ultraviolet absorption spectra of 1,2,3- and 1,3,5-trimethylbenzenes have been photographed in vapour phase at different vapour pressures on a Q-24 Zeiss Medium Quartz Spectrograph. Assuming C2v symmetry for the 1,2,3- and D3h symmetry for the 1,3,5-isomer, tentative assignments of the observed bands have been made in terms of various ground state and excited state fundamentals. The respective vibrational modes have also been suggested.
  • Toshio Kinugasa, Juziro Nishijo, Genzo Hashizume, Isamu Imanishi
    1971 Volume 44 Issue 8 Pages 2035-2038
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It was found by X-ray analysis that aminomalonic acid forms a solid complex with glycine in a molar ratio of 1 : 1 on crystallization from an aqueous solution. DTA-TGA of the solid complex at a heating rate of 1.0°C/min in air showed that the solid complex decarboxylates at higher temperature, but more slowly than aminomalonic acid and that both endothermic and following exothermic peaks which were distinctly observed in the region of decarboxylation of aminomalonic acid at temperatures 108–140°C are only slightly observed at 168–175°C. Activation energies in the thermal decomposition of aminomalonic acid and the solid complex, caluculated from themogravimetric curves, were 69.4 kcal/mol and 21.3 kcal/mol, respectively. The results indicate that aminomalonic acid is thermally more stabilized than the acid itself by forming the solid complex with glycine.
  • Kazushige Suzuki, Takehiko Watanabe
    1971 Volume 44 Issue 8 Pages 2039-2042
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The viscosity of dilute emulsion with disperse phase of volume fraction φ=0.005–0.06 was measured, and the dispersion state of emulsion droplets under shear was observed with a photomicroscope. Oil components used were aromatic hydrocarbons, i.e., benzene, o-xylene, and toluene, and saturated hydrocarbons, i.e., cyclohexane, decaline, n-hexane, etc. As emulsifier, Arlacel 60 or Arlacel 83 was used for W/O type emulsion and Tween 20 for O/W type one. For the W/O type emulsions of aromatic hydrocarbon of low emulsifier concentration (0.2%), Einstein’s equation could be applied to the viscosity at a high rate of shear in the range of φ below 0.02, in spite of the presence of aggregates of droplets in the flowing emulsion. When φ becomes 0.04–0.06, the deviation from Einstein’s equation was large. In the case of higher emulsifier concentration (1%), the deviation from Einstein’s equation was noticeable even for φ=0.01, when Arlacel 60 was used as stabilizer. The results may be brought about by the increase of effective volume fraction of disperse phase owing to the inclusion of continuous phase liquid in aggregates. In the case of W/O type emulsions of saturated hydrocarbon and O/W type ones, irrespective of the kind of oil phase liquid, the aggregates were completely redispersed into primary droplets at a high rate of shear, and Einstein’s equation could be applied.
  • Kazuo Sato, Atsuo Nishioka
    1971 Volume 44 Issue 8 Pages 2042-2045
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Proton spin-lattice relaxation measurements were carried out by the rapid-passage method on the hydroxyl and methyl protons of acetic acid in carbon tetrachloride, benzene-d6, and chloroform-d in order to investigate the effect of the self-association of acetic acid on the spin-lattice relaxation. It was found that there exists a maximum of the relaxation rate in carbon tetrachloride, and two maxima in benzene-d6 and chloroform-d, on dilution with a solvent. This relaxation behavior was attributed to the change in the self-association mechanism of acetic acid. We tried to keep the proton-density constant in all solution in order to avoid any ambiguity arising from the change in density by using the analogous deuterated compounds.
  • Shigeo Hayano, Masamichi Fujihira
    1971 Volume 44 Issue 8 Pages 2046-2050
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rates of the protonation of aromatic hydrocarbon radical anions with water in dimethylformamide (DMF)-water mixtures were measured by means of the decay of the visible absorption maxima of radical anions with time. The rates were found to be greatly accelerated by the increasing water content in DMF-water mixtures. This behavior suggests that the negative charge is much more localized in the transition state than in the original radical anion. The rate constants in DMF could be obtained by extrapolation. The correlation of these rate constants to the molecular structure of radical anions was discussed on the basis of the results of HMO calculations. This correlation and the solvent effect could be interpreted by means of the charge-transfer mechanism.
  • Shigeo Hayano, Masamichi Fujihira
    1971 Volume 44 Issue 8 Pages 2051-2055
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    From the viewpoint of the interaction between the oxidized or the reduced form of a depolarizer and solvents, the solvent effect on the half-wave potentials was studied. Another factor affecting the E1⁄2, i.e., pH or ion-pair formation, was also examined. The correction for the liquid junction potential was carried out by the use of the ferrocene standard. The reduction products, radical anions or dianions, were found to be stabilized by the hydrogen-bonding with water where the hydrogen-bond interaction of the dianion was stronger than that of the monoanion. Aromatic hydrocarbon radical anions, whose charges are dispersed over the molecule, were less susceptible to this solvent transfer than were the anthraquinone radical anion and the dianion, whose charges are strongly localized.
  • Yashige Kotake, Mitsuo Ono, Keiji Kuwata
    1971 Volume 44 Issue 8 Pages 2056-2062
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A new procedure for the interpretation of the amorphous EPR spectra of the group VIB hydride radicals, i.e., OH, SH, SeH, and TeH, is proposed. The point of this method is to combine the observed hyperfme structure of these radicals in the gas phase and the calculation of the anisotropic hyperfine coupling constant. For this purpose, the Slater orbital and analytical Hartree-Fock orbitals were examined as unpaired electron orbitals by the comparative calculation of the hfs constants. The accuracy of this method was evaluated successfully by applying it to the OH radical. Moreover, in the case of the SH radical the newly-observed spectra in the amorphous state could be assigned to the SH radical.
  • Hiroshi Kato, Kimihiko Hirao, Hideyuki Konishi, Teijiro Yonezawa
    1971 Volume 44 Issue 8 Pages 2062-2066
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    By using the closed-shell SCF MO method with the zero-differential overlap approximation for all valence electron systems previously presented by us, the electronic structures of trans- and cis- substituted ethylenes (treated substituent=CH3, Cl, Br, and I) are studied. The calculated values of the π and valence electron charges, and the total energies of these isomers are presented. The natures of the higher occupied MO’s, especially the lonepair MO’s, of chlorinated ethylenes are discussed in connection with the photoelectron observation. The calculated lowest π–π* singlet transition energies accord well with the observed values. As to the rotational energy changes, the calculated results show that, at the perpendicular configurations, the triplet states for all the treated compounds are lowest, while the intermediate states for the cis-trans isomerizations of these compounds may be common to both the isomers.
  • Isao Kusunoki
    1971 Volume 44 Issue 8 Pages 2067-2074
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Total cross sections for the scattering of potassium by He, Ne, Ar, Kr, and Xe have been measured in the thermal energy range. The velocity of potassium beam is selected by a velocity selector of a slotted disk type. To obtain accurate total cross sections, the pumping effect of a McLeod gauge for the pressure measurements, the fringe effect of the scattering chamber, corrections for angular resolution and for thermal motion of the target gases are taken into consideration. A new type of scattering chamber with a variable length is used to eliminate the error of the effective scattering path length. Velocity dependence of total cross sections has been obtained and glory undulations are observed for potassium-xenon systems. For argon, krypton, and xenon the van der Waals constants are calculated from the absolute total cross sections. The values of CK–Ar, CK–Kr, and CK–Xe are 237, 354, and 535×1060 erg·cm6, respectively, and are in good agreement with the theoretical ones of Dalgarno and Davison. For neon the velocity dependence of the total cross section can not be explained by the van der Waals potential, −Crs, where s=6. For helium the correction factors for thermal motion of the scattering gas are large and the value of s for attractive potential can not be determined unambiguously.
  • Haruhiko Tanaka, Hisao Negita
    1971 Volume 44 Issue 8 Pages 2075-2077
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The fractionation of tritiated water (HTO) was examined during the crystallization of sodium sulfate decahydrate, Na2SO4·10H2O, from a slightly supersaturated solution which contained a trace amount of tritium. No appreciable fractionation of HTO was found to occur in the crystallization under both stirred and unstirred conditions. The factors which may influence the degree of the fractionation were generally considered in connection with the studies by deuterated water. It was suggested that virtually all of the water of crystallization in sodium sulfate decahydrate should come from free water in its aqueous solution, and should integrate into the crystal in accordance with the volume-diffusion model. This model was supported also by the energetical consideration of the sodium ion in the crystallization.
  • Yoshikiyo Moroi, Kinshi Motomura, Ryohei Matuura
    1971 Volume 44 Issue 8 Pages 2078-2082
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Molecular interaction between long chain alcohols and corresponding alkyl sulfates, such as dodecyl alcohol-sodium dodecyl sulfate, tetradecyl alcohol-sodium tetradecyl sulfate and hexadecyl alcohol-sodium hexadecyl sulfate, was studied by measurement of heat of complex formation, differential thermal analysis and infrared spectroscopy. It was found that there were two kinds of complexes, I and II, differing in the composition of alcohols and corresponding sulfates. The former is stable at temperatures below the melting point of alcohol, the molar ratio of alcohol to sulfate being 0.53–0.63. The latter is stable at temperatures above the melting point of alcohol, its molar ratio being 1.0. The heat of formation of II is 7–8 kcal/mol, which suggests that the complex is formed by a force similar to hydrogen bonding between alcohols and sulfates. The peak temperature in the DTA curve due to decomposition of the complex is about 10°C lower in I than in II and the characteristic absorption bands in IR spectrum are 3480 cm−1 and 3520 cm−1 in I and II, respectively, which correspond to hydrogen bond between two components.
  • Tsutomu Okuda, Yoshihiro Furukawa, Hisao Negita
    1971 Volume 44 Issue 8 Pages 2083-2086
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    81Br NQR of titanium tetrabromide has been observed at temperatures between −196°C and 35.5°C, and its Zeeman effect has been measured at room temperature. The cubic form of titanium tetrabromide shows two resonance lines, as has been reported previously; their temperature coefficients change from positive to negative when the temperature is raised. The bond angles, ∠Br–Ti–Br, are in the range of 108.7° to 110.3°. The asymmetry parameters are 2.0 and 2.5%. On the other hand, the monoclinic form shows four resonance lines; 39.175, 39.184, 39.454, and 39.800 MHz at 11°C. The temperature coefficient of the lowest line is positive at the lower temperature, whereas those of the remainder are negative. The bond angles, ∠Br–Ti–Br, are found in the range of 108.8° to 110.1°. The asymmetry parameters are 1.2, 4.6, 2.1, and 3.5% for the bromine atoms in the order of increasing resonance frequencies. The ionic and double-bond characteristics of the Ti–Br bond in both forms are about 60 and 16%. These findings suggest that, in titanium tetrabromide. the crystal field has little effect on the molecular shape, the bond character, and the asymmetry parameter.
  • Shinya Muto, Katsuhiko Degughi, Yoshikazu Shimazaki, Yoshiaki Aono, Ke ...
    1971 Volume 44 Issue 8 Pages 2087-2090
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The absorption spectra of 7,7,8,8-tetracyanoquinodimethane (TCNQ) solubilized in surfactant solutions were found to be influenced by day light (hereafter referred to as light). The formation of the monomer band of TCNQ, anion radical in the aqueous solution of DPCl (dodecylpyridinium chloride), DPBr (dodecylpyridinium bromide) and C12E8 (homogeneous octaethylene glycol dodecylether) were enhanced by light. On the other hand, the spectra of TCNQ solubilized in surfactant micelle in the dark suggested that TCNQ exists as dimer anion radical form (TCNQ)2\ ewdot. Thus, in solubilized state of TCNQ in micelle there is an equilibrium between monomer TCNQ\ ewdot and dimer (TCNQ)2\ ewdot, which seems to be easily influenced by light and surfactant. Appearance of a monomer radical band was remarkable in DPCl, DPBr, and C12E8 but only the dimer band was found in SDS even in the light.
  • Katsuyoshi Nakamura, Setsuo Takamuku, Hiroshi Sakurai
    1971 Volume 44 Issue 8 Pages 2090-2095
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The γ radiolysis of cycloheptatriene (CHT) in the gas phase has been investigated as a function of the pressure (2–14 mmHg) and in the presence of various additives (NO, O2, NH3, N2O, and C3H8). The G values obtained at 10.5 mmHg and at a total dose of 1.1×1019 eV are as follows: hydrogen, 0.50; methane, 0.16; acetylene, 1.52; cyclopentadiene, 0.29; benzene, 0.65; toluene, 1.68; dimers, 2.99. The yields of toluene and cyclopentadiene decrease with the pressure and are not appreciably affected by these additives; this suggests a contribution of the excited CHT molecules formed by direct excitation to their formation. The formation of dimers and benzene is affected by a radical scavenger (O2, NO), indicating the importance of the radical processes. The reaction products obtained via a C7H7+ ion, which is well known to be produced by the irradiation of CHT, have not been observed, while in the radiolysis of CHT in the presence of benzene and a radical scavenger, biphenylmethane has been produced, presumably by a reaction of the C7H7+ ion with benzene. Therefore, it was assumed that the C7H7+ ion produced from CHT does not contribute to the dimer formation, but may initiate the ionic polymerization.
  • Takashi Kobayashi, Tamaichi Ashida, Natsu Uyeda, Eiji Suito, Masao Kak ...
    1971 Volume 44 Issue 8 Pages 2095-2103
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Crystals of the 2 : 3 complex of zinc-phthalocyanine and normal hexylamine were studied. They are monoclinic, space group P21c, with cell dimensions a=12.40, b=15.76, c=20.05, β=93.2° and there are four phthalocyanine and six hexylamine molecules per cell. The phthalocyanine molecule is not planar and the central zinc ion is displaced from the plane by 0.48 Å toward the nitrogen atom of the amine. Zinc ion is of a square pyramidal five coordination. There are two bonding states for the amine in the complex crystal. One is weakly bonded and can be easily released from the lattice and the other is strongly bonded and coordinated directly to the zinc ion. None of the atomic parameters of these amines except those of the coordinating nitrogen were exactly determined.
  • Yukio Yamamoto, Setsuo Takamuku, Hiroshi Sakurai
    1971 Volume 44 Issue 8 Pages 2104-2107
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Ar-, Kr-, and Xe-sensitized radiolyses of toluene was studied at room temperature in the gas phase. The discussion was concentrated on the formation of three isomers of methyldiphenylmethane (MDPM), which, it had been suggested in a previous paper on the direct radiolysis of toluene, were formed by the ion-molecule reaction of C7H7+ ions. The sensitization effect on the MDPM formation was extremely large in the case of Ar, and decreased in the order of Ar, Kr, and Xe. These results were explained in terms of charge transfer from these rare gases to toluene, resulting in the formation of the C7H7+ ions. The isomer distribution of MDPM’s in the raregas-sensitized radiolysis was considered on the basis of the reaction mechanism proposed previously. The sensitization effect on the formation of other products was also discussed briefly.
  • Masaji Miura, Toru Iwaki, Masayoshi Komuro, Kusao Tanaka, Kenji Ito
    1971 Volume 44 Issue 8 Pages 2107-2109
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The heats of immersion of silica gel, alumina, and silica-aluminas in benzene, cyclohexane, and a solution of n-butylamine in benzene have been studied in connection with the acid properties of the surfaces. It was found that n-butylamine interacts more strongly with the surfaces of silica-aluminas than is the case in an aqueous system, which was previously investigated. Further, the interactions of benzene with the surfaces of silica-aluminas were discussed on the basis of the results of the adsorption isotherms of benzene on the surfaces.
  • Etsuko Fujimoto, Kunio Kozima, Yoshiko Takeoka
    1971 Volume 44 Issue 8 Pages 2110-2115
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    By measuring the infrared intensities, the energy differences between two conformers have been determined for bromocyclohexane, iodocyclohexane, trans-1-bromo-2-chlorocyclohexane, 1-bromo-2-chloroethane, ethylene bromohydrin, and ethylene iodohydrin in dilute solutions, and for cyclohexanol, trans-2-chlorocyclohexanol, ethylene chlorohydrin, and ethylene bromohydrin in vapors.
    It was ascertained that the following relation holds for the energy differences:
    EtEg=(EaaEee)−(EaEe)−(Ea′−Ee′).
    Here EtEg is the energy difference between the trans and the gauche isomer of XH2C–CH2Y, EaaEee is that between the aa- and the ee-isomer of trans-1,2-C6H10XY, and EaEe and Ea′−Ee′ are those between the a- and the e-isomers of C6H11X and C6H11Y respectively, where X is a halogen and Y is a halogen or the O–H group.
  • Teijiro Tamura
    1971 Volume 44 Issue 8 Pages 2116-2119
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The coadsorption of nitric oxide, nitrogen, and oxygen on a polycrystalline rhenium filament was studied using flash desorption mass-spectroscopy. Substitutional desorption was not observed during the adsorption of nitric oxide, nitrogen, or oxygen on preadsorbed leayers. No oxygen or nitrogen adsorbs on rhenium saturated with nitric oxide. However, nitric oxide adsorbs on rhenium saturated with nitrogen or oxygen. The strength of the chemisorption bond between rhenium and adsorbed species becomes weaker in the order of: nitric oxide, oxygen, and nitrogen. When the same amount of nitric oxide molecules exist in various coadsorbed layers, the Tp of the nitrogen desorption spectrum from these layers is shifted to a lower temperature with an increase in the number of oxygen atoms in them, because the strength of the chemisorption bond of Re–N is weakened by the strongly-bonded Re–O. No desorption of the nitric oxide molecule from a coadsorbed layer of the “N2+O2” on rhenium was observed.
  • Akira Nakajima, Hiroaki Ohya-Nishiguchi, Yasuo Deguchi
    1971 Volume 44 Issue 8 Pages 2120-2123
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The EPR spectra of the TEMPOP triradical and the TEMPOS tetraradical in solution showed seven and nine absorption lines respectively, which were interpreted as the hyperfine interaction between unpaired electron and 14N nuclei in the case of |Jin|>>A. The paramagnetic susceptibilities of TEMPOP and TEMPOS were measured. In the case of TEMPOP, no typical short-range ordering effect was found, but the 1⁄χMT curve deviated from the Curie-Weiss law at very low temperatures. In the case of TEMPOS, the 1⁄χMT curve was divided into four regions. In the first and third regions, the 1⁄χMT curves both obey the Curie-Weiss law. The second region is the intermediate region between the first and third regions. In the last region, 1⁄χMT shows a slight deviation from the Curie-Weiss law of the third region. In order to explain this behavior, some spin-cluster models with three and four spins were applied.
  • Yuroku Yamamoto, Tsunehiko Tarumoto, Masahiro Tsubouchi
    1971 Volume 44 Issue 8 Pages 2124-2126
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Iodide was extracted from the aqueous phase into nitrobenzene in a wide pH range of 3–9 by use of tris(1,10-phenanthroline)iron(II) chelate cations and then determined spectrophotometrically at 516 mμ. Beer’s law was effective up to 8.0×105 M of iodide in the aqueous phase. Standard deviation of the determination was 1.1% at 15°C. The color intensity of the extracted species in nitrobenzene was constant for at least 3 hr. The distribution ratio was 1.02 at 15°C and 0.83 at 26°C. No serious interferences by foreign anions were observed except for perchlorate, chlorate, and thiocyanate. Cations did not essentially interfere with the determination.
  • Yoshiyuki Mido, Eiichi Sekido
    1971 Volume 44 Issue 8 Pages 2127-2130
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared spectra of the sodium salt of 8-mercaptoquinoline and its related compounds have been measured in the region between 4000 and 400 cm−1. Some substituent-sensitive bands have been investigated in order to find a clue to further infrared studies of its metal chelates. The thermal stabilities of the sodium salt have been examined by thermal gravimetric analysis and by differential thermal analysis. It has been shown that the sodium salt can be dried at temperatures between 100° and 200°C without any thermal change, and that, at ca. 210°C in air, the abrupt increase in weight of the sodium salt may be due to the absorption of oxygen. The effect of hydration on the sodium salt is discussed on the basis of results with regard to X-ray diffraction patterns, infrared spectra, and weights. The sodium salt is proposed to crystallize with two moles of water and to combine inequivalently with two waters of crystallization.
  • Yoshiyuki Mido, Eiichi Sekido
    1971 Volume 44 Issue 8 Pages 2130-2134
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared spectra of divalent metal thiooxinates have been measured in the region between 4000 and 400 cm−1, and the relationships between these spectral bands and the characteristics of the metal-ligand bonding and the structures of the thiooxinates have been discussed. The plots of the frequencies of the metal-sensitive bands around 990 and 670 cm−1 against the atomic weight of the metal make it possible to classify these metal thiooxinates into two groups, one of which includes Cu-, Co-, Ni-, and Mn-thiooxinate, and the other, Cd-, Zn-, and Pb-thiooxinate. The deviation of the point for Zn-thiooxinate from the line belonging to thiooxinates with such metal atoms as have no available d-orbitals has been compared with the case of oxinates. Moreover, from the appearance of the 450 cm−1 band in the latter group, the structure of these thiooxinates may be tetrahedral. As for the frequencies of the two metal-sensitive bands mentioned above, those of Pd- and Pt-thiooxinate are the highest and that of Ag(I)-thiooxinate, examined for the sake of comparison, is the lowest. The possibility of the analytical application of the metal-sensitive band around 670 cm−1 has been discussed.
  • Satoru Onaka
    1971 Volume 44 Issue 8 Pages 2135-2141
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared absorption spectra (2200–60 cm−1) have been measured for four analogous compounds, Cl3Sn–Mn(CO)5, Br3Sn–Mn(CO)5, (CH3)3Sn–Mn(CO)5, and Ph3Sn–Mn(CO)5. Normal coordinate analysis has been made for three molecules-Cl3Sn–Mn(CO)5, Br3Sn–Mn(CO)5, and (CH3)3Sn–Mn(CO)5- on the basis of a modified Urey-Bradley force-field. The calculated frequencies attain close agreement with validly-assigned frequencies. The force constant, K(Sn–Mn), for each molecule varies with the substituent on the tin atom, and increases in the order of: K(Sn–Mn) of Cl3Sn–Mn(CO)5>K(Sn–Mn) of Br3Sn–Mn(CO)5>K(Sn–Mn) of (CH3)3Sn–Mn(CO)5. The vibrational eigenvectors reveal that the Sn–Mn stretching vibrational modes are considerably coupled with other vibrational modes, especially with CMnC deformation and axial MnC stretching modes.
  • Yorikatsu Hohokabe, Noboru Yamazaki
    1971 Volume 44 Issue 8 Pages 2142-2144
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Catalytic activities of cobaloximes in the oxidation of formaldehyde were compared with each other and with the activity of aquocobalamin (vitamin B12a). All the cobaloximes showed much less activities than B12a. Chlorocobaloximes had the highest activities. Reaction order was found to be −0.18 with respect to the concentration of hydrogen ion, 0.71 to that of formaldehyde, and 0.49 to that of chloroaquocobaloxime. In anaerobic conditions, the reduced-state B12r considered to be an intermediate in the air-oxidation reaction of aldehyde was detected spectrochemically, but not the reduced-state of cobaloxime. A much slower reaction of aldehyde with cobaloximes as compared with cobalamin was attributed to the higher reduction potentials of the former.
  • Yorikatsu Hohokabe, Noboru Yamazaki
    1971 Volume 44 Issue 8 Pages 2145-2146
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Catalytic activities of cobaloximes in the decomposition reaction of formic acid were compared with each other and with those of cobalamins. In the cobalamin series, the activity decreased in the order aquocobalamin (vitamin B12a)>methylcobalamin>cyanocobalamin (vitamin B12). In the cobaloxime series, the activity decreased in the order Co(OH)(DH)2(H2O)>CoCl(DH)2(H2O)>Co(CN)(DH)2(H2O)>CH3Co(DH)2(H2O). Cobalamins had much greater activities than the corresponding cobaloximes. The reaction proceeded with uptake of oxygen. No hydrogen gas was evolved in the reaction. The reaction rate slightly decreased with the increase of pH between 6.0 and 7.0. The reaction rate changes with 0.39 power of formic acid concentration less than 1×103 M (comparable to that of cobaloxime), and becomes independent of the concentration greater than 1×103 M. It changed with 0.89 power of the concentration of hydroxoaquocobaloxime. Aquocobalamin was reduced to B12r in the presence of formic acid but not hydroxoaquocobaloxime in anaerobic conditions. The catalytic activities of cobaloximes lower than the corresponding cobalamins were attributed to the higher reduction potentials of the former.
  • Kazuo Maruyama, Micho Mashima
    1971 Volume 44 Issue 8 Pages 2147-2149
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    This paper is concerned with the application of the zone-melting technique to metal-chelate compounds. An organic solvent which is liquid at room temperature such as benzene, and several acetylacetonato and thenoyltrifluoroacetonato chelates as solutes were prepared. The effective distribution-coefficient k dependence on the molecular weight was revealed by the normal freezing technique. In the deployment process, the acetylacetonato chelates of Fe and Th were chosen as solutes because their k values were different. The experiment was carried out at 2 cm/hr, the rate of zone travel. When a 30-cm column was used, the “removal percentages” of Fe from Th were 41 and 85% for 3 and 5 zone passes respectively. However there was a 22% loss of Th in the latter case. Furthermore, a remarkable concentration was found, and it was shown that the concentration effect may be useful for micro-analysis. At this stage, a relatively large bubble of benzene was observed at the liquid and solid interface; therefore we can call this “three-phase zone-melting.”
  • Iwao Ojima, Takaharu Onishi, Toschitake Iwamoto, Naoki Inamoto, Kenzi ...
    1971 Volume 44 Issue 8 Pages 2150-2154
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    New thiourea derivatives, 3-diphenylphosphinothioyl-1 -phenylthiourea (PTTU-A), 3-diphenylphosphinothioyl-1,1-diethyl thiourea (PTTU-B), and 3-diphenylphosphinothioyl-1,1-dimethylthiourea (PTTU-C) were found to behave as bidentate ligands with transition metal ions such as Ni(II), Pd(II), Co(II), and Cu(II) to give a series of novel metal chelates. The structures of these complexes are discussed on the basis of magnetic susceptibilities, infrared spectra, electronic spectra, powder X-ray diffraction patterns and elemental analyses. Tentative assignments of two metal-sulfur stretching vibrations in the far infrared spectra were made for Ni-PTTU and Pd-PTTU, which have square-planar configurations. However, the structures of the Cu-PTTU complexes could not be determined by these methods because of the instability of the complexes. They were confirmed by electronic and ESR spectroscopies.
  • Satoru Onaka
    1971 Volume 44 Issue 8 Pages 2154-2157
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The new palladium (II) complexes with 2,2′-diaminobiphenyl (DABP) have been synthesized under various conditions. The hexa-coordinated palladium complex, [Pd(DABP)2Cl2], has been prepared under a high pressure. The square planar diamagnetic complexes, [Pd(DABP)2]X2 (X=Cl, Br), have been synthesized under atmospheric pressure. As to the [Pd(DABP)2]Cl2 complexes, two isomers, the yellow complex and the yellow-green complex, are obtained according to the temperature at which the complexes are synthesized. Both the complexes, the yellow and the yellow-green complexes, are similar with respect to the powder X-ray diffraction pattern and the IR spectra in the region from 4000 cm−1 to 200 cm−1, but are somewhat different with respect to the stability to air, the thermal stability, and the solubility in chloroform.
  • Hiroyuki Kojima, Shizuo Fujiwara
    1971 Volume 44 Issue 8 Pages 2158-2162
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Fourier analysis of the instantaneous AC polarographic current was performed with a computer on-lined to a potentiostat. From the Fourier spectra, the amplitudes and phase angles of both the fundamental and the second harmonic AC polarographic waves were obtained. In the Cd(II) system, the current amplitude DC potential curves and phase angle-DC potential curves for the fundamental and the second harmonic AC polarographic waves were compared with the theoretical curves. The method is applicable to the accurate analysis of electrode reaction kinetics.
  • Yoshiyuki Kawase, Seiji Yamagughi, Nobuo Oki, Fumiko Okumura
    1971 Volume 44 Issue 8 Pages 2163-2167
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The action of acetic acid, phenylacetic acid, or β-phenylpropionic acid and polyphosphoric acid on 5-, 7-, and 6-hydroxy-2,3-dimethylbenzofurans afforded 6-acyl-5-hydroxy-, 6-acyl-7-hydroxy-, and 5-acyl-6-hydroxybenzofurans, some of which were also obtained by the Friedel-Crafts acylation of the corresponding methoxybenzofurans. The hydroxyketones thus obtained were converted to dimethylfuro derivatives of 4-hydroxycoumarins and isoflavones, and 3-benzyl-4-hydroxyfurocoumarins were also prepared by the thermal condensation of the hydroxybenzofurans and diethyl benzylmalonate.
  • Masaaki Ito, Kazuo Abe, Hitoshi Takeshita, Mitsuyoshi Yatagai
    1971 Volume 44 Issue 8 Pages 2168-2170
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction of thujopsene with gaseous hydrogen bromide at low temperature affords a 48% yield of neopentyl type bromide. The reactivity of the homoallyl bromide was inspected. First, the neopentyl type bromide was derived to a diethyl widdryl malonate in order to demonstrate the reaction which indicates the involvement of homoallylcyclopropylcarbinyl ion system. The malonate was converted to a carboxylic acid and then to isomeric lactone. To demonstrate the reaction which suggests the retention of carbon frame work in the reaction, the reaction of the neopentyl bromide was extended to Grignard reaction. The Grignard reagent reacted with cyclohexanone gave a tertiary alcohol, whereas a dimeric hydrocarbon was also obtained through the Wurtz type condensation. The tertiary alcohol was converted to a dehydrated hydrocarbon and then a glycol.
  • Otohiko Tsuge, Kiyoshi Yanagi, Masako Horie
    1971 Volume 44 Issue 8 Pages 2171-2176
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The preparation of new tetraaminoethylenes was attempted by the reaction of chlorotrifluoroethylene (CTFE) with several amines. It has been found that CTFE reacted with piperidine and morpholine to give tetrapiperidino- (TPE) and tetramorpholinoethylene (TME) in moderate yields respectively, although no tetraaminoethylenes were formed in the reactions with diethylamine, pyrrolidine, aniline, N-alkylaniline, and diphenylamine. Also, it has been made clear that the compounds whose structures were previously assigned to the tetraaminoethylenes, obtained from 1,1-dimethoxytrimethylamine or ethyl orthoformate and secondary amines are the corresponding triaminomethanes. It has been found that TPE and TME reacted with halogens, halogen-, nitrocompounds, and aromatic carboxylic acids to form mainly the corresponding oxamidinium salts.
  • Sanji Hagishita, Kaoru Kuriyama, Keiji Shingu, Masazumi Nakagawa
    1971 Volume 44 Issue 8 Pages 2177-2181
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An unequivocal determination of the absolute configuration of 5,5′- and 6,6′-disubstituted bis-1,1′-spiroindane and the behavior of the CD spectra of some 5,5′-disubstituted ones are described.
  • Shozo Yanagida, Masaaki Yokoe, Masataka Ohoka, Saburo Komori
    1971 Volume 44 Issue 8 Pages 2182-2185
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    N-(α-Chlorobenzylidene)carbamoyl chloride (1) reacts with hydrazine hydrate to give 3-phenyl-1,2,4-triazolone (2), with sodium azide in the presence of water to give 5-phenyltetrazole (3), and with aliphatic nitriles in the presence of hydrogen chloride to give 6-chloro-2-phenyl-5-substituted-4(3H)-pyrimidones (5) and 4,6-dichloro-2-phenyl-5-substituted pyrimidines (6). However, the reaction of 1 with trichloroacetonitrile or pivalonitrile in the presence of hydrogen chloride did not give the expected triazines.
  • Yoshiro Ogata, Katsuhiko Takagi
    1971 Volume 44 Issue 8 Pages 2186-2191
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Photochemical migration of an alkyl group from nitrogen to ortho and para positions in N-substituted benzylanilines (I) has been studied. Quenching study suggests that the rearrangement proceeds via a triplet state. The rate of disappearance of N-(p-tolyl)-α-phenethylamine (III) in photolysis was found to be 3×107–3×108sec−1. Substituted benzylanilines (I) were synthesized to estimate their quantum yields of photorearrangement. A plot of the σ value for a substituent in the migrating benzyl group vs. logarithm of relative rate gives a positive ρ value with various quantum yields for intersystem crossing (0.1–1); the ρ value indicates that electron-withdrawing substituents in the benzyl group accelerate the rearrangement. A reaction scheme is presented.
  • Nobuhiro Nakamizo, Kazuo Shiozaki, Seiichi Hirai, Shiro Kudo
    1971 Volume 44 Issue 8 Pages 2192-2197
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A facile desulfurization procedure has been presented for the method that synthesizes hypoxanthine in one step by heating 4,5-diamino-6-hydroxy-2-mercaptopyrimidine with a desulfurizing agent in formic acid. When Raney nickel prepared in the usual way was used as the desulfurizing agent, it was necessary for the ratio of nickel atoms to sulfur atoms (the Ni/S ratio) to be more than 2.6 : 1. On the contrary, when the Raney alloy per se was used, the amount of nickel could be diminished to a catalytic amount (Ni/S 0.2–0.3). The higher the content of aluminum in the alloy, the smaller the Ni/S ratio required for the desulfurization. In contrast with usual desulfurization reactions carried out in neutral media, most of the sulfur was released from the reaction mixture as hydrogen sulfide. Although aluminum or iron powder by itself had little desulfurizing activity, its addition to the Raney alloy was useful in diminishing the Ni/S ratio. Furthermore, combinations of nickel or cobalt salts and aluminum or iron powder were as effective as the Raney alloy as desulfurizing catalysts. In the case of a combination of nickel formate and aluminum powder, a large portion of the nickel ion was proved to be reduced to metallic nickel. The desulfurization reaction also proceeded smoothly in an aqueous solution of hydrochloric or sulfuric acid. On the basis of these facts, a mechanism was proposed with which the active nickel catalyst is regenerated by such auxiliary metals as aluminum or iron.
  • Kagetoshi Yamamoto, Takashi Sohda, Ichiro Kawasaki, Takeo Kaneko
    1971 Volume 44 Issue 8 Pages 2197-2202
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    cis-4-Carboxy-5-isopropyl-8-methylhydrindane-1,6-dione was synthesized from cis-1-hydroxy-8-methylhydrindanone-5 as a useful intermediate for the synthesis of picrotoxin and dendrobine.
  • Shigeo Wake, Takeshi Mawatari, Yoshio Otsuji, Eiji Imoto
    1971 Volume 44 Issue 8 Pages 2202-2206
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The photolyses of alloxan monohydrate (1) were carried out in water, 2-propanol, and dioxane. Irradiation in water produced alloxantin dihydrate (2), glyoxal (5), oxaluric acid (6), parabanic acid (7), and oxalyl diureide (8). However, when the photolyses were conducted in 2-propanol and dioxane, 2 and 5 were isolated as the main products. A detailed examination of the changes in the product distributions in the three solvents led to the conclusion that 2 and 5 are produced through the pathways involving the radical fission of the C–OH and C–CO bonds in 1. On the other hand, 6, 7, and 8 were supposed to be produced by the pathways involving the photochemical hydrolysis of 1 to alloxanic acid (13).
  • Takao Yoshioka, Susumu Higashida, Syoji Morimura, Keisuke Murayama
    1971 Volume 44 Issue 8 Pages 2207-2210
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A stable N-oxyl radical, 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (I), afforded 1-hydroxy-2,2,6,6-tetramethyl-3-(2,2,6,6-tetramethyl-4-oxopiperidinoxy)-4-oxopiperidine (IX) by hydrogen-abstraction followed by the coupling reaction of the N-oxyl radical I with the C radical III derived from I. The product IX was characterized as the monoacetate (X), monobenzoate (XI), urethane (XII), semicarbazone (XIII), triol (XIV), triacetate (XV), and a new N-oxyl radical (XVI). It has been confirmed that i) the extremely stable N-oxyl radical abstracts the α-methylene-hydrogen of the ketone which affords a thermodynamically stable conjugated ketone, ii) radical I acts as a scavenger toward a C-radical intermediate and iii) the decomposition of radical I proceeds via the C-radical to give phorone (V).
  • Tetsuo Nozoe, Kahei Takase, Satoko Fukuda
    1971 Volume 44 Issue 8 Pages 2210-2213
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    1-Phenylazulene (I) and 2-phenylazulene (II) were synthesized from the troponoid compound. 3-Phenyl-(III) and 3-benzoyl-2H-cyclohepta[b]furan-2-ones (IV) were prepared by the reaction of 2-chlorotropone with ethyl phenylacetate and with ethyl benzoylacetate respectively. The reactions of III with malononitrile or ethyl cyanoacetate gave 1-phenylazulene derivatives, from which I was derived. On the other hand, the reactions of IV with ethyl cyanoacetate or diethyl malonate gave 2-phenylazulene derivatives, from which II was derived.
  • Tetsuo Nozoe, Kahei Takase, Satoko Fukuda
    1971 Volume 44 Issue 8 Pages 2215-2217
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    7-Isopropyl-2,4-dimethylazulene (Se-guaiazulene) (I) was synthesized from 4-isopropyl-7-methyltropolone (II), which had itself been derived from 4-isopropyltropolone. The tropolone, II, was then converted to 3-acetyl-5-isopropyl-8-methyl-2H-cyclohepta[b]furan-2-one (VI) via the p-tolylsulfonyloxytropone derivative derived from II. The application of the azulene synthesis to VI gave 3-cyano-7-isopropyl-2,4-dimethylazulene-1-carboxylic acid (VII), from which I was obtained by the removal of the carboxyl and cyano groups.
  • Tetsuo Nozoe, Kahei Takase, Masafumi Yasunami
    1971 Volume 44 Issue 8 Pages 2218-2221
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction of 2-methoxytropone and its bromo derivatives with bromine was examined in various solvents. The treatment of 2-methoxytropone or 5-bromo-2-methoxytropone with bromine in methanol gave an addition product, 2,6-dibromo-7,7-dimethoxy- (II) or 2,4,6-tribromo-7,7-dimethoxy-2,4-cycloheptadien-1-one (XIV) respectively, together with the substitution products. On the contrary, the treatment of 2-methoxytropone with bromine in anhydrous ethanol, chloroform, or carbon tetrachloride gave a reddish complex compound. In aqueous ethanol or acetic acid, however, it gave 3,5,7-tribromotropolone. A possible reaction mechanism involving the nucleophilic attack of a methanol molecule on 2-methoxytropones at the 2-position is presented to account for the formation of the addition products.
  • Tetsuo Suami, Yukio Sakota, Kinnichi Tadano, Shigeru Nishiyama
    1971 Volume 44 Issue 8 Pages 2222-2225
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Hydrogenation of 2,3-O-cyclohexylidene-5-nitro-1,2,3,4-cyclopentanetetrol, subsequently followed by hydrolysis and acetylation, afforded (1,4/2,3,5)- and DL-(1,2,3/4,5)-5-acetamido-1,2,3,4-tetra-O-acetyl-1,2,3,4-cyclopentanetetrol (3 and 14). Beginning with (1,4/2,3,5)-5-acetamido-1,4-di-O-acetyl-2,3-O-cyclohexylidene-1,2,3,4-cyclopentanetetrol (2), two hitherto unknown (1,2,3,4,5)- and DL-(1/2,3,4,5)-5-acetamido-1,2,3,4-tetra-O-acetyl-1,2,3,4-cyclopentanetetrol (10 and 12) were prepared. The structures were established by proton magnetic resonance spectra.
  • Haruo Masai, Kenkichi Sonogashira, Nobue Hagihara
    1971 Volume 44 Issue 8 Pages 2226-2230
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Electronic spectra of trans-[L2M(C≡CR)2], (L=tertiary phosphine or tertiary stibine, and M=Ni, Pd or Pt) have been studied in solution from 220 mμ to 360 mμ. Nickel and platinum complexes showed three intense absorption bands. The lowest energy band was particularly sensitive to substituents of alkynyl groups. This band was assigned empirically to the transition between the molecular orbitals involved in metal-alkynyl bonds. The possibility of π-interaction between the two alkynyl groups through central metal was discussed in relation to the influence of R.
  • Shuzo Akiyama, Kazuhiro Nakasuji, Masazumi Nakagawa
    1971 Volume 44 Issue 8 Pages 2231-2236
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The syntheses of 1,1′-, 9,9′-, and 1,9′-dianthryl-, 2,2′-, 3,3′-, and 9,9′-diphenanthryl-, 1,1′-and 2,2′-dipyrenyl-, and 6,6′-dichrysenylacetylenes according to the pyrolytic reactions of the corresponding β-ketoalkylidenetriphenylphosphorane derivatives (intramolecular Wittig reaction) were described.
feedback
Top