Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 45 , Issue 2
Showing 1-50 articles out of 88 articles from the selected issue
  • Zen-ichi Yoshida, Tsunetoshi Kobayashi, Akihiko Konishi
    1972 Volume 45 Issue 2 Pages 309-312
    Published: 1972
    Released: March 27, 2006
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    The electronic spectra of sodium nitrocyclopentadienide and sodium formylcyclopentadienide have been measured in several solvents. The electronic states of these compounds have been calculated by variable integrals methods I and II (modified Pariser-Parr-Polpe method). The longest wave-length strong absorption band of nitrocyclopentadienide (304 mμ) or formylcyclopentadienide (280 mμ) in isooctane has been assigned to the superimposed band of two intramolecular chage-transfer transitions from the five-membered ring to the nitro or formyl group. Agreement between the calculated and observed transition energies in isooctane is satisfactory.
  • Zen-ichi Yoshida, Tsunetoshi Kobayashi, Hidenori Yamada
    1972 Volume 45 Issue 2 Pages 313-315
    Published: 1972
    Released: March 27, 2006
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    The electronic spectra of 2-nitropyrrole and 3-nitropyrrole have been measured in various solvents and compared with the values calculated by the variable integrals method II. Agreement between the observed and the calculated transition energies is satisfactory. From eigenvectors of both nitropyrroles, the localization of molecular orbitals to the moiety of molecule has been discussed. The π-electon densities and π-bond orders of both molecules have also been calculated.
  • Zen-ichi Yoshida, Tsunetoshi Kobayashi
    1972 Volume 45 Issue 2 Pages 316-321
    Published: 1972
    Released: March 27, 2006
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    The electronic states of fulvene, 6-vinylfulvene, 6-aminofulvene, 6,6-dialkoxyfulvene, 6-amino-6-alkoxyfulvene, heptafulvene, 8-vinylheptafulvene, sesquifulvalene, and fulvalene have been investigated with the variable integrals methods. The effect of bond alternation is taken into account in the SCF procedure. Agreement between the calculated and observed transition energies is satisfactory.
  • Katsutoshi Ohkubo, Hirokazu Kanaeda
    1972 Volume 45 Issue 2 Pages 322-325
    Published: 1972
    Released: March 27, 2006
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    The decomposition reactions of hydroperoxides (ROOH) by sulfonium compounds or some nucleophiles (sulfides, phosphites, and transition metal ions) were treated by the extended Hückel method, augmented by the use of d-orbitals. We obtained serveral findings. First, ROOH was more reactive to nucleophiles and was energetically more stable than (ROOH)2. Second, the order of the ability for the ROOH decomposition, sulfonium compounds>>sulfides>phosphites\gtrsimthiophene, was in good agreement with that of the AO populations of the nonbonding lone pair orbitals of the above compounds. Third, the distinguished ability of the sulfonium compound may be attributed to the contribution of the partially-occupied sulfur d-orbitals, in particular, the lowest unoccupied dz2-orbital; in the ROOH decomposition, these orbitals interact with the lowest unoccupied antibonding pσ-orbital of the O–O in ROOH at the Oβ atom in the direction of the O–O axis. Finally, it was concluded that the sulfur d-orbitals contribute to the long-range interaction (S–Oβ>3.0 Å) between ROOH and sulfonium compounds.
  • Tadashi Yoshida, Tetsuya Ohsaka, Shoji Tanaka
    1972 Volume 45 Issue 2 Pages 326-331
    Published: 1972
    Released: March 27, 2006
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    The adsorption of polyvinylpyrrolidone (PVP), known as a water-soluble polymer, at the electrolyte/DME interface was examined by observing the differential capacity vs. the time relation, under conditions where the adsorption process was mainly controlled by diffusion. In the case of a relatively low bulk concentration and a short adsorption time, the adsorption rate of PVP at−500 mV(SCE) was controlled almost wholly by the diffusion of the adsorbate to the DME. The relation between the time required to attain the saturated adsorption and the bulk concentration was explained approximately by the Koryta equation, based on the linear diffusion. PVP showed no tendency to form multi-layers within the range of bulk concentrations and adsorption times observed. The maximum surface concentration of PVP decreased almost linearly with the increase in its mean molecular weight. The number of constitutive segments adsorbed per unit of area to form a monolayer at the interface was almost constant, independent of the mean molecular weight. The activation energy for the diffusion was found to be ca. 4.7 kcal/mol. On the basis of the results obtained, the configuration of PVP adsorbed at the interface was discussed.
  • Seiichiro Hironaka, Kenjiro Meguro
    1972 Volume 45 Issue 2 Pages 332-336
    Published: 1972
    Released: March 27, 2006
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    Poly (methyl acrylate) prepared by radical polymerization of methyl acrylate was saponified partially in acetone-water mixtures (5 : 2 and 100 : 1 by volume), using sodium hydroxide as the catalyst. Saponification in an acetone-water mixture of a 5 : 2 ratio by volume proceeded in a homogeneous state, but the reaction solution of a 100 :1 ratio by volume was in a white-turbid state, in which saponification proceeded in a heterogeneous state. The properties of the monolayers of polymers saponified in different states were studied at the air/water interface by measuring the surface pressure. The limiting areas obtained on distilled water for each polymer saponified in these two systems decreased linearly with an increase in the degree of saponification. However, the monolayers of polymer saponified in a homogeneous system were more stable on sodium chloride solution than those obtained in a heterogeneous system, and gave the limiting areas on solutions above 5% corresponding with the theoretical values calculated from the areas per methyl acrylate and acrylic acid residue and the degree of saponification. This can be explained by the fact that some of the hydrophilic parts of the saponified polymers submerged into the water phase were squeezed out onto the water surface by the salting out effect. On the other hand, those values obtained in a heterogeneous system neither corresponded to the theoretical values nor gave reproducible areas at high concentrations. These facts may be due to the differences in the states of the saponified polymers.
  • Keizo Suzuki, Yoshihiro Taniguchi, Toshishige Enomoto
    1972 Volume 45 Issue 2 Pages 336-338
    Published: 1972
    Released: March 27, 2006
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    The effect of pressure on the gelation of macromolecules, such as gelatin, polyvinyl alcohol, and methyl cellulose, was investigated in order to clarify which binding forces contribute to their gel formations. The values for ΔH and ΔV accompanying the gel formation were calculated from the Eldrige-Ferry’s plot and the Clausius-Clapeyron equation respectively. The values for ΔH and ΔV in the gel fromations of gelatin and polyvinyl alcohol are both negative, while those in methyl cellulose are both positive. From the thermodynamical considerations, it has been found that the formation of hydrogen bonds results in negative values of ΔV Fand ΔH, while that of hydrophobic bonds results in positive values of ΔV and ΔH. Therefore, it may be assumed that the main binding forces in the gelations of gelatin and polyvinyl alcohol may be attributed to hydrogen bonds, and that those in methyl cellulose may be attributed to hydrophobic bonds, at least up to 6000 atm.
  • Haruhiko Tanaka
    1972 Volume 45 Issue 2 Pages 339-343
    Published: 1972
    Released: March 27, 2006
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    The temperature dependence of the fractionation of tritiated water (HTO) was examined during the crystal growth of alum from its tritiated aqueous solution. When the ratios of the mole fractions of HTO in the water of crystallization to that of the mother liquid, S, at various temperatures are compared, the following order is established:
    S19.90S29.50>S36.52>S41.95>S47.43>S53.70S69.50,
    where the suffixes represent the crystallization temperatures, and where S19.90=0.975 and S69.50=0.949. The concept of the hydration of ions developed recently was applied to the problem of the crystal growth from the solution. Two kinetic parameters, such as the relaxation time of the aluminum ion for entering the surface, τc, and that of the hydrated aluminum ion, Al(OH2)63+, for the exchange of the water with bulk water, τe, were taken into account to explain the fractionation. A surface-diffusion mechanism was suggested as essential in the crystal growth of alum from the solution. The activation free energy for the crystal growth from an unstirred solution was found to be 18.17 kcal/mol, a value which was in good agreement with the value given by Bennema.
  • Masakatsu Koshinuma, Akio Nakamura, Tsutomu Seimiya, Tsunetaka Sasaki
    1972 Volume 45 Issue 2 Pages 344-347
    Published: 1972
    Released: March 27, 2006
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    Two types of apparatus using an unbonded strain gauge of a cantilever type for the measurement of surface tension were constructed. One is a sensitive electromicrobalance equipped with an extended arm attached to the cantilever of the strain gauge. The apparatus proved suitable as a surface balance in a completely closed system. By this apparatus, the measurement of surface tension ranging from 0 to 74 dyn/cm is possible with the accuracy of ±0.10 dyn/cm. The other type was constructed by connecting the sensing lever of strain gauge to the arm of a torsion balance with a strip of phosphor bronze. This device together with a counterbalance on the opposite side of the arm also proved to be useful as a tensiometer. Accuracy of this apparatus was a little better than that of the extended arm type balance, although a larger space is required. Both apparatus are inexpensive, easy to construct and simple to operate, and are suitable for the self-recording of time dependence of surface tension or weight change in general with sufficient accuracy. Equations proposed for the time dependence of surface tension of surfactant solution were checked by using the strain gauge tensiometer of the extended arm type.
  • Jun Sasaki, Kazuo Tajima, Tsunetaka Sasaki
    1972 Volume 45 Issue 2 Pages 348-351
    Published: 1972
    Released: March 27, 2006
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    Adsorption of sodium dodecyl sulfate (NaDS) and calcium dodecyl sulfate (Ca(DS)2) at the aqueous surface was measured by a radiotracer method using tritium labelled compounds at constant ionic strength of 1×10−2 and 7.5×10−3 adjusted by the addition of NaCl and CaCl2, respectively. The adsorbed amounts increased with increasing concentration of dodecyl sulfates in both cases, and approached saturation values of 3.65×10−10 mol/cm2 at 25°C for NaDS and 3.8×10−10 mol/cm2 at 55°C for Ca(DS)2. The amounts calculated from surface tension data by applying the Gibbs adsorption isotherm were confirmed to be in good agreement with the values directly measured. The adsorbed amounts of chloride ion, generally assumed to be zero, were confirmed to be negligible in the concentration region from zero up to critical micelle concentration.
  • Naosato Yoshida, Shuichi Hamada
    1972 Volume 45 Issue 2 Pages 351-355
    Published: 1972
    Released: March 27, 2006
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    The viscosities, ηm, of mixtures of oligotrifluorochloroethylene and n-heptadecane were expressed as follows: ηm=[(1−ΦR)−n(1−ΦR)]ηH+[ΦR+n(1−ΦR)]2⁄[ΦR⁄ηR+n(1−ΦRH], where ΦR is the volume fraction of the oligotrifluorochloroethylene in the mixture; ηR and ηH, the viscosities of oligotrifluorochloroethylene and n-heptadecane respectively, and n, a parameter. The two components were considered to be comparatively well compatible with each other, because the parameter, n, was small (here about 0.1). The free-volume fractions, fT, of the mixed systems, as calculated from the WLF parameters, were larger than those calculated by assuming a simple additivity between those of the two components. This effect is considered to be caused by the mitigation of physical interactions among oligotrifluorochloroethylene molecules, which are dispersed by n-heptadecane as good compatibility is achieved between the two components.
  • N. K. Mehrotra, T. C. Pant, M. C. Saxena
    1972 Volume 45 Issue 2 Pages 356-358
    Published: 1972
    Released: March 27, 2006
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    Relaxation time and mutual viscosity of seven substituted benzenes, p-toludine, o-nitroaniline, 2,4-dichloroanisole, 2,3-dichloroanisole, 2,5-dichloronitrobenzene, 3,4-dichloronitrobenzene, and 4-chloro-1,3-dinitrobenzene have been determined in the 3.13 cm (9585 MHz) microwave region, and at three different temperatures 20, 30, and 40°C. Correlation of mutual viscosity with relaxation time leads to the conclusion that the mutual viscosity is a better representation of the resistance to the rotation of the individual solute molecule.
  • Yoshihiro Sensui
    1972 Volume 45 Issue 2 Pages 359-361
    Published: 1972
    Released: March 27, 2006
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    The self-diffusion of chloride ions in the powdery crystals of manganese dichloride was studied in the temperature range of 200–420°C by the use of the isotopic-exchange method. The activation energies for self-diffusion were determined to be 0.95 and 1.6eV in a lower and a higher temperature region respectively. From these, the activation energy for the migration of chloride ions and the formation energy of an anion vacancy or a pair of an anion and a cation vacancy were deduced.
  • Tsuguo Yamaoka, Hiroshi Kashiwagi, Saburo Nagakura
    1972 Volume 45 Issue 2 Pages 361-365
    Published: 1972
    Released: March 27, 2006
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    1-Nitrenopyrene (Py-N) was produced by the photo-decomposition of 1-azidopyrene (Py-N3) in the benzene solution at 77°K and at room temperature. At 77°K, Py-N was found to be stable, and its electronic absorption and ESR spectra were measured. The result shows that its ground state is triplet and the fine structure constant, D, is equal to 0.73 cm−1. At room temperature, 1-nitrenopyrene was found to be converted easily into 1,1′-trans-azopyrene (trans-Py-N=N–Py) in the oxygen-free benzene solution and into 1-nitropyrene (Py-NO2) in addition to Py-N=N-Py in the oxygen-containing benzene solution. The decay process of Py-N as a reaction intermediate and the formation processes of the reaction products were studied by the flash-photolysis technique, and from an analysis of the results, the rate constants at 23°C were determined to be 2.1×109lmol−1 sec−1 and 1.4×103sec−1 for 2Py–N→trans-Py-N=N–Py and for Py–N+O2→Py-NO2, respectively.
  • Toshinobu Imanaka, Yasuaki Okamoto, Kazunori Takahata, Shiichiro Teran ...
    1972 Volume 45 Issue 2 Pages 366-370
    Published: 1972
    Released: March 27, 2006
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    In order to estimate the reactivity of each hydroxyl group, the exchange reaction of deuterium with the hydroxyl groups on the surfaces of the HX, HY, and CaHX zeolites and aerosil was investigated kinetically by an infrared method. The hydroxyl groups appearing at 3660 cm−1 on the HX and HY zeolites were more readily exchanged with deuterium than were the other hydroxyl groups on the two zeolites. However, in the case of the CaHX, the order of activities of each hydroxyl group changed with the pressure of deuterium. The rate equation for the reaction is expressed by a Langmuir-type equation. This fact indicates the homogeneity of each hydroxyl group on zeolite. It was found that adsorbed water and carbon dioxide catalyzed the exchange reaction. Furthermore, a compensation effect between the apparent activation energies and the frequency factors occurs in this reaction.
  • Kohji Watanabe, Jun Yamauchi, Hiroaki Ohya-Nishiguchi, Yasuo Deguchi, ...
    1972 Volume 45 Issue 2 Pages 371-375
    Published: 1972
    Released: March 27, 2006
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    The ESR spectra of α,α,γ,γ-tetraphenylallyl radical have been first observed. An abnormal ESR hyperfine splitting of this radical has been compared with the ESR hyperfine splitting of other tetraphenylallyl-type radicals; it can be explained very well by introducing the idea of a twisted-allyl model of the molecule.
  • Satohiro Yoshida, Toshikatsu Iguchi, Shingo Ishida, Kimio Tarama
    1972 Volume 45 Issue 2 Pages 376-380
    Published: 1972
    Released: March 27, 2006
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    The interactions between vanadium(V) oxide and carriers were investigated in the vanadium oxide catalysts supported on silica and γ-alumina by measuring X-ray diffraction patterns, ESR spectra, solubilities into 0.3 N ammoniacal solutions and reduction rates by benzene. A part of vanadium oxide on the carriers was insoluble in an ammoniacal solution, while unsupported vanadium oxide was easily soluble, and the reduction rates of the catalysts were remarkably affected by the carriers and the vanadium oxide contents. ESR spectra revealed that the vanadium oxide was stabilized by interaction with carriers as a square pyramidal one (VO5) and a tetrahedral one (VO4) on the surfaces of γ-alumina and silica, respectively. Massive vanadium(V) oxide crystals grew on these interacted layers with the increase of the oxide contents.
  • Asahi Suzuki
    1972 Volume 45 Issue 2 Pages 380-383
    Published: 1972
    Released: March 27, 2006
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    To elucidate the effect of long alkyl chains on the surface properties of polypeptides, various poly-γ-benzyl-L-glutamate (PBLG) hexylamides or dodecylamides with different degrees of polymerization were synthesized and their monolayers were examined. PBLG-alkylamides with a low degree of polymerization form expanded type monolayers on water and their surface pressure-area (π-A) curves have two plateaus. The lower plateau in the π-A curve is not seen in the curves of PBLG-alkylamides with a degree of polymerization of more than 10. The lower plateau in the π-A curve is due to the behavior of the terminal alkyl groups. The effect of temperature on the properties of monolayers was examined. Structures formed in the monolayers were discussed.
  • Yuichi Fujimura, Hiroyuki Yamaguchi, Takeshi Nakajima
    1972 Volume 45 Issue 2 Pages 384-388
    Published: 1972
    Released: March 27, 2006
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    A semiempirical SCF CI MO method used in combination with the variable bond-length technique, which has proved to be quite successful in predicting the ground-state geometrical structures of conjugated molecules, has been applied with modifications suitable to their excited states. The values of the parameters appearing in the expression of the resonance integral were adjusted so as to reproduce both the absorption and fluorescence spectra of benzene. The lower three singlet states (1B2u, 1B1u, and 1E1u) and the lowest triplet state (3B1u) of benzene, the lower two singlet states 1B1u and 1B2u) of naphthalene, the lower two singlet states (1B2 and 1A1) of azulene, and the lowest singlet state of heptalene are examined. It is predicted that the 1B1u and 3B1u states of benzene have the antiquinoidal and quinoidal conformations of the D2h symmetry respectively, and that the symmetry of the lowest singlet state of heptalene is higher than that (C2h) of the ground state.
  • Hiroshi Kudo
    1972 Volume 45 Issue 2 Pages 389-391
    Published: 1972
    Released: March 27, 2006
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    The Stage-II annealing process of 64Cu recoil atoms in neutron-irradiated α-copper phthalocyanine was carefully examined. The isothermal annealing curve above 270°C showed anomalous inflection point. It was found that the Stage-II annealing process of the α-crystal consisted of a “normal” monotonous annealing process and a “delayed” process caused by the crystal-structural transformation. The results of a kinematic analysis suggested that the fluctuation of the matrix and the change in the crystalographic factors due to the structural transformation play a triggering role in the delayed annealing reaction.
  • Hiroshi Kudo
    1972 Volume 45 Issue 2 Pages 392-395
    Published: 1972
    Released: March 27, 2006
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    In order to elucidate the effect of the crystal structure on the chemical behavior of 64Cu recoil atoms in copper phthalocyanine, the author studied the mixed system of copper and metal-free phthalocyanine. It was found that the initial retention increased both in the mixed crystal and in the mixed-disk target. The addition of metalfree phthalocyanine sensitized the target to the thermal annealing reaction, and the rate of the reaction in the mixed crystal was faster than that in the unmixed crystal. The electron acceptor in the target was also found to increase the initial retention. The results were discussed in terms of the electrical properties of the target, which were changed by the change in the spatial arrangement of the molecules.
  • Akira Imamura, Tsuneo Hirano, Chikayoshi Nagata, Teiji Tsuruta
    1972 Volume 45 Issue 2 Pages 396-401
    Published: 1972
    Released: March 27, 2006
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    The optical rotational strengths of the methyl derivatives of cyclohexanone were calculated by means of various types of molecular orbitals, which were converted from those used in the CNDO/2 method. One of them is represented as a Sla ter-basis atomic orbital transformed from molecular orbitals on a CNDO basis by using the overlap matrix. Another was obtained only by modifying the normalization coefficient of the molecular orbitals. From the results, the two-center matrix elements in the calculation of rotational strengths was found to be not negligible, hence, the above-mentioned transformation was indicated to be indispensable. Good agreement with the experimental results was found for the transformed molecular orbitals, especially for those with a modification of the normalization coefficient. The theoretical grounds for these transformations are discussed. The formulae for the matrix elements of the gradient operator which are necessary for the calculation of the rotational strength are given in the appendix.
  • Mamoru Jinguji, Yuji Mori, Ikuzo Tanaka
    1972 Volume 45 Issue 2 Pages 401-407
    Published: 1972
    Released: March 27, 2006
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    The linewidths of the single-quantum transitions of O(3P1) and O(3P2) in gaseous diluents, such as oxygen molecules and an inter gas, are measured with an ESR spectrometer of a usual type. The cross sections calculated from the pressure broadening are given. With regard to the multiple-quantum transitions in the Zeeman sub-levels of O(3P2) the dependence of the linewidths on the pressure is duscussed. The spin-lattice relaxation time, T1 for the single-quantum transitions of O(3P2) or O(3P2) is evaluated by employing the standard power saturation technique, and the effectiveness of an inert gas on T1 is studied. The spin-lattice relaxation between the Zeeman sublevels of the O atom is caused by the coupling between the orbital momentum and the electron-spin state upon collision. With regard to the multiple-quantum, the relaxation mechanism is also studied. Finally, we study the relationship between the spin-lattice relaxation time, T1, and the corresponding probabilities of ΔMJ=±1, ΔMJ=±2, ΔMJ=±3, and ΔMJ=±4 transition induced by collisions.
  • Yoshio Matsunaga, Yoshihiro Narita
    1972 Volume 45 Issue 2 Pages 408-414
    Published: 1972
    Released: March 27, 2006
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    3,3′5,5′-Tettrahalo- and 3,3′,5,5′-tetrabromo-p-diphenoquinones were found to form series of complex anion-radical salts of the M+(Q2) or M+2(Q3)2− type with various onium cations. These complex salts are darkcolored, almost black in many cases, and show electronic absorptions extending into the rock-salt region. In addition, bluish green-colored simple salts could be isolated with a few cations. The complex salts exhibit electrical resistivities in orders from 10 to 104 ohm cm at room temperature. Neither the pattern due to the quinone molecule nor that due to the semiquinone ion is present in their vibrational spectra. A single carbonyl stretching vibration band appears around 1600 cm−1, intermediate between that in the quinone and that in the semiquinone salt.
  • Taro Tachibana, Kazuko Kayama, Hideko Takeno
    1972 Volume 45 Issue 2 Pages 415-422
    Published: 1972
    Released: March 27, 2006
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    The bivalent metal soaps of optically-active 12-hydroxyoctadecanoic acid were found to crystallize out in the form of twisted fibers from aqueous or anhydrous ethanol solutions. Most soaps of this class produced both righthanded and left-handed fibers from the same specimen, more of the latter in the case of the D-enantiomer. An enantiomorphic relationship of the sense of twist was clearly demonstrated by using both enantiomers of the Ca soap. Under a high-resolution electron microscope, it was observed on the Sr soap that Sr atoms are arranged in lines along the fiber axis with a periodicity of 33–40 Å, showing that the hydroxyoctadecanoate chains of the soap molecules are aligned approximately parallel to the width of the fiber. The twisting of the soap fibers was associated with the layer structure characteristic of soap.
  • Shigeo Koizumi, Yoshio Matsunaga
    1972 Volume 45 Issue 2 Pages 423-428
    Published: 1972
    Released: March 27, 2006
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    The 1,6-diaminopyrene-p-chloranil complex is dark blue when crystallized from chloroform and brown when crystallized from benzene. These two substances are distinctly different in X-ray diffraction, electronic spectrum, vibrational spectrum, and also electrical resistivity. The brown form, the resistivity of which is about 105 ohm cm, can be transformed into a third form, exhibiting only a few ohm cm, by compression in the presence of benzene or some other aromatic solvents. Dimorphic forms are also found with the complexes of trichloromonobromo-and dichlorodibromo-p-benzoquinones. One of these forms is of a similar nature to the dark blue-colored p-chloranil complex. The other form is brown. Only the brown form is obtainable for the complexes of mono-chlorotribromo-p-benzoquinone and p-bromanil. All the brown complexes except that of p-chloranil are similar and exhibit resistivities of the order of 103 ohm cm. In addition, black products exhibiting resistivities of several ohm cm can be prepared by using acetone as the solvent with 1,6-diaminopyrene and tetrahalo-p-benzoquinones. Contrary to the afore-mentioned complexes, no definite composition can be assigned to these low-resistivity products.
  • Masaji Miura, Michiko Kodama
    1972 Volume 45 Issue 2 Pages 428-431
    Published: 1972
    Released: March 27, 2006
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    The conductivity studies of the aqueous solution of sodium dodecyl sulfate (SDS) over the concentration range of 0–0.12 M revealed that there exists a so-called 2nd critical micelle concentration (CMC) at about 65 mM in addition to the 1st CMC at 8.3 mM. The 2nd CMC was greatly influenced by additives; sodium chloride lowered the 2nd CMC, whereas organic substances, such as dodecyl alcohol and n-hexane, raised it. Moreover, the specific conductivity-concentration curve of the pure SDS solution broke upward at the 2nd CMC, and its slope increased in the presence of sodium chloride, while it bent toward the concentration axis in the presence of a certain amount of dodecyl alcohol or n-hexane. These facts may afford a clue for explaining the micelle structure above the 2nd CMC.
  • Tadashi Iwaghido
    1972 Volume 45 Issue 2 Pages 432-437
    Published: 1972
    Released: March 27, 2006
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    Alkali metal picrates are extractable from an aqueous solution into nitrobenzene. The picrates exist mainly as the dissociated form in both the aqueous and the nitrobenzene phases, whereas picric acid exists mainly as the undissociated form in the organic phase. The distribution ratio of the picrates and picric acid at any pH can well be explained in terms of these equilibrium constants. The distribution coefficient of picric acid is evaluated to be 102.63.
  • Taira Imamura, Masatoshi Fujimoto
    1972 Volume 45 Issue 2 Pages 438-441
    Published: 1972
    Released: March 27, 2006
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    The kinetics of the non-complementary reaction of Fe(III) with Variamine Blue was studied under nitrogen atmosphere in perchlorate media of ionic strength μ=1.0M. The iminoquinone form of Variamine Blue was followed spectrophotometrically by a stopped-flow technique. The rate constants of the stepwise reaction, Fe(III)+(V.B.) \oversetkα\ ightleftarrows Fe(II)+(V.B.)sox, Fe(III)+(V.B.)sox \oversetkβ→ Fe(II)+(V.B.)ox+2 H+, were evaluated to be kα=3.28×102 and kβ=4.29×102 M−1 sec−1 at pH\simeq2.2 and 25°C. The apparent activation energy was 10±1 kcal·mol−1 for both kα and kβ. The formation rate was not seriously affected by hydrogen ion concentration (pH 2.2–0.77).
  • Taira Imamura, Masatoshi Fujimoto
    1972 Volume 45 Issue 2 Pages 442-444
    Published: 1972
    Released: March 27, 2006
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    A stopped-flow apparatus was used to study the kinetics of the redox reaction of Tl(III) with Variamine Blue under nitrogen atmosphere in acid (0.2–0.6 M) perchlorate media of ionic strength μ=1.0 M. The observed second-order rate constant increases inversely with hydrogen ion concentration. The proposed mechanism involves the overall rate-determining steps
    Tl3++(V.B.)\oversetk1\ ightleftharpoonsTl++(V.B.)ox+2H+
    TlOH2++(V.B.)\oversetk2\ ightleftharpoonsTl++(V.B.)ox+H2O+H+
    where (V.B.) and (V.B.)ox are a reduced form and an oxidized form of Variamine Blue respectively. The rate constants are evaluated to be k1≤102 M−1 sec−1, and k2=3.6×104 M−1 sec−1 at 25°C. The activation energy E2 for k2 is 11±0.8 kcal·mol−1.
  • Kosuke Izutsu, Sachiko Sakura, Taitiro Fujinaga
    1972 Volume 45 Issue 2 Pages 445-450
    Published: 1972
    Released: March 27, 2006
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    The polarographic behavior of alkali metal ions in hexamethylphosphoramide (HMPA) has been found to be greatly influenced by the cations of the supporting electrolytes. With 0.05 M Et4NClO4 as the supporting electrolyte, cesium and rubidium ions give diffusion-controlled, reversible waves at−2.32 and −2.35 V, respectively, vs. the Ag/0.1 M AgClO4 electrode, but sodium and lithium ions are not reduced until the reduction of the supporting electrolyte (−3.1 V). The potassium ion gives a wave at −2.37 V with a limiting current controlled by the rate of the preceding process. In 0.05 M Bu4NClO4 solutions, the reduction wave of the potassium ion is diffusion-controlled, but that of the sodium ion is kinetic and is very small. The lithium ion is not reduced until −3.1 V. In 0.05 M LiClO4, even the sodium ion is reduced reversibly with E1⁄2 at −2.47 V, while the reduction of the lithium ion starts from −2.65 V. In mixed supporting electrolytes, the presence of the tetraethylammonium ion is the determining factor of the electrode processes. From the measurements of the electrocapillary curves and of the conductivities, the effect has been attributed to the change in the double-layer properties with the cations of the supporting electrolytes.
  • Hiroshi Kobayashi, Yasuo Yanagawa
    1972 Volume 45 Issue 2 Pages 450-456
    Published: 1972
    Released: March 27, 2006
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    Tetraphenylporphiniron(II) was synthesized and isolated in a pure state. The iron(II) porphin was in the state of S=2. The spin state of iron(II) porphin varies with the axial ligand field. Oxygeneous axial ligands such as tetrahydrofuran and dioxane gave an intermediate spin state (S=1), while nitrogeneous ligands such as pyridine gave a diamagnetic state (S=0). The electronic spectra of tetraphenylporphin complexes of iron(II) were measured for the three types of the spin state.
  • Yukio Nakamura, Mitsuru Gotani, Shinichi Kawaguchi
    1972 Volume 45 Issue 2 Pages 457-461
    Published: 1972
    Released: March 27, 2006
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    Dibromo(acetylacetone)cobalt(II), a new complex containing an acetylacetone molecule as the bidentate ligand, was formed by the reaction of tris(acetylacetonato)cobalt(III) with bromine in dichloromethane, and characterized by elemental and thermogravimetric analyses and electronic and infrared spectra. The same compound was also prepared by direct addition of acetylacetone to anhydrous cobalt(II) bromide. The radical nature of the redox step involved in the reaction pathway from the starting cobalt(III) chelate to the product cobalt(II) complex of acetylacetone was demonstrated by polymerization of methyl methacrylate and styrene remarkably enhanced by the reaction system.
  • Yuzo Nishida, Sigeo Kida
    1972 Volume 45 Issue 2 Pages 461-465
    Published: 1972
    Released: March 27, 2006
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    Comprehensive elucidation of optical and magnetic properties of low-spin cobalt(II) complexes of various types has been attempted. The g-values and magnetic susceptibilities of the complexes have been calculated, the necessary numerical data being obtained from the spectral data and reasonable assumptions. Fairly good agreement has been obtained between the calculated and experimental values.
  • Yutaka Fukuda, Kozo Sone
    1972 Volume 45 Issue 2 Pages 465-469
    Published: 1972
    Released: March 27, 2006
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    Six new mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine and a bidentate ligand, i.e., [Cu tmen en] (ClO4)2, [Cu tmen en] (NO3)2·H2O, [Cu tmen en](SO4)·4H2O, [Cu tmen gly](ClO4), [Cu-tmen ox] ·4H2O and [Cu tmen aca](ClO4) were prepared, and their visible absorption spectra were compared with those of the bis-chelate ions and molecules, [Cu en2]2+, [Cu gly2], [Cu ox2]2−, and [Cu aca2]. The results obtained indicate that steric factors play an important role in the formation and structure of these mixed chelates. The effects of various organic solvents on the electronic spectra of these chelates were also studied. (tmen=N,N,N′,N′-tetramethylethylenediamine, en=ethylenediamine, gly=glycinate ion, ox=oxalate ion, aca=acetylacetonate ion.)
  • Youkoh Kaizu, Hiroshi Kobayashi
    1972 Volume 45 Issue 2 Pages 470-477
    Published: 1972
    Released: March 27, 2006
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    Bipyridinetetracarbonylchromium, -molybdenum and -wolfram and their related complexes were reduced with sodium metal in tetrahydrofuran. Some products in the first stage of reduction were isolated. On the basis of the electronic absorption spectrum and the electron spin resonance, the complex formed in the reduction was concluded to be a complex coordinated by mononegative ion of bipyridine. Metal dσ orbital in the complex is still higher than bipyridine π* orbital, even if it is fairly lowered by a positive charge arising from the “metal to carbonyl” back-donation. Trapped electrons in the bipyridine π* orbital are, however, readily transferred into dσ orbital depending upon molecular environment. This gives rise to the formation of a pentacoordinate complex or complex dimer evolving carbon monoxide.
  • Takehisa Hata, Toyozo Uno
    1972 Volume 45 Issue 2 Pages 477-481
    Published: 1972
    Released: March 27, 2006
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    Azomethine derivatives of 8-hydroxyquinoline-2-carbaldehyde with aromatic and aliphatic amines and their aminomethyl derivatives were synthesized for the purpose of investigating their applications as analytical reagents. Spot tests with metal ions revealed that azomethine derivatives form intensely colored chelates, whereas aminomethyl derivatives form less intensely colored chelates. The acid dissociation constants were determined by means of potentiometric titration in 50 v/v% aqueous dioxane solution at 25±0.1°C. The values of pKNH+ and pKOH of 8-hydroxyquinoline-2-carbaldehyde, 2-(o-hydroxyphenylaminomethyl)-, 2-(p-chlorophenylaminomethyl)-, 2-(p-tolylaminomethyl)- and 2-(naphthylaminomethyl)-8-quinolinol are lower than those of 8-quinolinol. The phenyl substituent in 2 position of oxine moiety exerts an acid strengthening effect on these ligands. The basicity of the ligand N,N′-bis- (8-hydroxy-2-quinolylmethyl)ethylenediamine is higher than that of other oxine derivatives.
  • Hiroyuki Koyama, Tamotsu Yoshino
    1972 Volume 45 Issue 2 Pages 481-484
    Published: 1972
    Released: March 27, 2006
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    Four cyclic triamines of a medium ring size (9–12-membered ring) which form three mutually-adjacent five- and/or six-membered chelate rings on complexation, such as 1,4,7-triazacyclononane (abbreviated TACN), 1,4,7-triazacyclodecane (TACD), 1,4,8-triazacycloundecane (TACUD), and 1,5,9-triazacyclododecane (TACDD) were synthesized and isolated as their trihydrobromides. The complexation of TACN and TACD with a cobalt-(III) salt yielded metal complexes of a sandwich-type structure, such as [Co(TACN)2]Br3 and [Co(TACD)2]Br3·H2O, which were then isolated. In the case of TACUD, a complex [Co(TACUD)BrCl2] containing only one molecule of the triamine was isolated. However, although the formation of a cobalt (III) complex with TACDD in solution was inferred spectroscopically, no expected complex was isolable. On the basis of the spectrophotometric data, the ligand-field strength was found to increase in the following order:
    [Co(NH3)6]3+<[Co(TACD)2]3+<[Co en3]3+<[Co(TACN)2]3+.
  • Yukio Nakamura, Nobuko Kanehisa, Shinichi Kawaguchi
    1972 Volume 45 Issue 2 Pages 485-489
    Published: 1972
    Released: March 27, 2006
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    When bis (acetylacetonato)cobalt(II) is allowed to react with twice molar quantity of bromine in dichloromethane, cobalt(II) bromide and γ-bromoacetylacetone are produced ultimately. From a deep blue solution of an equimolar reaction mixture at 0°C an intermediary product was isolated and characterized to be dimeric bromo(acetylacetonato)cobalt(II) by means of elemental analysis and molecular weight determination. The structure of this compound was inferred to be tetrahedral from absorption spectra and magnetic data. Acetylacetonate groups were supposed to act as bridging ligands on the basis of IR data in the lower frequency region. Dibromobis(acetylacetonato)dicobalt(II) was also derived from dibromo(acetylacetone)cobalt(II) by the reaction with sodium acetylacetonate in acetylacetone at 0°C.
  • Koji Tanaka, Toshio Tanaka
    1972 Volume 45 Issue 2 Pages 489-491
    Published: 1972
    Released: March 27, 2006
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    Dimethyltin-bis(N,N-dimethylthioselenocarbamate), (CH3)2Sn[SSeCN(CH3)2]2, dimethyltin-bis(N,N-dimethyldiselenocarbamate), (CH3)2Sn[Se2CN(CH3)2]2, and dimethyltin-bis(N-methyl-N-phenyldiselenocarbamate), (CH3)2Sn[Se2CN(CH3)(C6H5)]2, react with dibromoalkanes to give bis(1-thia-3-selenacycloalkyl-2-dimethylimminium)dimethyltin tetrabromide, (Remark: Graphics omitted.) (m=2, 3), 1,3-diselenacycloalkyl-2-dimethylimminium dimethyltin bromides, (Remark: Graphics omitted.) (n=1, m=2 and n=2, m=3), and 1,3-diselenacyclopentyl-2-methylphenylimminium bromide, (Remark: Graphics omitted.), respectively. The infrared and PMR spectra indicate that the positive charges of 1-thia-3-selena- and 1,3-diselenacycloalkylimminium ions are more delocalized in the higher homologs than in the lower ones.
  • Sadao Matsuura, Masaki Yamamoto, Yasuyuki Kaneko
    1972 Volume 45 Issue 2 Pages 492-495
    Published: 1972
    Released: March 27, 2006
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    The structures of two blue-fluorescent substances, asperopterfn-A and -B, isolated from Aspergillus oryzae were investigated. Asperopterin-B was identified as 2-amino-3,4,7,8-tetrahydro-6-hydroxymethyl-8-methyl-4,7-dioxopteridine (7) by studying its chemical degradation, pKα values, and UV spectra; the structure was confirmed by synthesis. Asperopterin-A was shown to be the β-D-ribofuranoside of 7, 2-amino-3,4,7,8-tetrahydro-8-methyl-4,7-dioxo-6-pteridinylmethyl β-D-ribofuranoside (10).
  • Takeo Saegusa, Yoshihiko Ito, Shimpei Tomita, Hideo Kinoshita
    1972 Volume 45 Issue 2 Pages 496-499
    Published: 1972
    Released: March 27, 2006
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    It has been found that some binary systems of a copper compound (or metallic compounds) and an isocyanide catalyze the Michael addition reaction. As the copper component, Cu2O, metallic copper and copper acetylacetonate are effectual, whereas CuCl, CuCl2, and CuO are ineffectual. The catalyst of copper isocyanide complex is characterized by the selective activation of cyano olefin compounds such as acrylonitrile. This was demonstrated by the competitive addition of an active hydrogen compound to acrylonitrile and methyl acrylate. Some results of kinetics and spectroscopic studies have been explained by assuming a scheme involving coordination of olefin onto copper-isocyanide complex.
  • Fujio Suganuma, Miyuki Hagiwara, Hiroshi Mitsui, Tsutomu Kagiya
    1972 Volume 45 Issue 2 Pages 500-506
    Published: 1972
    Released: March 27, 2006
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    The γ-ray induced polymerization of ethylene in bulk or in solution in the presence of 26.9–67.3 g of 1,2-dichlorotetrafluoroethane (R-114) was carried out in a 100-ml reactor under a pressure of 210–400 kg/cm2 and at 30°C, with a dose rate of 1×104–9×104 rad/hr. The rate of the polymerization and the molecular weight of the polymer formed increased with the reaction time and the pressure. The rate also increased upon the addition of an appropriate amount of R-114. On the other hand, the molecular weight decreased with an increase in the amount of R-114. The dose-rate exponents of the rate and the molecular weight were found to be 0.8 and −0.2 respectively. These results were analyzed kinetically, and the rates and the rate constants of the initiation, propagation, transfer, and termination reactions were evaluated. Further, the roles of R-114 in the polymerization were discussed.
  • Hirokazu Tokunaga, Kin-ya Akiba, Naoki Inamoto
    1972 Volume 45 Issue 2 Pages 506-509
    Published: 1972
    Released: March 27, 2006
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    Reaction of diarylmethylenetriphenylphosphoranes with sulfur gave thiobenzophenones and triphenylphosphine sulfide in good yields. Reaction of benzylidenetriphenylphosphoranes with sulfur gave triphenylphosphine sulfide and 5,7-diphenyl-l,2,3,4,6-pentathiepane. More active alkylidenetriphenylphosphoranes such as isopropylidene- or sec-butylidenetriphenylphosphorane gave the corresponding phosphonium betaine containing sulfur atoms or phosphonium salt produced through air oxidation and hydrolysis of the betaine. α-Benzoylbenzylidenetriphenylphosphorane did not react with sulfur. Reactivity of alkylidenephosphoranes toward sulfur was briefly discussed.
  • William E. Parham, Shoji Kajigaeshi, Siemen H. Groen
    1972 Volume 45 Issue 2 Pages 509-515
    Published: 1972
    Released: March 27, 2006
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    The ring opening reactions of six known or new 2,2-dichlorocyclopropyl phenyl sulfides have been carried out with potassium t-butoxide in t butyl alcohol and with pyridine. The products were enynes, butadienes, allenes and, as minor products, α,β-unsaturated aldehydes containing the phenylmercapto group. Reaction of a mixture of cis- and trans-1,1-dichloro-2-methyl-3-phenylmercaptocyclopropane (2) with pyridine gave unchanged trans-isomer. This apparent selectivity is explained on the basis of the steric effects for ring opening.
  • Kazuo Tsujimoto, Mamoru Ohashi, Teijiro Yonezawa
    1972 Volume 45 Issue 2 Pages 515-519
    Published: 1972
    Released: March 27, 2006
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    The photochemical decomposition of several 1-substituted benzotriazoles was investigated. It was observed that in contrast to the thermolytic decompositions of 1-benzyl and 1-benzoylbenzotriazole, the intermediates produced by the loss of nitrogen from these compounds upon irradiation react with hydrogen-donating solvents to yield either reduced or substituted products. The possibility of the presence of an antiaromatic benzoazacyclopropene as an intermediate can be excluded on the basis of the fact that the photolysis of 4′,5-dichloro-l-phenylbenzotriazole gave 3,6-dichlorocarbazole as the sole product. The acetone-sensitized photolysis of 1-benzoylbenzotriazole causes a Wolff rearrangement giving a cyclopentadiene derivative. On the basis of extended Hückel molecular orbital calculations on the intermediates, it is concluded that the photochemical loss of nitrogen from benzotriazoles gives excited-state 1,3-diradicals, while the thermolytic decompositions afford ground-state ones.
  • Yasuhiko Dozen
    1972 Volume 45 Issue 2 Pages 519-525
    Published: 1972
    Released: March 27, 2006
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    All the fourteen isomers of naphthalenetricarboxylic acids have been synthesized by the oxidation of trimethylnaphthalenes, dimethylacetonaphthones, dimethylnaphthoic acids, methylnaphthalenedicarboxylic acids, β-(dimethylnaphthoyl)propionic acid, or β-(acenaphthoyl)propionic acids with aqueous sodium bichromate or potassium ferricyanide. Most of these naphthalenetricarboxylic acids, acid anhydrides, and trimethyl esters are new compounds.
  • Kiyoshi Hasegawa, Syuzi Hirooka
    1972 Volume 45 Issue 2 Pages 525-528
    Published: 1972
    Released: March 27, 2006
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    Some derivatives of N-(2-phenylethene-l-sulfonyl)-N′-alkylthioureas of the R1C6H4CH=CHSO2NHCSNHR2 2 type were synthesized by a reaction between 2-phenylethene-l-sulfonamides 1 and isothiocyanates in acetone in the presence of K2CO3. A new heterocyclic system, 3-alkylamino-5-phenyl-1,1-dioxo-5,6-dihydro-l,4,2-dithiazine 3, was obtained by the intramolecular Michael cycloaddition of 2 in weakly basic media, and also by the thermal cyclization of 2. The carbon-sulfur bond in 3 could be cleaved to give 2 again in strongly basic media.
  • Makoto Kaneta, Noboru Sugiyama
    1972 Volume 45 Issue 2 Pages 528-531
    Published: 1972
    Released: March 27, 2006
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    From the leaves and stems of Arthraxon hispidus Makino, aconitic acid, luteolin, luteolin-7-glucoside, and a new flavone, arthraxin, have been isolated. Luteolin, luteolin-7-glucoside, and arthraxin were also isolated from Miscanthus tinctorius Hackel, and tricin was isolated from Miscanthus sinensis Anderss and Phragmites communis Trinius.
  • Shinkiti Koto, Shonosuke Zen, Satoshi Omura, Toju Hata
    1972 Volume 45 Issue 2 Pages 532-535
    Published: 1972
    Released: March 27, 2006
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    Purine nucleosides of L-mycarose and L-cladinose, neutral branched-chain sugars of macrolide antibiotics, synthesized by a fusion method with the aid of dichloroacetic acid. The structure of these synthesized nucleosides was determined on the basis of the results of elemental analyses and the ultraviolet absorption and proton magnetic resonance spectra, as well as on the basis of the optical rotatory dispersion.
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