Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 3
Showing 1-50 articles out of 85 articles from the selected issue
  • Yoshihito Takahashi
    1971 Volume 44 Issue 3 Pages 587-589
    Published: 1971
    Released: March 27, 2006
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    On chlorine gas and several oxysalts of chlorine, the values of the wavelength shift of ClKα1,2 lines and the spectra of ClKβ lines were measured. We thus verified our assumption that the Kβ′ line results from the bias of valence electrons from the atom of the third-period element to the oxygen atom in the oxyanion; this can be explained in terms of the relationship between the chemical structure and the ClKβ spectrum of the hypochlorite ion. The relationship between the relative intensity of the Kβ′ line and the wavelength shift of the Kα1,2 lines was linear, just as in the cases of oxygen-sulfur compounds.
  • Teijiro Tamura
    1971 Volume 44 Issue 3 Pages 590-595
    Published: 1971
    Released: March 27, 2006
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    The chemisorption of nitric oxide and nitrogen on a polycrystalline rhenium filament was studied using flash-desorption mass spectroscopy. For the chemisorption of nitric oxide, the initial sticking probability was found to be close to unity, with a saturation coverage of 5.2×1014 molecules/cm2 at room temperature. Nitric oxide adsorbs nondissociatively, and dissociation occurs at an elevated temperature. The rate of the desorption of nitrogen from the nitric oxide layer is roughly proportional to θ2. The majority of the oxygen in the nitric oxide layer was presumed to be liberated as rhenium oxide. The nitrogen adsorption was investigated in order to compare it with the nitric oxide adsorption. The saturation coverage and the initial sticking probability were 1.08×1014 molecules/cm2 and 0.003 respectively.
  • Hisashi Ueda, Dairokuro Yashiro
    1971 Volume 44 Issue 3 Pages 595-599
    Published: 1971
    Released: March 27, 2006
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    Particles of polyvinyl chloride were coated with small amounts of various aromatic compounds from benzene solutions and were then irradiated in a vaccum. The ESR spectra of the specimen thus obtained were recorded. Though the amount of the coated additives, in the ratio of 1 molecule for 100 monomer units of PVC, was small, strong effects on the ESR spectra were observed. The additives coated on the surface affect the ESR spectra in two ways. They cause a decrease in the total ESR absorption intensity; this was observed with all the additives studied. They also often transform the ESR spectrum; this was observed with several additive compounds, such as p-benzoquinone, tetramethylphenylenediamine-2·HCl, chrysene, hydroquinone, nitrosonaphthol, perylene, and diphenylpicrylhydrazine. Only the conduction of the excitations, holes and electrons formed in the bulk particles, to the surface of the particle can explain these results. On the surface of the particle, the excitation or the electric charge is transferred to the additive by means of an intermolecular interaction with it. The possibilities for the mechanism of the conduction of the excitation and the electric charges, and the ionization processes are discussed.
  • Takeo Hisano, Toshio Terazawa, Ichiro Takeuchi, Shinzo Inohara, Hirosh ...
    1971 Volume 44 Issue 3 Pages 599-603
    Published: 1971
    Released: March 27, 2006
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    This paper will describe that metallic aluminum was deposited electrolytically from a solution of aluminum bromide in dimethyl aniline with a current efficiency of 95% or more under optimum conditions. The superposition of a sinusoidal alternating current (AC) on the electrolysis direct current (DC) affected the properties of coatings and the throwing power of solutions to a great extent. A smooth, white-bright, ductile, and adherent coating was obtained under such appropriate conditions as that the frequency of AC was 60 Hz, the AC to DC ratio of 2 to 3. Aluminum dissolved anodically, and it was deposited at the cathode. The freezing temperature-composition diagram indicated the occurrence of two stoichiometric molecular complexes, AlBr3·C6H5N(CH3)2 and AlBr3·2C6H5N(CH3)2, and the former was isolated.
  • Hiroko Yamabe, Hiroshi Kato, Teijiro Yonezawa
    1971 Volume 44 Issue 3 Pages 604-610
    Published: 1971
    Released: March 27, 2006
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    The electronic structure and the electronic transition of three cyclic disulfides, (CH2)3S2, (CH2)4S2, and (CH3)2S2, are calculated by the semi-empirical ASMO SCF method in order to study the interaction of the neighbouring lone pairs of the S–S bond in connection with the ability of reductive scission. It is concluded that the absorption at 2500–3000 Å is the transition of n–σ* and that the variation in the maximum for the various cyclic disulfides and the chain disulfide are induced by the change in the dihedral angle that a molecule can take. The electronic structure and the reactivity of (CH3)2S2, CH3SSH, and CH3SCOCH3 are then discussed on the basis of an extended Hückel calculation. It is suggested that there is the possibility of an interaction between two molecules, R2S2, through the S–S bond of each molecule, in the HO of one molecule and in the LV of another.
  • Hiroko Yamabe, Hiroshi Kato, Teijiro Yonezawa
    1971 Volume 44 Issue 3 Pages 611-616
    Published: 1971
    Released: March 27, 2006
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    The MO calculation of the transannular interaction of eight-membered model systems, containing S,O,N, or C atoms in the position opposed to the C atom of the C=O group, are made by the extended Hückel method and the semi-empirical ASMO SCF method. The relation between the bond order (Prs value or EAB value) and the infrared absorption frequency, νC=O, is discussed. The electronic absorption maxima in the 221 mμ–235 mμ region are assigned to π–π* type transitions of intramolecular charge transfer from the interacting atom, X, to the C=O group. The absorptions in the region from 217 mμ to about 190 mμ are n–σ* type transitions. In the model calculation of the NH3 and HCHO system, it is shown that the interaction is large, the lone pair being directed to the C atom.
  • Sanji Hagishita, Kaoru Kuriyama
    1971 Volume 44 Issue 3 Pages 617-623
    Published: 1971
    Released: March 27, 2006
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    A calculation based on Longuet-Higgins and Murrell’s method using the MO’s of aniline and phenol obtained by the SCF-MO-CI calculation is carried out for the π-electron structures of (−)-6,6′-diamino-(I) and (−)-6,6′-dihydroxy-bis-1,1′-spiroindane (II). These wave functions are then used to calculate the rotation strengths of these compounds. The circular dichroism curves calculated from the results, assuming a Gaussian curve, are compared with the observed spectra; a quantitative agreement with the experimental value is found. The nature of the transitions and the origin of the optical activity are also discussed.
  • Hiroshi Kashiwagi
    1971 Volume 44 Issue 3 Pages 624-629
    Published: 1971
    Released: March 27, 2006
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    Effects of inclusion of doubly excited configurations in semi-empirical SCF-CI calculations are studied for the π-electrons of the four non-alternant hydrocarbons, fulvene, heptafulvene, vinylfulvene, and fulvalene. Transition energies to lower excited states are little affected by inclusion of doubly excited configurations. However, oscillator strengths change substantially and a good agreement with experiment is obtained. Dipole moments of ground states are affected by about 20%.
  • Tadao Hinohara, Seikichi Cho, Toshifumi Morita
    1971 Volume 44 Issue 3 Pages 629-637
    Published: 1971
    Released: March 27, 2006
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    For the analysis of the characteristic nature of the first absorption band of diphenylamine (DPA), calculations of the electronic states of DPA and its analogous compounds, diphenylether (DPE) and diphenylmethane (DPM), were carried out and the solvent effects on the fluorescence spectra of these compounds were investigated. The calculated results show that the first excited states of these three compounds are mainly benzene B2u. However, in DPA, the ionic state (CTs) is located very closely to the B2u state. It seems reasonable to say, therefore, that, in solution, the ionic state lowers its energy down to the position of the B2u state and that the first absorption band observed in the solution is a superposed band of two transitions, G→B2u and G→CTs. To confirm this assumption, the value of Δμ, which is the dipole-moment change between the ground and excited states, is estimated from the solvent effect on the fluorescence spectrum. The observed value of Δμ for DPA is intermediate between the theoretical values for the lowest (B2u) and the second excited state (CTs) ; from this fact it may be inferred that the mixing of CTs to the lowest excited state (B2u) is increased in the excited equilibrium state.
  • Yasuo Ueno, Isamu Sano
    1971 Volume 44 Issue 3 Pages 637-641
    Published: 1971
    Released: March 27, 2006
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    Droplets of aqueous NaCl solution aerosols generated by atomization were collected on an AgNO3 containing film, by measuring microscopically the sizes of the AgCl spots formed on the film, the diameters of the droplets were determined with the aid of the calibration curve between the spot and droplet diameters. It was found that the calibration curve can be expressed by a relation Dd3=Kds2, where Dd is the volume average diameter of the droplets, ds the surface average diameter of the spots and K a constant. The meaning of K was considered.
  • Shin Suzuki, Kazuyuki Sugita
    1971 Volume 44 Issue 3 Pages 641-643
    Published: 1971
    Released: March 27, 2006
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    Photographic plates were prepared by coating an emulsion consisting of mercurous acrylate, polyvinyl alcohol and water on glass plates. They were found to be sensitive to light ranging from 250 nm to 340 nm. A dark brown image with density ca. 0.6 above the fog was formed by a printing-out process. The latent image could be amplified with the reducing developers such as hydroquinone or metol. Image formation was ascribed to metallic mercury which was isolated by photoreduction and/or reduction of mercurous ion.
  • Koichi Niihara, Seishi Yajima
    1971 Volume 44 Issue 3 Pages 643-648
    Published: 1971
    Released: March 27, 2006
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    Oxyfluoride phases for the rare earth Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Y have been prepared by heating a mixture of lanthanon fluorides, LnF3, and lanthanon oxides, Ln2O3. Three phases were identified. The rhombohedral phases, LnOF, have a stoichiometric composition, and the tetragonal phases, Ln4O3F6, have a comparatively large nonstoichiometric composition range. The third cubic phase, with a fluorite-type structure, was observed in the SmOF-Sm4O3F6 region after quenching from a high temperature. This establishes that both the rhombohedral SmOF and the tetragonal Sm4O3F6 transform to the cubic phase and form a complete solid solution in the high-temperature range. It is postulated that the rhombohedral and tetragonal phases are pseudo-cubic from the fact that the diffraction patterns of these two phases are closely similar to that of the fluorite type.
  • Masao Hashimoto, Michiko Hashimoto, Taro Isobe
    1971 Volume 44 Issue 3 Pages 649-652
    Published: 1971
    Released: March 27, 2006
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    The potential energy of the acetylene crystal was calculated as a function of the rotational molecular orientations. The potential energy of this crystal has two kinds of minima, not a double minima; one arises from the quadrupole-quadrupole interaction, to which the high-temperature is due, while the other arises from the overlap repulsion interaction with which the low temperature structure is coincident. It was suggested that the mechanism of the phase transition in this crystal is a rotational transition between the two molecular orientations.
  • Shigetaka Koda, Akio Takenaka, Tokunosuké Watanabé
    1971 Volume 44 Issue 3 Pages 653-658
    Published: 1971
    Released: March 27, 2006
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    The crystal structure of π-cyclooctenyl-π-cycloocta-1,5-dienecobalt, Co(C8H13)(C8H12), has been established by successive Fourier analyses. The atomic parameters were refined by least-squares techniques using three-dimensional X-ray data to an R factor of 0.125. The complex molecule crystallizes in the space group P21c with four molecules in the unit cell of dimensions: a=10.78, b=7.30, c=17.81 Å, β=104.2°. The four cobalt atoms lie nearly on the face-centered positions in the unit cell and are sandwiched between the two ligands, cyclooctenyl C8H13 and cyclooctadiene C8H12. The seven nearest Co···C distances range from 2.02 Å to 2.09 Å. Atoms Co, C(1), C(3) and the respective centers of the two double bonds, C(9)–C(16) and C(12)–C(13), in C8H12 ring are coplanar to within 0.08 Å. The conformation of C8H13 is of the tub form and C8H12 of the boat form. The two lengths of the double bonds in C8H12 are 1.41 Å and 1.39 Å, while those in the allyl part in C8H13 are 1.35 Å and 1.46 Å, respectively. The average distance of the remaining twelve C–C bonds is 1.54 Å.
  • Teiichiro Ogawa, Iwao Fujita, Motoyoshi Hatada, Kozo Hirota
    1971 Volume 44 Issue 3 Pages 659-662
    Published: 1971
    Released: March 27, 2006
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    Spectroscopic studies of a molecular beam bombarded by a low energy electron beam were carried out for several simple organic molecules. The collision chamber resembled the ionization chamber of a mass spectrometer, and the electrons were accelerated at about 270 V. The spectrum of methane showed lines of excited hydrogen atoms and bands of excited CH radicals. The spectra of chlorinated methanes showed lines of excited chlorine atoms and bands of excited hydrogen chloride positive ions (HCl+*) in addition. Even the spectrum of a mixture of methane and carbon tetrachloride revealed bands of HCl+*. Dependence of emission intensities on target currents and gas pressures indicated the origin of the excited hydrogen atoms and CH radicals to come from direct fragmentation and the excited HCl+ ions from a bimolecular process.
  • Yôichi Iida
    1971 Volume 44 Issue 3 Pages 663-667
    Published: 1971
    Released: March 27, 2006
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    The cation radical salts of phenothiazine bromide, phenothiazine bisulfate monohydrate, and phenothiazine picrate were prepared. The absorption spectra in a dilute hydrochloric acid solution and the solid-state spectra of the salts were examined. The solid-state spectra showed a strong charge-transfer band and blue-shifts of the high-energy bands, unlike the absorption spectra in solution. The magnetic susceptibilities of these salts were measured at room temperature. They were found to be diamagnetic, with values almost corresponding to those of the diamagnetic contribution of the salts, except for that of the picrate. These spectroscopic and magnetic properties were discussed on the basis of the charge-transfer interaction between the phenothiazine cation radicals. The properties of the usual phenothiazine-picric acid charge-transfer complex and the holoquinoid phenothiazine perchlorate were investigated in association with those of the cation radical salts.
  • Tetsu Yamamuro, Ikuzo Tanaka, Norisuke Hata
    1971 Volume 44 Issue 3 Pages 667-671
    Published: 1971
    Released: March 27, 2006
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    Carbostyril dimerizes photochemically in ethanol to yield its dimer. In order to clarify the primary process of this photochemical dimerization, studies by means of steady-light irradiation and flash spectroscopy and measurements of the absorption spectrum of the intermediate and of the phosphorescence spectrum at 77°K were carried out under various conditions. The transient absorption was observed around 430 mμ, it was identified as being due to a TT transition of carbostyril. Experiments on both the decay kinetics of the triplet species and the quantum yield of the carbostyril disappearance under various conditions revealed that the photochemical dimerization of carbostyril proceeded through a bimolecular interaction between the triplet and the unexcited molecules.
  • Masashi Tanaka, Jiro Tanaka
    1971 Volume 44 Issue 3 Pages 672-674
    Published: 1971
    Released: March 27, 2006
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    The electronic spectra of cytosine, one of DNA bases, have been studied. The absorption spectra of single crystals of cytosine and its derivatives are presented, and the direction of the transition moment of the first π→π* band is determined to be inclined at about +100° from the N1–C4 line toward the C5 atom. The second π→π* band is shown to have polarization direction at +30° inclined to the reference axis.
  • Nobuko Sakai, Ichimin Shirotani, Shigeru Minomura
    1971 Volume 44 Issue 3 Pages 675-679
    Published: 1971
    Released: March 27, 2006
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    The pressure dependence, up to 7 kbar, of the electronic absorption spectra of ion-radical salts composed of the alkali metal cation and the chloranil or bromanil anion radical in the crystalline state at room temperature, and the temperature dependence, down to 134°K, of the dimerization of chloranil anions in an ethanol solution at 1 bar have been studied. The absorption band in the visible region shows a blue shift with an increase in the pressure for Li+ and Na+ salts, while for K+ and Rb+ salts the spectra are insensitive to the pressure. The anion radicals seem to be in the dimeric electronic state for the former and to be in the monomeric state for the latter, in the crystalline state.
  • Toshio Ishii, Mitsuo Muramatsu
    1971 Volume 44 Issue 3 Pages 679-681
    Published: 1971
    Released: March 27, 2006
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    The effect of additives (urea, potassium chloride, butanol, and thioglycol) to spreading solutions upon spread-ability of ovalbumin monolayers has been studied in terms of the rate constants and the limiting areas for intermediate (fast) and final (slow) processes of uncoiling of the protein molecule. It has been found that the addition results in the disappearance of the first (fast) process, which appeared upon spreading without additives. In the second (slow) process, the rate constant is found to be the same as that for the case without additives regardless of the type of the additives. Sodium dodecyl sulfate (SDS) added to the spreading solution is showed a peculiar behavior, which is explained in relation to the interaction between the protein and SDS molecules.
  • Hiroyuki Yamaguchi, Takeshi Nakajima
    1971 Volume 44 Issue 3 Pages 682-686
    Published: 1971
    Released: March 27, 2006
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    The ground-state electronic properties and electronic spectra of pyracylene (I), acepleiadylene (II), and dipleiadiene (III) have been studied by using the semi-empirical SCF LCAO-π-MO method, which allows for bond order-bond length correlation at each iteration. It is shown that the I and III molecules do not belong to, respectively, the pentalenoid and heptalenoid systems, as was expected from the HMO energy diagram. The predicted chemical reactivities, diamagnetic anisotropics, and electronic spectra for I and II are in good agreement with the available experimental data. The calculated C–C bond lengths indicate that the I, II, and III molecules are all both aromatic and polyolefinic. The upfield shift of the NMR spectrum and the unusually low value of the first half-wave potential for I can be well explained in terms of, respectively, the diamagnetic anisotropy and the energy of the lowest vacant SCF MO, calculated by using the predicted equilibrium configuration that corresponds to the aromatic model (Ia).
  • Takaya Iida, Nobuharu Takai, Takeo Yamabe
    1971 Volume 44 Issue 3 Pages 686-688
    Published: 1971
    Released: March 27, 2006
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    The reaction process of an equimolar mixture of mono- and disodium orthophosphates was examined to serve as a reference for the considerations of the mechanism of the formation of sodium tripolyphosphate. Differential thermoanalysis, thermogravimetric analysis, X-ray diffraction analysis and thin-layer chromatographic analysis were done. Particularly, the reaction mechanisms (the formation of liquid Na3HP2O7, etc.) were also examined by the use of the “32P” radioisotope. The reaction process is as follows:
    (Remark: Graphics omitted.)
    A feedback phenomenon of Na2H2P2O7 was observed.
  • Hayami Yoneda, Masayuki Muto, Tetsuo Baba, Takao Miura
    1971 Volume 44 Issue 3 Pages 689-692
    Published: 1971
    Released: March 27, 2006
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    The dissolved state of ions in solution was investigated through the study of separation mechanism of a series of tervalent hexammine-type cobalt(III) complexes in thin-layer chromatography and in electrophoresis. The results obtained are summarized as follows. In the case of strongly hydrated complexes, a strongly hydrated anion has a greater tendency towards association than a weakly hydrated anion. On the contrary, in the weakly hydrated complexes, a weakly hydrated anion is associated more easily than a strongly hydrated anion. From these findings, ionic association was presumed to occur through direct contact of a complex cation and an anion.
  • A. A. Yadav, S. M. Khopkar
    1971 Volume 44 Issue 3 Pages 693-696
    Published: 1971
    Released: March 27, 2006
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    A new method is developed for the rapid extraction and direct photometric determination of antimony. With 20% TBP-toluene 3 to 15 μg of antimony is extracted from 2M hydrochloric acid containing 1 M magnesium chloride. From the organic phase, antimony is directly determined photometrically at 640 nm as its complex with brilliant green. Antimony can be selectively extracted in the presence of a large number of cations and anions. The total operation requires only 20 min.
  • Mutsuo Kodama, Sozo Takahashi
    1971 Volume 44 Issue 3 Pages 697-700
    Published: 1971
    Released: March 27, 2006
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    In this experiment, we studied the complex formation equilibria of the lead(II) ion with aspartic acid and iminodiacetic acid by using the polarographic method. In acetate buffer solutions (5.80>pH>3.70), the lead(II) ion forms one normal complex, PbX0, and two mixed ligand complexes involving the acetate ion, PbX(Ac)and PbX(Ac)22−, with aspartic acid. On the other hand, with iminodiacetic acid, it forms a normal complex, PbX0, and only one mixed ligand complex, PbX(Ac). By observing the effects of the concentrations of the hydrogen ion, the acetate ion, and aspartic acid or iminodiacetic acid on the half-wave potential of the lead(II) ion, their formation constants were determined to be as follows:
    (Remark: Graphics omitted.)
  • Ryokichi Tsuchiya, Akira Uehara, Eishin Kyuno
    1971 Volume 44 Issue 3 Pages 701-704
    Published: 1971
    Released: March 27, 2006
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    Thermochemical functions of the deaquation-olation on K[Co(OH)L4(H2O)] type complexes in the solid phase were determined by means of derivatography and UV spectral measurements and the mechanisms were discussed on the basis of the results. In the above formula, L4, denotes nitrilotriacetate (nta), nitriloisopropionicdiacetate (nipda), d,l-α-amino-n-butyric-N,N-diacetate (α-abda), l-leucine-N,N-diacetate (lda), l-valine-N,N-diacetate (vda), d-α-phenylglycine-N,N-diacetate (pgda), or d,l-α-phenylalanine-N,N-diacetate (pada) ions. These complexes were found to liberate one mole of coordinating water upon heating and to turn into the olated compound bridged with two OH groups at the same time. From an estimation of enthalpy change and activation energy for the reaction, it was found that the reaction is apt to take place more easily as the structural complexities of chelating agents increase and that the reaction always proceeds in the first order. We might conclude that the evolution of coordinating water is the rate-determining step in the reaction.
  • Ryokichi Tsuchiya, Yasuo Nakata, Eishin Kyuno
    1971 Volume 44 Issue 3 Pages 705-708
    Published: 1971
    Released: March 27, 2006
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    The complex, cis,trans-[CoCl2(NH3)2en]ClO4, regardless whether its state is monohydrate or anhydride, was isomerized to trans,cis-form by heating in a solid phase. In the kinetic study on perchlorate in a closed system, it was found that the isomerization of the hydrated compound proceeded through a second order reaction with respect to the remaining fraction of the starting compound with the activation energy, E=29.5 kcal mol−1, while that of the anhydrous one proceeded through a first order reaction with E=51.4 kcal mol−1. On the other hand, derivatographic analyses showed that the enthalpy change in the dehydration partly including isomerization was ΔH=13.9 kcal mol−1 for the monohydrated perchlorate and the activation energy was E=39.9 kcal mol−1, whereas the enthalpy change of isomerization of the anhydrous perchlorate was ΔH=−2.1 kcal mol−1. From the results, it is believed that the “Aquation-anation” mechanism on the crystal surface is predominant in the isomerization for the hydrate, but it proceeds through some intramolecular reactions for the anhydride.
  • Ryokichi Tsuchiya, Masatatsu Suzuki, Eishin Kyuno
    1971 Volume 44 Issue 3 Pages 709-712
    Published: 1971
    Released: March 27, 2006
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    The exchange-isomerization of the complex, cis(dichloro), trans(diammine)-[CoCl2(NH3)2en]SCN·H2O to cis(chloro isothiocyanato), cis(diammine)-[CoCl(NCS)(NH3)2en]Cl, was investigated by means of both derivatographic and isothermal methods. The reaction took place immediately after the liberation of crystalline water. The thermochemical functions were obtained to be ΔH=(5.5±1.0) kcal/mol and E=(22.8±2.0) kcal/mol for the dehydration, while those for the exchange-isomerization were ΔH=(4.8±1.0) kcal/mol and E=(62.3±3.0) kcal/mol, respectively. As a probable reaction mechanism for the exchange-isomerization, a certain seven coordinated intermediate in the reaction pathway was introduced.
  • Makoto Watanabe, Kazuo Tanabe, Tomoyoshi Takahara, Tamotsu Yamada
    1971 Volume 44 Issue 3 Pages 712-715
    Published: 1971
    Released: March 27, 2006
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    Glassy and crystalline substances of the NaPO3-Sb2O3-Na2O system with P/Sb ratios in the range from 1.0 to 300 were prepared by heating NaPO3Sb2O3, and Na2CO3 at 1000°C and by then quenching the melts of the mixtures. Samples with P/Sb ratios smaller than 5.0 were obtained as crystalline substances containing amorphous substances. The chemical compositions of these crystalline substances were estimated from the data obtained by X-ray diffractometry and paper chromatography. Samples with P/Sb ratios larger than 7.0 were obtained as glassy substances. Condensed phosphates were separated by paper-chromatographic analysis, and the average degree of the polymerization of the phosphates was measured by the pH-titration method. It has been found that the crystalline substances in the samples with P/Sb ratios in the range from 1.0 to 5.0 were Sb2O5, NaSbO3, and an unknown crystalline substance. Assuming that the glasses have the P-O-P, P-O, P-O-Sb, and Sb-O linkages, a theoretical treatment of the degree of polymerization of condensed phosphates has been made and compared with the experimental data. It has been concluded that the glasses with P/Sb ratios larger than 7.0 have P-O-P, P-O, and P-O-Sb linkages.
  • Joyo Ossaka, Shin-ichi Iwai, Mitsuhiro Kasai, Toshiaki Shirai, Shuichi ...
    1971 Volume 44 Issue 3 Pages 716-718
    Published: 1971
    Released: March 27, 2006
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    A sharp exothermic peak at 980°C, which is found characteristic of allophane in its differential thermal analysis, shifted to the lower-temperature side and broadened as the iron content in the iron-coprecipitated samples increased. In the case of the iron-mixed samples, however, this exothermic peak did not shift, and a new broad exothermic peak, which was ascribed to hydrated ferric oxide, appeared. The crystallization processes in the heat-treated samples were found to depend on the coexistence state and the quantity of the iron. The dimensions of a unit cell of the mullite, crystallized at 1200°C from the iron-coprecipitated samples, varied with the iron content. The iron-mixed samples, however, showed little change in their cell dimensions. It is concluded that there are two states of the coexistence of iron in the allophanes. In one of them, iron ions form solid solutions of the allophane, i.e., as an iron-allophane. In the other, iron is in the mixture as the hydrated ferric oxide. The maximum amount of iron in the solid solution was estimated to be 5 wt% in the iron-allophane.
  • Kiyoshi Matsuoka
    1971 Volume 44 Issue 3 Pages 719-722
    Published: 1971
    Released: March 27, 2006
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    The solid solutions in the system FeO-Fe2O3-TiO2 were synthesized under hydrothermal conditions up to 700°C and 2.5 kb (PH2O). The results of X-ray diffraction, chemical and thermomagnetic analyses indicated that the products always consisted of magnetite-ulvöspinel or hematite-ilmenite solid solutions and, in some cases, rutile was also formed. The presence of the solid solutions of magnetite and ulvöspinel indicates a reducing atmosphere during the treatment. When PH2O increased from 1 kb to 2.5 kb, the FeO contents in the products decreased.
  • Haruko Ito, Junnosuke Fujita, Tasuku Ito
    1971 Volume 44 Issue 3 Pages 723-725
    Published: 1971
    Released: March 27, 2006
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    The proton magnetic resonance (PMR) spectra of the phenanthroline ligand in [Co(phen)3]Cl3, [Co(phen)2-(en)]Cl3 (new complex) and [Co(phen)(en)2]Cl3 were measured in deuterium oxide and analyzed as ABX systems. Significant up-field shifts of signals were observed only for the protons 2 and 9 of [Co(phen)3]3+ and the proton 2 of [Co(phen)2(en)]3+, not for the proton 9 of [Co(phen)2(en)]3+ nor the protons 2 and 9 of [Co(phen)(en)2]3+. The up-field shift was considered to be due to the effect of the ring current of the other phenanthroline ligands, since the protons 2 and 9 of [Co(phen)3]3+ and the proton 2 of [Co(phen)2(en)]3+ lies very close and to above the neighboring aromatic ligand.
  • Satoru Onaka, Yukiyoshi Sasaki, Hirotoshi Sano
    1971 Volume 44 Issue 3 Pages 726-730
    Published: 1971
    Released: March 27, 2006
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    The electronic configuration around the tin atom for a series of organotin-manganese compounds, R3−xXxSn–Mn(CO)5, has been studied by 119Sn-Mössbauer and 1H- and 55Mn-NMR spectroscopies. All the results obtained from these spectroscopic measurements show that the Mn(CO)5 group is a stronger electron donor than the methyl, phenyl, or halogen group and that the tin-manganese bond prefers the sσ-character whereas the tin-halogen bond prefers the pσ-character. The relationship between the 55Mn-chemical shift and the 119Sn-isomer shift indicates some σ-electron withdrawal from manganese to tin. The phenyl group reduces the magnitude of quadrupole splitting more than the methyl group; this fact may be due to the mesomeric effect of the phenyl group through the π-bond between tin and ligand atoms. The relationship among the 119Sn-isomer shift, the 1H-chemical shift, and the coupling constant J(119Sn-1H(CH3)) is also shown.
  • Akira Ouchi, Toshio Takeuchi, Yayoi Ohashi
    1971 Volume 44 Issue 3 Pages 731-734
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Copper(II), nickel(II), and cobalt(II) complexes of alkylthioglycolic acids, R·S·CH2COOH (where R=ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and s-butyl), were synthesized. Except for some copper complexes, these are new compounds. The attempt to synthesize the solid zinc complexes by the same method has not yet been successful. The relative stabilities of these complexes in the solid state seem to be Zn(II)<Co(II), Ni(II)<Cu(II), considering the yield of the syntheses of the products as well as the solvolizing tendency of the complexes. The nickel and cobalt complexes are expected to be in an octahedral form from the magnetic moments as well as from their electronic spectra. The relation between Taft’s substitution constants and the wave numbers of the maxima of the absorption spectra of these complexes in the solid state is not clear.
  • Takayoshi Yoshimori, Ikuko Matsubara, Tatsuhiko Tanaka, Kazuo Yoshida, ...
    1971 Volume 44 Issue 3 Pages 734-737
    Published: 1971
    Released: March 27, 2006
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    The purities of tin metals are determined directly by precise coulometric titration. The sample is dissolved with hydrochloric acid in a nitrogen atmosphere. The solution is then introduced into a hot antimony column. The reduced tin(II) ions are titrated with electrolytically-generated iodine. The titration is accomplished in a special cell by the use of which any disturbance of atmospheric oxygen is avoided. The titration efficiency under these acidic media was decreased when the current density was increased more than several mA/cm2. The results obtained by two different analysts for the sample of the pure tin metal (5-nine) were 99.996 and 99.991%. The standard deviations of the results were 0.025 and 0.016% respectively. The tin in the other tin metals and in Zircaloy samples was determined satisfactorily without the use of any experimental factor.
  • Yorikatsu Hohokabe, Noboru Yamazaki
    1971 Volume 44 Issue 3 Pages 738-741
    Published: 1971
    Released: March 27, 2006
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    Various cobaloximes with the general formula [CoX(DH)2B] (X: Cl, CN, OH, or CH3. DH: Dimethylglyoximato monoanion. B: Bases such as water, nicotinamide, pyridine, imidazole, or a low molecular weight copolymer of acrylamide and 4-vinylpyridine, etc.) were examined for catalytic activity in the H2O2 decomposition reaction. Cyanocobaloximes have less activities than other cobaloximes. The effect of changing the axial bases of cobaloximes was found to be small. When methylcobaloxime was used as a catalyst, the lag time was observed in the dark, while with the irradiation of visible light the reaction proceeded without induction period. An extensive study on chloroaquocobaloxime revealed that the rate is proportional both to the concentration of H2O2 and to the concentration of cobaloxime and inversely proportional to [H+]. It was found that the decomposition of H2O2 with cobaloximes proceeds with a gradual and partial degradation of cobaloximes.
  • Haruko Ito, Junnosuke Fujita
    1971 Volume 44 Issue 3 Pages 741-744
    Published: 1971
    Released: March 27, 2006
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    A new purple complex of (1,9-diamino-1,4,6,6,9-pentamethyl-3,7-diazanona-3-ene) (l-propylenediamine)nickel(II) perchlorate and the known yellow complex, (octamethyl-1,4,8,11-tetraazacyclotetradecadiene)nickel(II) perchlorate, were obtained by the reaction of tris(l-propylenediamine)nickel(II) perchlorate and acetone without any irradiation by ultraviolet light. The structure of the purple complex was estimated from its absorption and circular dichroism spectra in acetonitril and in an aqueous solution, and from its infrared spectrum in the solid state. The complex was found to take an octahedral [NiN6]-type structure in acetonitril and a planar [NiN4]-type structure in aqueous solution. The (1,9-diamino-1,4,6,6,9-pentamethyl-3,7-diazanona-3-ene)nickel(II) perchlorate and (1,9-diamino-1,4,6,6,9-pentamethyl-3,7-diazanona-3-ene)(ethylenediamine)nickel(II) perchlorate complexes were also prepared.
  • Mitsuo Yamane, Tadashi Iwachido, Kyoji Tôei
    1971 Volume 44 Issue 3 Pages 745-748
    Published: 1971
    Released: March 27, 2006
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    Alkali metal picrates in an aqueous solution are extractable by nitrobenzene. The investigations of the equilibria in and between the aqueous and organic phases show that the larger the association constants in the aqueous phase and the dissociation constants in the organic phase, the greater the extractability of the salts. The extremely low extractability of alkali metal picrates can be well explained in terms of such equilibrium constants.
  • Yoshiyuki Kawase, Setsuko Takata, Etsuko Hikishima
    1971 Volume 44 Issue 3 Pages 749-753
    Published: 1971
    Released: March 27, 2006
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    Another route to the synthesis of nitro, amino, and acetamino derivatives of 2,3-dimethylbenzofuran was explored. The cyclo-dehydration of 3-(m- and p-nitrophenoxy)butanones by means of polyphosphoric acid or sulfuric acid afforded 2,3-dimethyl-4- and -5-nitrobenzofurans, which were then converted by reduction to the corresponding 4- and 5-aminobenzofurans. The 4-, 5-, 6-, and 7-aminobenzofurans were prepared by the Hofmann reaction of the corresponding carboxylic amides. The amines thus obtained were converted to 4-, 5-, and 6-acetaminobenzofurans by acetylation. The 5-, 6-,-and 7-acetaminobenzofurans were also prepared by the cycliza-tion of 3-(p-, m-, and o-acetaminophenoxy)butanones. The 7-nitrobenzofuran was prepared by the Sandmeyer reaction of 7-aminobenzofuran. The four aryloxybutanones, 2,3-dimethyl-4- and -7-nitrobenzofurans, 4-amino-2,3-dimethylbenzofuran, and 2,3-dimethyl-4-, -5-, -6-, and -7-benzofurancarboxylic amides are new compounds.
  • Hiroshi Takeuchi, Toshikazu Nagai, Niichiro Tokura
    1971 Volume 44 Issue 3 Pages 753-756
    Published: 1971
    Released: March 27, 2006
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    Gomberg’s trityl (1-diphenylmethylene-4-trityl-2,5-cyclohexadiene) (I) was isomerized by protonic acids such as HCl and phenol in benzene to form p-benzhydryltetraphenylmethane(II). p-(Benzhydryl-α-d)-tetraphenylmethane (III) was formed by the treatment of I with phenol-d. Ph3CH and Ph3CCl were treated under the same conditions, but II was not obtained. It was not formed either by the reaction of phenylazotriphenylmethane with phenol. This observation indicates that H+ adds to the terminal methylene of I to form the cyclohexadienyl cation followed by deprotonation to give II. Similarly, treatment of 1-(phenyl-p-tolymethylene)-4-(diphenyl-p-tolylmethyl)-2,5-cyclohexadiene (IV) with HCl in benzene afforded α,α,α′-triphenyl-α,α′-(di-p-tolyl)-p-xylene (V). The results support the view that Gomberg’s trityl is not hexaphenylethane but 1-diphenylmethylene-4-trityl-2,5-cyclohexadiene as suggested by Lankamp et al. (Tetrahedron Lett., 1968, 249). 1,1,2,2-Tetraphenylethane and 1,1,2,2-tetra-o-tolylethane not having the cyclohexadiene structure could not be isomerized by protonic acids (HCl and PhOH) in benzene. Thus, isomerization of this type is characteristic of the cyclohexadiene structure such as that of Gomberg’s trityl.
  • Takeki Matsui, Niichiro Tokura
    1971 Volume 44 Issue 3 Pages 756-761
    Published: 1971
    Released: March 27, 2006
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    The rates of reactions of N,N-dimethylbenzylamine or its derivatives with methyl iodide in fourteen nonaqueous solvents at 30°C have been studied. The effects of the solvents on reactivities and Hammett’s ρ values have been examined. For establishing the relationship between ρ and solvent polarity, a unique solvent parameter for reactivity ξ0 was defined, which measures the relative solvent polarity in determining the order of reaction rate with respect to solvent. There is a linear relationship between ρ and ξ0, but protic and aromatic solvents show deviation from this relation in a particular way. The liner relationship provides a common basis for explaining both substituent and solvent effects. This suggests the importance of solvent reorientation accompanied by an activation process. It is argued that the hydrogen-bonded solvation of reactant amines and solvation of the leaving group are responsible for abnormal behaviors in protic and aromatic solvents.
  • Mamoru Ai
    1971 Volume 44 Issue 3 Pages 761-765
    Published: 1971
    Released: March 27, 2006
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    In the present work, the vapor-phase partial oxidation of cis-2-butene was carried out using V2O5-MoO3 catalysts with different compositions, at 350°C, and at a butene content of 0.65% in air, in order to elucidate the effect of the addition of MoO3 to the V2O5 catalyst on the selectivity and the mechanism for maleic anhydride formation. Two types of catalytic specificities were found, depending upon the Mo content: in the range of less than 20 atom% Mo, the specificity was similar to that of V2O5 alone, while in the range of more than 50 atom% Mo, a different specificity was observed, one which gave 1.2 times the yield of maleic anhydride than did V2O5 alone or the Mo-poor catalysts. The increase in the selectivity of butene to maleic anhydride which occurred when a large amount of MoO3 was doped is considered to be caused by the increase in the selectivity of the C4H4O→MA step, not in that of the C4H8→C4H6 or C4H6→C4H4O step. The selectivity of the side pathway in the C4H8→C4H6step was so great that no satisfactory maleic anhydride yield from butene can be expected by the use of the V2O5-MoO3 catalyst.
  • Tran Dinh Tuong, Mitsuhiko Hida
    1971 Volume 44 Issue 3 Pages 765-771
    Published: 1971
    Released: March 27, 2006
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    The effects of the medium, the additives, and the oxidation state of the copper catalyst on the rate of the Ullmann condensation reaction of sodium 1-amino-4-bromoanthraquinone-2-sulfonate and aniline in an aqueous buffered solution were investigated. The reaction rate was not affected by the ionic strength but depended very largely on the hydrogen-ion concentration. It was also established that the reaction was retarded by the addition of anions which can coordinate to copper; the retarding effect was in the order: F<<Cl<Br<I<CN. The inhibiting effects of copper-chelating agents and oxygen were also observed. No marked difference, except a slight increase in initial rate, was observed when cuprous chloride was used as the catalyst instead of cupric sulfate. The effect of the substituents of aniline on the reaction rate can be expressed by Yukuwa-Tsuno’s equation, in which the parameters, ρ and r, were −2.20 and 0.50 respectively. The experimental results are discussed.
  • Takehisa Ohashi, Shinichi Takeda, Mitsuo Okahara, Saburo Komori
    1971 Volume 44 Issue 3 Pages 771-777
    Published: 1971
    Released: March 27, 2006
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    To study the reactivity of the sulfonamide radical in various reaction systems, the photodecomposition of N-t-butyl and N-methyl-N-chloroalkanesulfonamides was investigated. In benzene, the competitive hydrogen abstraction by the chlorine atom occurred to an appreciable extent and the participation of the chlorine atom was retarded with N2-flow control. In an aqueous solution (AcOH-H2O, t-BuOH-H2O), the quantitative conversion to γ-and δ-chloroalkanesulfonamide was observed; this was thought to be due to the intramolecular hydrogen abstraction by the sulfonamide radical and to the lowering of the reactivity of the chlorine atom because of the solvation by H2O. In an acid solution (AcOH-H2O-H2SO4), a higher preference for 1,5 hydrogen transfer was found; this was caused by the protonated sulfonamide radical. The formation ratio of γ- to δ-chloroalkanesulfonamide in several solvents was determined, and the reactivity of the sulfonamide radical was discussed. From the reaction products obtained, several aliphatic sultams were synthesized.
  • Jitsuo Tsurugi, Masaru Iida, Ren Nakao, Tsugio Fukumoto, Niro Murata
    1971 Volume 44 Issue 3 Pages 777-780
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    γ-Induced hydrostannation of ethyl acrylate, allyl acetate, and vinyl acetate with triethyltin and tri-n-butyltin hydrides was attempted. The hydrostannation of ethyl acrylate and allyl acetate gave the corresponding adducts in almost quantitative yield. (2-Acetoxyethyl)-tri-n-butyltin expected from hydrostannation of vinyl acetate with tri-n-butyltin hydride could not be isolated. However, NMR and IR spectra indicated the formation of the adduct, which was found to decompose into ethylene and tri-n-butyltin acetate. The decomposition of the adduct was discussed in comparison with other adducts.
  • Ichiro Hirao, Yasuhiko Kato, Tsunetoshi Hayakawa, Hiromichi Tateishi
    1971 Volume 44 Issue 3 Pages 780-784
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction of 5-nitro-2-furimidoylhydrazine (I) with diacetyl or furil gave 3-(5-nitro-2-furyl)-5,6-disubstituted-1,2,4-triazine derivatives (IIa, b). Refluxing I in a large excess of ethyl orthoformate afforded 3-(5-nitro-2-furyl)-5-ethoxy-1,2,4-triazoline (III) and bis[3-(5-nitro-2-furyl)-1,2,4-triazolyl]methyl ethyl ether (IV). By heating with ethyl orthoformate, III was converted to IV. When III or IV was heated in diluted sulfuric acid, 3-(5-nitro-2-furyl)-1,2,4-triazole (V) was produced. The reactions of I with cyanogen bromide in refluxing methanol and with nitrous acid in diluted hydrochloric acid gave the corresponding 3-(5-nitro-2-furyl)-5-amino-1,2,4-triazole (VI) or -1,2,4,5-tetrazole (VIII) respectively. When heated in acetic anhydride, the VI afforded monoacetyl compound (VII), while the VIII yielded 5-(5-nitro-2-furyl)-2-methyl-1,3,4-oxadiazole (X). The structures of these compounds were discussed on the basis of their IR and NMR spectra.
  • Yasuji Fujita, Shin-ichi Fujita, Hisashi Yoshikawa
    1971 Volume 44 Issue 3 Pages 784-786
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Cinnamomum japonicum Sieb. is sometimes divided into several varieties on the basis of morphological differences in the leaves. The essential oils of samples of this plant from various parts in Japan were examined from the viewpoint of chemotaxonomy. The results obtained from the materials gathered at Mt. Satsuki, Ikeda-shi, Osaka Prefecture, will be reported here first. The characteristics of the oil of the leaves and branchlets are the abundant presence of 1,8-cineole and p-cymene. The rich existence of linalool in the branchlet oil may also be a characteristic of this plant.
  • Yasuo Wakatsuki, Shun-ichi Nozakura, hunsuke Murahashi
    1971 Volume 44 Issue 3 Pages 786-791
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The infrared spectra of [Cl2M Olefin]2 (olefin=vinyl alcohol, vinyl ethers, and their derivatives, M=Pt and Pd) have been studied in the 4000–100 cm−1 frequency region. A normal coordinate analysis of the coordinated vinyl alcohol indicated that the lone-pair electrons of oxygen conjugated with π-electrons of the double bond to some extent, even in the coordinated state. The coordination strengths of vinyl alcohol, vinyl ethers, and their derivatives have been examined by comparing the metal-olefin streching vibrations.
  • Yoshio Hirabayashi, Masateru Mizuta, Masana Kojima, Yukio Horio, Hideh ...
    1971 Volume 44 Issue 3 Pages 791-793
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Studies have been made of the kinetics of the reactions of thiol acids (thiostearic acid and thioacetic acid) with anilines, such as aniline and p-methoxy-, p-ethoxy-, p-methyl-, m-methyl-, p-chloro, m-chloro-, and m-nitrosubstituted anilines, in a chlorobenzene solution. The rate is given by k(RCO–SH) (X-C6H4-NH2). The activation energy for the reaction of thiostearic acid with aniline is 5.3 kcal/mol. The Hammett plots give a straight line, with a value of ρ=−2.40 for the reactions of thiostearic acid or thioacetic acid with the anilines; the mechanism of the reaction of thiol acids with anilines is discussed.
  • Yoshiaki Fukushima, Noboru Nohara, Y\={o}ji Hashida, Shizen Sekiguchi, ...
    1971 Volume 44 Issue 3 Pages 794-798
    Published: 1971
    Released: March 27, 2006
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    Various substituted ditriazinylamines were synthesized by the reaction of N,N-bis(4,6-dichloro-s-triazin-2-yl)amine, N,N-bis(4-chloro-6-phenyl-s-triazin-2-yl)amine, or 2-chloro-4-phenyl-s-triazin-2-yl-2′,4′-dichloro-s-triazin-2′-ylamine with nucleophilic reagents. The reaction of N,N,N-tris(4,6-dichloro-s-triazin-2-yl)amine with sodium methoxide was also examined. In this case, various products were obtained, depending upon the amount of sodium methoxide used. A Hammett plot of the substituent constants (∑σm) vs. the pKa′ or the imino proton shifts of the above-mentioned ditriazinylamines gives a linear relationship.
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